Note: Descriptions are shown in the official language in which they were submitted.
-- 1 --
~1229~
RESIN COMPOSITION, C~RABLE
COMPOSITION AND COATING COMPOSITION
This application is a divisional application of
the Applicant's parent application Serial No. 2,011,357.
The present invention relates to a fluorine-type
resin composition, a curable composition and a coating
composition.
Conventional methods of curing resins containing
hydroxyl group(s) as functional group include those
comprising curing such hydroxyl-containing resin with a
crosslinking agent such as a diisocyanate compound,
melamine resin or the like. These methods, however, has
drawbacks. Diisocyanates are toxic and give a coating
which is unsatisfactory in weatherability and likely to
yelIow. Further the resin composition has a short pot
life. Use of melamine resins necessitates baking at high
temperatures of about 140~C or above and provides a -~
coating poor in resistance to acids, scratching, staining
and weather.
Low-temperature curable nontoxic one-package
resin compositions are available. For example, Japanese -~
Unexamined Patent Publication No.67553/1985 discloses a
resin composition comprising an aluminum chelate compound
and a vinyl polymer comprising as a monomer component
alkoxysilane compound such as methacryloxypropyl-
trimethoxysilane.
2~298~
Yet these conventional resin compositions are
not fully satisfactory. Since the silanol group formed by
the hydrolysis of alkoxy group attached to silicon atom is
the sole crosslinking functional group, the above
composition requires a large quantity of water for
curing. Consequently large amounts of by-products, such
as alcohol, resulting from the hydrolysis give impaired
properties to the cured product. Further when the
composition is cured in the presence of only the moisture
in air, the composition initially becomes cured at the
surface, with its interior generally remaining
incompletely cured, so that the curing is likely to result
in a shrunk product having a deteriorated fatness.
It is an object of the present invention to
provide a resin composition usable in combination with a
metal chelate to give a curable composition which has
excellent storage stability even in the form of one-
package composition and which is useful as, e.g., a
coating composition.
It is another object of the invention to provide
a curable composition and a coating composition which are
excellent in low temperature curability and which give a
coating outstanding in properties such as resistance to
weather, acids, scratching and staining, mechanical
properties and the like.
-" 21229~
Other objects and features of the invention will
become apparent from the following description.
We conducted extensive research in an attempt to
achieve the above objects. Consequently, we have found
that a resin composition which comprises a fluorine-type
resin and which contains components each having one or two
of (i) hydroxyl group, (ii) silanol group and/or
hydrolyzable group attached directly to silicon atom and
(iii) epoxy group can be used in combination with a metal
chelate compound to provide a curable composition that has
excellent storage stability despite that said curable
composition is in the form of a one-package resin
composition. Purthermore, it has also been found that
said curable composition is readily curable without
causing the foregoing prior art problems and is unlikely
to pose toxicity problem. Moreover, the composition can
be used as a coating composition that gives a coating
excellent in resistance to weather, acids, scratching and
staining and the like. The present invention has been
accomplished on the basis of these novel findings. -~
According to the present invention there are
provided:
1) a resin composition comprising three components,
i.e., a hydroxyl group-containing compound (A), an epoxy ~ ~
group-containing compound (B), and a compound (C) - -
21229~
-- 4 --
containing hydrolyzable group directly attached to silicon
atom and/or silanol group, at least one of compound (A),
compound (B) and compound (C) being a fluorine-containing
resin (hereinafter referred to as "Invention l");
2) a resin composition comprising two components,
i.e., a hydroxyl group-containing compound (A), and a
compound (D) containing hydrolyzable group directly
attached to silicon atom and/or silanol group together
with epoxy group, at least one of compound ~A) and
compound (D) being a fluorine-containing resin
(hereinafter referred to as "Invention 2");
3) a resin composition comprising two components,
i.e., a compound (E) containing hydroxyl group together -~
with hydrolyzable group directly attached to silicon atom
and/or silanol group, and an epoxy group-containing
compound 1~), at least one of compound (E) and compound
(B) being a fluorine-containing resin (hereinafter
referred to as "Invention 3");
4) a resin composition comprising two component,
i.e., a hydroxyl group- and epoxy group-containing
compound (F) and a compound (C) containing hydrolyzable
group attached directly to silicon atom and/or silanol
group, at least one of compound (F) and compound (C) being
fluorine-containing resin (hereinafter referred to as
"Invention 4");
.
' 21229~
5) a curable composition comprising one of the
resin compositions as defined in the above items 1) to 4)
and as a curing catalyst a metal chelate compound; and : ~ :
6) a coating composition containing as an essential
component one of the compositions as defined in the above
items 1) to 5).
Throughout the specification, the term
"hydrolyzable group" used herein refers to a group which
is directly attached to silicon atom and which hydrolyzes
in the presence of water or moisture to give silanol
group. Examples of such hydrolyzable groups include those
represented by the following formulas. -
-O-R' (I)
O . .
-O-C-R" (II) ~ ~ :
~ R "'
-O-N=C ( I I I )
R " " :~
~ R "'
-O-N ( IY)
R" " ~ :
~R"'
-N ~ (y)
R" " ~ :
O ~:
-N-C-R "' ( VI )
R " "
2~229~5
- 6 -
In the foregoing formulas, R' is an alkyl having
1 to 4 carbon atoms, R", R"' and R"" are the same or
different and each represent an alkyl group having 1 to 8
carbon atoms, an aryl group or an aralkyl group.
Examples of the Cl_8 alkyl group in the above
formulas are methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-
octyl, iso-octyl, etc. In the above formulas and
throughout the specification, examples of the aryl group
are phenyl, tolyl, xylyl, etc. and examples of the aralkyl
group are benzyl, phenethyl, etc.
In addition to the above, examples of the
hydrolyzable group directly attached to silicon atom may
include a group _Si-H group.
In this specification, silanol group and the
above hydrolyzable group directly attached to silicon atom
are referred to as "silane group".
It is suitable that the silane groups in the
resin composition of the invention be hydrolyzable groups
of the formulas (I) and (II) attached to silicon atom and
silanol group in view of high storage stability,
curability and the like.
Invention 1
A. Hydroxyl group-containing compound (A)
With respect to Invention 1, hydroxyl group-
2~ 8~ :
- 7 -
containing compound (A) may be a compound which has at
least 2 hydroxyl groups on the average per molecule and -
which preferably has a number average molecular weight of
about 1,000 to 200,000, more preferably about 3,000 to
80,000. If the number of hydroxyl groups is less than 2
on the average per molecule, curability (gel fraction
ratio) of the resulting resin composition tends to become
insufficient, and hence undesirable. From the view point ;~
of weather resistance, water resistance or the like, it is
preferable that the number of hydroxyl groups is 400 or
less on the average per molecule. If the number average
molecular weight of compound (A) is less than 1,000, the -
. :.
properties of the resulting coating such as impact
resistance and weather resistance becomes impaired whereas
with the molecular weight of more than 200,000, compound
(A) tends to have lower compatibility with other
components and cause insufficient curing, thereby giving -~
insufficient weather resistance to the resulting coating.
Hydroxyl group-containing compound (A) includes
hydroxyl-containing compound (A-l) which is free of
fluorine and hydroxyl-containing compound (A-2) which
contains fluorine, and each is described below.
(i) Fluorine-free hydroxyl group-containing compound (A-l)
Examples of fluorine-free hydroxyl group-
containing compound (A-l) are those listed in the
:-- 2122~
following items 1 to 6).
1) Hydroxyl-containing vinyl resin
Typical examples of such resin include a polymer
comprising as monomer component a hydroxyl-containing
polymerizable unsaturated monomer (a), and when required
another polymerizable unsaturated monomer (b).
~ydroxyl-containing polymerizable unsaturated monomer (a):
Typical of such monomer are the compounds
represented by the formulas (l) to (4):
C H2 --C H
(1)
O R'
wherein Rl is a hydrogen atom or a hydroxyalkyl group;
- C H2 = C H
(2)
C H 2 - O - R '
wherein Rl is as defined above;
C H 2 = C Z o
C O C m H 2m~ ~C C p H ~p~~ ~ (3)
wherein z is a hydrogen atom or a methyl group, m is an
integer of 2 to 8, p is an integer of 2 to 18, and q is an
integer of O to 7;
21229~ :~
g ~
C H 2 = C Z :
C O~T 1 --~) S ~T2 --~~ H ::
Il (4) ~-
O ~:
wherein Z is as defined above, Tl and T2 are the same or
different and each represent a Cl_20 bivalent hydrocarbon
group, and s and v are each an integer of O to 10 with the
proviso that the sum of s and v is 1 to 10.
~ he hydroxyalkyl group in the formulas (1) and
(2) has 1 to 6 carbon atoms. Specific examples thereof
are -C2H40H, -C3H6oHt C4H8~H' et
Examples of the Cl_20 bivalent hydrocarbon group
in the formula ( 4 ) are given below.
-- (C}12 ) 2 --~ -- (CH2 ) 3 --~ --CH2 --
- CH2 CHCH2 - ~ - (CH2 ) 3 CH (CH2 ) 3 -
CH3 CH3
CH 3
--CHz CH2 C CH2 CH2 --~ -- (CH2 ) lo --
C}13
- -- (CH2 ) 12 --~ -- (CH2 ) 18 --~ --O--'
--C~ ' --CH2 ~--CH2 --
Examples of the monomer component of the formula
(1) are CH2=CHOH, CH2=CHOC4H80H, etc.
: :
: 2~229~
- -- 10 --
Examples of the monomer component of the formula
(2) include those represented by the following formulas.
CH2 = CHCH2 OH
CH2 = CHCH2 O CH2 CH2 OH
CH2 = CHCH2 OtCH2 CH2 Ot~-H
CH2 = CHCH2 O~CH2 CH2 O ~ H
Examples of the monomer component of the formula
(3) include those represented by the following formulas.
CH2 = C(CH3 ) COOC2H4 OH
CH2 = CHCOOC3 H6 OH
O
CH2 = C(CH3 ) cooC3H6 -O-tC-CH2 CH2 -
- CH2 CH2 CH2 ~)1 7 H
Examples of the monomer component of the formula
(4) include those represented by the following formulas.
CH2 = C(CH3 )COO-teH2 CHCH3 O) 5 - 6 H
CH2 = CHCOO~CH2 CH2 0)4 _ 5 H ~ -
CH2 = C(CH3 )COO-tCH2 CH2 O) 7 _ ~ H
CH2 = CHCOO~CH2 CH2 CH2 CH2 O) 4 - ~ H
CH2 = C(CH3 )COO-tCH2 CH2 0) 5 - 6
~ CH2 CHCH3 O) 5 - 6 H ~-~
.
.'
,. 2122g~ : ~
Also usable as the monomer (a) is an adduct of
any of hydroxyl-containing unsaturated monomers of the
formulas (1) to (4) with ~-caprolactone, y-valerolactone
or like lactone.
Another polymerizable unsaturated monomer ~b):
Typical of such monomer are those shown below as
tb-l) to tb-6). ~ ;
(b-l) Olefin-type compounds such as ethylene,
propylene, butylene, isoprene, chloroprene, etc.;
(b-2) Vinyl ethers and allyl ethers such as ethyl
vinyl ether, propyl vinyl ether, isopropyl vinyl ether,
butyl vinyl ether, tert-butyl vinyl ether, pentyl vinyl ;
ether, hexyl vinyl ether, i~ohexyl vinyl ether, octyl
vinyl ether, 4-methyl-1-pentyl vinyl ether and like chain-
like alkyl vinyl ethers, cyclopentyl vinyl ether,
cyclohexyl vinyl ether and like cycloalkyl vinyl ethers,
phenyl vinyl ether, o-, m- or p-tolyl vinyl ether and like
aryl vinyl ethers, benzyl vinyl ether, phenethyl vinyl
ether and like aralkyl vinyl ethers, etc.;
~ b-3) Vinyl esters and propenyl esters such as vinyl
acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate,
vinyl caproate, vinyl isocaproate, vinyl pivalate, vinyl
caprate and like vinyl esters, isopropenyl acetate,
isopropenyl propionate and like propenyl esters, etc.;
(b-4) Esters of acrylic or methacrylic acids such as Cl-
, ": - , . - ~ ,., ' . .' '.. ,,: ' . '' : ~ . ':
p~
2~22~
- 12 -
C18 alkyl esters of acrylic or methacrylic acids including
methyl acrylate, ethyl acrylate, propyl acrylate,
isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl
acrylate, lauryl acrylate, methyl methacrylate, ethyl
methacrylate, propyl methacrylate, isopropyl methacrylate,
butyl methacrylate, hexyl methacrylate, octyl methacrylate
and lauryl methacrylate, C2-C18 alkoxyalkyl esters of
acrylic cr methacrylic acids including methoxybutyl
acrylate, methoxybutyl methacrylate, methoxyethyl
acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate
and ethoxybutyl methacrylate, etc.;
(b-5) Vinyl aromatic compounds such as styrene, ~-
methyl styrene, vinyltoluene, p-chlorostyrene, etc., and
(b-6) Acrylonitrile, methacrylonitrile, etc.
2) Hydroxyl-containing polyester resin
The resin is prepared by esterification or ester
interchange reaction of a polybasic acid with a polyhydric
alcohol. Examples of useful polybasic acids include the
compounds having 2 to 4 carboxyl groups or methyl
carboxylate groups per molecule such as phthalic acid or
anhydride, isophthalic acid, terephthalic acid, maleic
acid or anhydride, pyromellitic acid or anhydride, -
trimellitic acid or anhydride, succinic acid or anhydride,
sebacic acid, azelaic acid, dodecanedicarboxylic acid, ~-
dimethyl isophthalate, dimethyl terephthalate and the
212298~
- 13 -
~;
like. Examples of useful polyhydric alcohols are alcohols
having 2 to 6 hydroxyl groups per molecule such as
ethylene glycol, polyethylene glycol, propylene glycol,
neopentyl glycol, 1,6-hexanediol, trimethylolpropane,
pentaerythritol, glycerin, tricyclodecanedimethanol,
etc. When required, monobasic acids are usable for
preparation of the resin and such monobasic acids include
fatty acids of castor oil, soybean oil, tall oil, linseed
oil or the like, and benzoic acid.
3) Hydroxyl-containing polyurethane resin
Isocyanato-free resins prepared by modifying a
hydroxyl-containing vinyl resin of the above item 1),
hydroxyl-containing polyester resin of the above item 2)
or the like with a polyisocyanate compound such as
tolylene diisocyanate, xylylene diisocyanate,
hexamethylene diisocyanate, isophorone diisocyanate or the ~
like. ~-
4) Hydroxyl-containing silicone resin
Alkoxysilane-free and silanol-free resins ~
prepared by modifying a hydroxyl-containing vinyl resin of z
the above item 1), hydroxyl-containing polyester resin of
the item 2) or the like with a silicone resin such as Z-
6018 or Z-6188 (trademarks for products of Dow-Corning
Corp.), or SH 5050, SH 6018 or SH 6188 (trademarks for
products of Toray Silicone Co., Ltd.).
2 1 2 ~ 9 8 ~
- 14 -
(ii) Fluorine-containing hydroxyl group-containing
compound (A-2)
Examples of hydroxyl group-containing compound
(A-2) which contains fluorine are those listed in the
following items 1) to 5).
1) Hydroxyl- and fluorine-containing resin
Typical examples of such resin include a polymer
comprising as monomer components a hydroxyl-containing
polymerizable unsaturated monomer (a), a fluorine-
containing polymerizable unsaturated monomer (c) and when
required another polymerizable unsaturated monomer (b).
Fluorine-containing polymerizable unsaturated monomer (c):
. . . ,:
Typical of the monomer (c) are the compounds of
the forumals (5) and (6)
CX2=CX2 l5)
wherein the groups X are the same or different and each
represent a hydrogen atom, a chlorine atom, a bromine
atom, a fluorine atom, an alkyl group or a haloalkyl ~ :
group, provided that the compound contains at least one :~
fluorine atom;
C H 2 =
C = O '
(6
O C n H2n R
wherein Z is as defined above, R2 is a fluoroalkyl group
21 229~
- 15 -
and n is an integer of 1 to 10.
The alkyl group in the formula ~5~ has 1 to 6
carbon atoms, preferably 1 to 4 carbon atoms. Specific
examples are methyl, ethyl, propyl, isopropyl, butyl,
pentyl, etc. The haloalkyl group in the formula (5) has 1
to 6 carbon atoms, preferably 1 to 4 carbon atoms.
5pecific examples are CF3, CHF2, CH2F, CC13, CHC12, CH2C1,
C~C12' (CP2)2cF3~ (CF2)3CF3, CF2CH3, CF2CHF2, CF2Br,
CH2Br, etc.
Examples of the monomer of the formula (5)
include the compounds represented by the following
formulas.
CF2 5 CP2 ~ CHF5 CF2 ~ CH2 5 CF2
CH2 = CHF ~ CCQ F 5 CF2 ~ CHCQ = CF2
CC Q 2 5 CF2 ~ CC Q F = CC Q F ~ CHF = GC Q 2
.
CH2 5CCQ F ~ CCQ 2 =CCQ P ~ CF3 CF5CF2
CF3 CF= CHF ~ CF3 CH= CF2 ~ CF3 CF= CH2
CHF 2 CF= CHF ~ CH3 CF= CF2 ~ CH3 C~= CH2
CF2 CQ CF5CF2 ~ CF3 CCQ 5C~2
CF3 CF=CF CQ- ~ CF2 CQ CC2 = CF2
CF2 CQ C~5CP CQ ~ CF CQ 2 CF5CF2
CF2 CCQ 5CCQ F ~ CF3 CCQ 5CCQ 2
CCQ F 2 CF5CCQ 2 ~ CCQ 3 CF=CF2
CF2 CQ CCQ 5CCQ 2 ~ CFCQ 2 CCQ 5CCQ 2
CF3 CF= CH C Q ~ CC Q F2 CF= CH C Q ~
- '-
21 22 ~ 8 r~
- 16 -
CF3 CCQ = CH CQ ~ CHF 2 CCQ = CCQ
C~z CQ CH= CCQ 2 ~ CF2 C~ CCQ = CH CQ
CCQ 3 CF= CH CQ ~ CF2 I CF= CF
CF2 BrCH= CF2 ~ C~3 CBr = CHBr~
CF2 CQ CBr = CH2 ~ CH2 BrCF= CCQ 2
CP3 CBr= CH2 ~ CFz CH= CHBr~
CF2 BrCH= CHF ~ CF2 BrCF= CF
CF3 CFz CF= CF2 ~ CF3 CF= CFCF
CF3 CH- CFCF3 ~ CF2 = CFCF2 CHF
CF3 CF2 CF= CH2 ~ CF3 CH= CHC~3 ~
CF~ = CFCF2 CH3 ~ CF2 = CFCH2 CH3 ~ :
CF3 CH2 CH= CH2 ~ CF3 CH= CHCH
CF2 = CHCH2 CH3 ~ CH3 CFz CH= CH
CFH 2 CH= CHCFH 2 ~ CH3 CF2 CH= CH
CH2 = CFCH2 CH3 ~ CF3 (CF2 ) 2 CF= CF
CF3 (CF2 ) 3 CF= CF
The fluoroalkyl group in the formula (6) has 3
to 21 carbon atoms. Specific examples are C4Fg,
(cF2)6cF(cF3)2~ C8F17~ ClOF21' etc-
Examples of the monomer of the formula (6)
include the compounds represented by the following
formulas.
'- 21229~
CH~
CH2 = C-COO- C2 H4 -C4 ~9
CH3
CH2 = C-COO- C2 H4 -(C~2 3 6 CF' CF~3
CH3
CH2 = C-COO- C2 H4 -C8 F17
CH3
CH2 = C-COO- C2 ~4 -Clo F'21
These monomers are usable singly or at least two
of them can be used in mixture.
Use of the monomer of the formula (S) gives a
coating outstanding in resistance to acids and weather,
and use of the monomer of the formula (6) forms a coating :
excellent in water repellency.
2) Hydroxyl-containing silicone resin which further
contains fluorine
Alkoxy-free and silanol-free resins prepared by
modifying the above hydroxyl- and fluorine-containing
resin with the silicone resin used in the above item 4).
3) Hydroxyl-containing esterified fluorine-containing
~ 212~g~
- 18 -
resin
This resin is a hydroxyl-containing resin
prepared by esterifying the above hydroxyl group-
containing resin IA) with a copolymer comprising as
monomer component the foregoing fluor.ine-containing
polymerizable unsaturated monomer (c), a carboxyl-
containing polymerizable unsaturated monomer (d), and if
desired, another polymerizable unsaturated monomer (b). ::
Carboxyl-containing polymerizable unsaturated monomer (d)~
Typical of monomer (d) are the compounds :
represented by the formulas (7) and (8):
R3 'C = C--R OH (7)
wherein R3 is a hydrogen atom or a lower alkyl group, R4
is a hydrogen atom, a lower alkyl group or a carboxyl
group, and R5 is a hydrogen atom, a lower alkyl group or a
carboxy-lower alkyl group; ~:
R6 o
C H 2 = C--C--O--C m H ~m--C O O H (8)
wherein R6 is a hydrogen atom or a methyl group, and m is
as defined above.
Preferred lower alkyl groups in the formula (7) -
..
2~229~
- 19 -
are those having 1 to 4 carbon atoms, especially methyl.
Examples of the monomer of the formula (7) are
acrylic acid, methacrylic acid, crotonic acid, itaconic
acid, maleic acid, maleic anhydride, fumaric acid, etc.
Examples of the monomer of the formula (8) are :
2-carboxyethyl acrylate or methacrylate, 2-carboxypropyl
acrylate or methacrylate, 5-carboxypentyl acrylate or : :
methacrylate, etc.
Also usable as the monomer (d) is an adduct of 1
mole of hydroxyl-containing polymerizable unsaturated
monomer (a) with 1 mole of a polycarboxylic acid anhydride
compound such as maleic anhydride, itaconic anhydride,
succinic anhydride, phthalic anhydride or the like.
4) Hydroxyl-containing urethane fluorine-containing resin
Hydroxyl-containing resin prepared by modifying
the foreqoing hydroxyl containing compound (A-l) with the
foregoing polyisocyanate compound, and hydroxyl-containing
resin prepared by reacting (i) an isocyanato-containing
fluorine-containing resin comprising as monomer component
a fluorine-containing polymerizable unsaturated monomer
(c), an isocyanato-containing polymerizable unsaturated
monomer (e), and when required another polymerizable
unsaturated monomer (b) with (ii) the foregoing hydroxyl-
containing compound (A-l) such that the resulting resin
will contain hydroxyl group(s).
' 21229~5
- 20 -
Isocyanato-containing polymerizable unsaturated monomer
(e)~
Typical examples of the monomer (e) are those :
represented by the formulas (9) and (10) ;:
R 6
C H 2 = C--C O O ( C n H 2n) N C O
wherein R6 and n are as defined above, examples of the
monomer of the formula (9) being isocyanato-ethyl acrylate
or methacrylate; and
'
C H2 = C ~Cn H2n--N C O
R7 (10) :-
R 6
wherein R6 and n are as defined above and R7 is a hydrogen
atom or an alkyl group having 1 to 5 carbon atoms,
examples of the monomer of the formula (10) being ~,~-
dimethyl-m-isopropenyl benzyl isocyanate.
Also usable is a reaction product of 1 mole of -~
the hydroxyl-containing polymerizable unsaturated monomer
(a) and 1 mole of a polyisocyanate compound. Examples of
such polyisocyanate compounds are tolylene diisocyanate, :~
1,6-hexamethylene diisocyanate, 4,4'-diphenylmethane :~
diisocyanate, 4,4'-diphenyl ether diisocyanate, phenylene :'
~ :-~
.: . ,
- 2~2~5 :
- 21 -
.
diisocyanate, naphthalene diisocyanate, biphenylene
diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate,
dicyclohexylmethane 4,4'-diisocyanate, p-xylylene
diisocyanate, m-xylylene diisocyanate, bis(4-isocyanato-
phenyl)sulfone, isopropylidenebis(4-phenylisocyanate),
lysine isocyanate and isophorone diisocyanate, polymers
thereof, biurets thereof, etc.
Also usable as the isocyanato-containing
fluorine-containing resin is a reaction product prepared
by reacting a hydroxyl-containing resin (A-2~ with, e.g.,
the above polyisocyanate compound.
5) Other hydroxyl-containing fluorine-containing resin
Hydroxyl-containing resin prepared by
polymerizing an epoxy-containing polymerizable unsaturated
monomer (such as glycidyl acrylate or methacrylate), a
fluorine-containing polymerizable unsaturated monomer lc)
and when required another polymerizable unsaturated
monomer (b) in the presence of a copolymer comprising as
monomer component a carboxyl-containing polymerizable
unsaturated monomer (d), a hydroxyl-containing
polymerizable unsaturated monomer (a) and if desired
another polymerizable unsaturated monomer (b).
B. Epoxy group-containing compound (B)
Epoxy group-containing compound (B) is a
compound which has at least 2, preferably 2 to 300, epoxy
: ~ " . -. . . . :- - , :. .. ,:, ,: : ,; - .. ; .. . ", .. ..
212~
- 22 -
groups on the average per molecule and which preferably
has a number average molecular weight of about 120 to
200,000, more preferably about 240 to 80,000. If the
number of epoxy groups is less than 2 on the average per
molecule, curability of the resulting resin composition
(gel fraction ratio) tends to become insufficient. It is
difficult to obtain such compound having a number average
molecular weight of less than 120, and if the number
average molecular weight is more than 200,000, compound
(B) tends to have lower compatibility with other
components, thereby giving insufficient weather resistance
to the resulting coating.
(i) Fluorine-free epoxy-containing compound (B) -
Examples of epoxy group-containing compound lB)
which is free of fluorine are those represented by the
following formulas.
R6 R6 ~
-:
CH2-C-Ra-0-R~-0-R~-C - CHz (11)
O ~
:,
:::
. ~,
2~ 2298a
- 23 -
O
F~6 C R6
CHz-C-R8-N N-R8-C--CH2
O C C O
b~ \ /\\
O N O
(12)
R~
R6_C
O
H2C
. .
C--O--R 8--C~--~C H 2 ( 13 ) ~ :
~C_o-F~-7C /c~
.
"
. ," i, .. ~ ~,, ; ,.,~.. " . ~ .
21229~
-- 24 --
R6 Rq R9 R9 R6
C~2~C--R~- I i--0~ ~--03;~ i--C~ ~CH2 (
C~-C--CH,-0~1l~ o-CH2-li--CH
c\/c~30 (16) ~ ~
C\2--C--R8--0--R8~co ( 17 )
2122Q~5
- 25 -
R6 o ~
C\2/c-R8-oc-R8 ~ ~ O (18)
o
wherein R6 is as defined above, R8 is a Cl_8 bivalent
hydrooarbon group, and groups R6 and groups R8 may be the
same or different, groups R9 are the same or different and
each represent an alkyl group having 1 to 8 carbon atoms,
an aryl group or an aralkyl group, groups R10 are the same
or different and each represent a hydrogen atom or an
alkyl group having 1 to 4 carbon atoms, and w is O or an
integer of 1 to 10.
Examples of the above Cl_8 bivalent hydrocarbon
group may be selected from those already exemplified with
respect to Cl_20 bivalent hydrocarbon group.
Examples of the compounds of the formulas (11)-
(18) are as follows.
;
:
~ CH2-CH-CH2-O-CHzCHz-O-CH2-C~-CH2
.
2f 2298~
- 26 -
O
Il .
C
CH2-CH-CH2-N N-GHz-CH-GH2
\ / I I \ /
O C C o
O N O ;~
H2C
--
HC .
O ,~
H ~ C
C~CH--CH,--o~3c~o--CH,--CH--~CH,
I H3 I H,
C~2~CH--(CH2)3--Si--0~ O3--(CH2),--C~CH2 '
O CH3 CH3 0
i
,
.
-: 2~229~
-- 27 --
O CH,
~C - O - C H z - C~ ~C H 2
IJ~o Cl H 3
C--O- CH2--C~ ~CH2
CH2--CH~
CH2~CH--CH2--O--CH2~o
CH3 1~
CH2--C--CH2-OC--CH2~o
: ~ 2~2~9~ :
- 28 -
' -' , ',
.'
Further examples of fluorine-free epoxy compound
include those represented by the formulas.
o~C-O-C~7~o ~Lo~
~ )CH ~
0~ 0 0~ _~o
Also usable as the polyepoxy compound is an adduct of
Q~
~ CH20~ with a polyisocyanate compound. Examples of
such polyisocyanate compounds are organic diisocyanates
such as hexamethylene diisocyanate, trimethyl hexa- - -
methylene diisocyanate and like aliphatic diisocyanates;
hydrogenated xylylene diisocyanate, isophorone
diisocyanate and like cyclic aliphatic diisocyanates;
tolylene diisocyanate, 4,4i-diphenylmethane diisocyanate
and like aromatic diisocyanates; an adduct of the organic
diisocyanate with a polyhydric alcohol, a low-molecular-
weight polyester resin, water or the like; a polymer of
such organic diisocyanates, biurets, etc. Representative
commerical products of polyisocyanate compounds are those
. .
~1 ' ' . ' .
,, 212298~
available under the trademarks: "BURNOCK D-750, -800, DN
-950, DN-970 and 15-455" (products of Dainippon Ink And
Chemicals Incorporated), "DESMODUL L, NHL, IL, N3390"
(products of Bayer AG, West Germany), "TAKENATE D-102,
-202, -llON and -123N" (products of Takeda Chemical
Industries, Ltd.~, "COLONATE L, HL, EH and 203" (products
of Nippon Polyurethane Kogyo K.K.), "DURANATE 24A-9OCX"
(product of Asahi Chemical Industry Co., Ltd.), etc. Also
usable as the epoxy compound (B) are an adduct of a
compound of the formula
O
o~c ~o
with a polybasic acid; a product prepared by oxidizing an
esterification product having unsaturated group such as a
group ~ in the molecule with a peracetic acid or the
like, examples of the esterification product being an
esterification product of 900 in number average molecular
weight prepared by esterifying tetrahydrophthalic
anhydride, trimethylol-propane, 1,4-butanediol and the
like.
Also usable as epoxy group-containing compound
(B) is a polymer comprising as monomer component an epoxy-
containing polymerizable unsaturated monomer (f) and if
desired another polymerizable unsaturated monomer (b). :~
. j:
- 2 ~ 2 2 ~ 8 ~ ~
- 30 -
Epoxy-containing polymerizable unsaturated monomer (f3:
The monomer (f) is a compound containing epoxy
group and radically polymerizable unsaturated group in the
molecule, Bxamples of the radically p~lymerizable
unsaturated group include the groups represented by the
formulas .
~ 6
C H2 = C--C ~ O--
6 o
1~ _
C H 2 = C--C--C ~
~ 6 o ~-:
,.................. I 11 ':
C ~I2 = C--C ~ N~
C H 2 = C H C ~ 2 --~-- ~:
C ~I 2 = C H O-- ~
CH2 --C H-- -
R 6
C H 2 = C ~
In the foregoing formula, ~6 i5 as defined
above. :
Examples of the epoxy-containing polymerizable
unsaturated monomer (f) having radically pol~merizable
unsaturated group CH2=C(R6~COO- include the compounds
2~2298~
- 31 -
represented by the formulas (193 to (31).
CH2=C-C-O-R~-C - CH~ (19)
\O
CH2=C-C-O ~ O (20)
R6 O~ ~ (21)
C H ,= C - C--O--R ~ f3o (22)
CH,=C-C-O-R8 (23)
CH2=l-C-O-R~ ~ O ~ (243
:::
~ .............. I
'.'6 ' , . .
. ~ .. '.'.' ' ' '
212~9~ :
- 32 ~
Rl6 0~ C--0--CH2~0 (25)
HO
H I C--0--R ~CH 2 -o--c~co ( 26)
R6 o
CH2=C--C--0--R8--ICH~O (27) ::
H ~
R6 o
CH2= C - C--~ \CH~O ( 2 8 )
HO CH2--0
CH,=C--C--~0 CH? (29)
R6 o ~ o R6 R6 o
CH2=1--1-0-R~--Ot1-R11--O~C--~-R1~--N--l-O-R8~0 ~::
(30) :~:
R6 o ~ o R6 R6 o
CH2=C--l-O--R~--O~l--Rlt--o~l--N--R11--N--C-O-R~
( 3 1 )
:::
:,' ' ~ ~ : ' : '
i ' ' ~", , ., ~ , ! : . . .
2~22~8~
- 33 -
In the foregoing formulas, R6, R8 and w are as
defined above, R11 is a Cl_20 bivalent hydrocarbon group,
the groups R6 are the same or different, the groups R8 are
the same or different and the groups Rll are the same or
different.
Specific examples of the monomers of the
formulas (19) to (31~ are those represented by the
following formulas.
CH3 0
CH.=C - C- O - CH-CH\ /CH,
CH,=CH-C-O ~ O
I C O (CH2)5-O ~ O
CH,=C - C-O-CH,
2122n85
- 34 - ~;
CH2= CH--~C--O--(CH2) 2 ~o
CH2=C--C--O--(CH ) ~0~
OH G
O O
CH2=CH--C--O--CH~C--O-CH2--C~~
,
CH2=C--C--O--(CH2)s~CH2~0~ IJ ~D~
:
CH2=CH--C--O--CH2--JCH~CO
O H
CH, O
HO~XCH~-O
',
212298~
- 35 -
Examples of the epoxy-containing polymerizable
unsaturated monomer (f) having radically polymerizable
unsaturated group CH2=C(R5)-C-N' are those represented by
O ' -
the formulas (32) to (34).
R6 o R6 "~
CH2-C--C--N--RaV~~ (3~)
R6 o R6
.
~ ~,
C H2= C--~--N R~ 8_~3
(34) :
In the foregoing formulas, R6 and R8 are as
defined above, the groups R6 are the same or different,
and the groups R8 are the same or different.
Specific examples of the compounds of the
formulas (32) to (34) include those represented by the
following formulas.
- 36 -
0 ~H,
CIH3 ~ Cl2H5 ~
CH2=C - C-N-C2H4 ~ 0
O CHs
CH2=CH--C--1~--CH2--o--CH2~0
Examples of the epoxy-containing polymerizable
unsaturated monomer (f) havins radically polymerizable
unsaturated group CH2=C(R6)-e-C~ are inclusive of those
O . :
represented by the formulas (35) to (37
CH2=C-~C-R8 ~ 0 (35~
O , .
R' ~3 (36)
'''
:, .
~,
21229~5 :
- 37 -~
CH2=C-C-R8-l - CH2
~ 0/ (37)
In the foregoing formulas, R6 and R8 are as
defined above, the groups R6 are the same or different,
and the groups R8 are the same or different.
Specific examples of the compounds of the
formulas ~35) to (37) are those represented by the
following formulas. I ;~
CH2=C (CH,)ICl-CH2-CH
O ,- ~
CH2=C (CH,)~C-CH2-(CH2)2 ~ o : ~-~
O
CH2=CH C-CH2-CH2-C\ /CH2
O O
Examples of the epoxy-containing polymerizable
unsaturated monomer (f) having radically polymerizable
unsaturated group CH2=C(R6)-C-N~ are those exemplified
21229~
-- 38 -
above and represented by the formulas ( 38 ) to ( 43 ) .
C H ~ = C--ICl--I - R8~ W ~ ( 3 8 )
C H~ = C--C--N--R~O ( 3 9 )
R6 R6
CH,=C--C~ _C~CH~ (4~
C H2 - I--C - N--C~ N--R1l--H--C ~0--R ~C ( 41 )
C H2 = C--b I IIC~ o3~ ( 4 2 )
U 1 ~
2~98~
- 39 -
In the foregoing formula, R6 r R8, Rll and w are
as defined above, the groups R6 are the same or different, ~:
the groups R8 are the same or different and the groups Rll -
are the same or different. :
Specific examples of the compounds of the
formulas (38) to (43) are those represented by the
following formulas.
,
CH =C (CH3)C-N-CH2 ~ o
CH2=CH ICI--I (CH2)2~o
CH2=C (CH3)~C-I_CH2_C\ -/CH2
O CH3 0
O O
CH2=CH -- Cll--IN--C NH ( H
CH~=C (CH~)C--N C~(CH~s~OC~O
O CH3 0
CH~=CH --C--N-C--CH~ CCo
O '.~ ~ '
212298~ '
- 40 -
Examples of the epoxy-containing polymerizable
unsaturated monomer ~f) having radically polymerizable
unsaturated group CH2=CHCH20- are those represented by the
formulas ~44) to (47), ~ ~
R6 :
CH2=CHCH20-R8-l\ /CH2
CH2=CHCH20-R8 ~ 0 (45)
.
CH,=CHCH,0-R~ ~ 0 (46)
CH2=CHCH20-R -I ~ 0 ~47)
OH h
In the foregoing formulas, R6 and R8 are as
defined above and the groups R8 are the same or different. :
Specific examples of the compounds of the
formulas (44) to (47) include those represented by the
following formulas.
,-~' 2l2298~ ~:
ICH3
CH2=~HCH20-CH2-C\ /CH2
~ ,
CH.=CHCH.0-CH. ~ o
CH2=CHCH20--(CH2)2~,co 1 ~
CH2=CHCH20-CH2-l ~ -
Examples of the epoxy-containing polymerizable
- ::
unsaturated monomer (f) having radically polymerizable
unsaturated group CH2=CH0- are inclusive of those ~ :
represented by the formulas (48) to (50).
~: 21 22~9 8~
- 42 ~- :
R6 (48)
CH2=CHO-R8-C\ /CH2
o
CH2=CHO-R~ ~ O (49~
CH2=CHO-R~ - ~ O (50)
In the foregoing formulas, R6 and R8 are as
defined above and the groups R8 are the same or different.
Specific examples of the compounds of the --
formulas (48) to (50) are those represented by the
following formulas.
CH2=CHO-(CH2)3-l\ /CH2 ~.
O
- 4~ï2298~
CH2=CHO-CH2 ~ o
CH2=CHO--CH2 ~ o :'
Examples of the epoxy-containing polymerizable
unsaturated monomer (f) having radically polymerizable
unsaturated group CH2=C~- include the compounds
represented by the formulas ~51~ to (53).
CH2-CH-R~-l~ /CH2 (51) ~ ;~
CH:=CH-~ ~ O (52)
C H 2 = C H - R8~o ; '-;
(53~
In the foregoing formulas, R6 and R8 are as
defined above and the groups R8 are the same or different.
298~
Specific examples of the compounds of the
formulas (51) to (53) include those represented by the
following formulas.
CH2=CH-CH2-C\ /CH2
CH2=CH-CH2 ~ o
CH2=CH-CH2 ~ o
Examples of the epoxy-containing polymerizable -
unsaturated monomer (f) having radically polymerizable
unsaturated group CH2=C(R6) ~ include the compounds
represented by the formulas (54) to (58).
CH2=C ~ R
O (54)
CH2=C ~ O-R~ ~ ~ (55)
~ 45 ~ 21 2298 5
CH2=C ~ R1~-H-C-O- R~O (s6)
CH2=C
CH2=C ~ R11 ~ O (58)
~' ~
In the foregoing formulas, R6, R8 and Rll are as
defined above, the groups R6 are the same or different and
the groups Rll are the same or different.
Specific examples of the compounds of the
formulas (54) to ~58) include those represented by the
following formulas.
CH2=C (CH3) ~ -CH2-C\ /CH2 -~
- 46 ~~ 2~229~
CH2=CH . ~ -CH2 ~ o
O
CH2=C (CH~) ~ g-NC-OCH2 ~ o
CH2=C (CH~) ~ (CH2)2 ~ o
CH2=CH ~ ~ CH2 ~ o
Also usable as epoxy group-containing compound
(B) is a reaction product prepared by reacting-the
foregoing hydroxyl-containing compound (A-l) with a
compound containing one isocyanato group and one epoxy
group in the molecule such that at least 1 mole of the
latter compound is used per hydroxyl group of the
hydroxyl-containing compound (A 1) so as to consume all of
the hydroxyl groups of the hydroxyl-contain;ng compound
- 47 -
2~2~9~
(A-l). Examples of said compound containing one
isocyanato group and one epoxy group in the molecule are
those represented by the following formulas.
.~'
CH3 O :
OCN~NHCOCH~
O CH,
o ~ (CH2 ~ OC-NH ~ NCO
OCH.~c~OC--NH--CH ~
OCH2 CH2NCO
~ ~ CH3 : -
o~CH2--O~C~CH2~0~C--NH~CH~
CH3 CH2NCO
212298~ ''
¦ ~ CH3
CH~ CH2NCO
0
CH2-CH-CH2-OC-NH-(CH2 ~ CO
o
(ii) Fluorine-containing epoxy-containing compound (B)
Examples of epoxy-containing compound ~B) whic~
contains fluorine are a copolymer prepared by
copolymerizing fluorine-containing polymerizable
unsaturated monomer ~c), epoxy-containing polymerizable
unsaturated monomer (f) and, if desired, another
polymerizable unsaturated monomer (b); and a re~in
prepared by reacting the foregoing fluorine-containing
hydroxyl-containing compound (A-2) with the above compound
which contains one isocyanato group and one epoxy group in
the molecuie.
C. Silane compound (C)
- 49 ~ 2~22~
Silane compound (C) is a compound which contains
at least 1 silane group on the average per molecule. If
the number of silane groups is less than 1 on the average
per molecule, the resulting composition will have inferior
curability (gel fraction ratio). As the number of silane
groups increases, the reaction between silane groups and
epoxy groups preferentially takes place, reducing the
number of epoxy groups which are needed to react with
hydroxyl groups, and consequently impairing the curability
of the resulting coating (gel fraction ratio). Thus the
number of silane groups is preferably 2,500 or less on the
average per molecule. Furthermore, silane compound (C)
has a number average molecular weight of 104 to 200,000.
It is difficult to obtain such compound having a number ~
average molecular weight of less than 104, and if the -
number average molecular weight is more than 200,000,
silane compound (C) tends to have lower compatibility with
other components, thereby g~ving insuffcient weather -~
resistance to the resulting coating.
(i) Fluorine-free silane group-containing compound tC)
Examples of fluorine-free silane group-
containing compounds (C) are those of the following items.
1) Polysilane compound
Examples of polysilane compound are those
represented by the formulas (59) to (61).
-- 50 --
2~229~
yr
Y ' - S i - Y ~ ( 5 9 )
r
~ 9
Y'--S i-Y' (60)
I,
R 9
R9 --S i --Y' (6 1 )
Y'
. .
In the foregoing formulas, the groups Yrare the
same or different and each represent a hydrogen atom, a
hydroxyl group or a hydrolyzable group exemplified above,
R9 is as defined above and the groups R9 are the same or
different.
Specific examples of the comp~unds having the
formulas (59) to (61) are dimethyldimethoxysilane,
dibutyldimethoxysilane, diisopropyldipropoxysilane,
diphenyldibutoxysilane, diphenyldiethoxysilane, diethyl-
disilanol, dihexyldisilanolmethyltrimethoxysilane,
methyltriethoxysilane, ethyltriethoxysilane,
propyltrimethoxysilane, phenyltriethoxysilane,
.
'~
, t ~ r
2 ~ 2 2 9 ~
phenyltributoxysilane, hexyltriacetoxysilane, methyl- - I
trisilanol, phenyltrisilanol, tetramethoxysilane,: ~; :
tetraethoxysilane, tetrapropoxysilane, tetraacetoxysilane,
di-iso-propoxydivalerooxysilane, tetrasilanol, and the :
compounds represented by the formulas
O C H~ C O--I i - O C C H~
bCH3 0 ICl CH~
O
C2HsIC2Hs C2Hs
C2HsO--S i--OC2Hs >C=NO--S i--ON=C<
OC2Hs C2Hs CH3 C2Hs :~
-
1~l CH3 C3H7 CH3
CH30- i--OCC2Hs >N--S i--N<
C~C Hs
C2Hs CH3 C2Hs 1~1
>NO--Si--ON< ~J O
C2Hs ~ C2Hs C4H~O~ NCCH3
C~H~ CH~
:
2~2~9~5
- 52 -
Condensation products of such polysilane
compounds are also usable.
The above silane compounds preferably have a
number average molecular weight of 104 to 40,000, more
preferably 104 to 30,000. Silane compounds having a
number average molecular weight of less than 104 are not
readily available, whereas those having a number average
molecular weight of more than 40,000 tends to have lower
compatibility with other components, thereby giving
impaired weather resistance to the resulting coating.
2) A homopolymer of silane group-containing
polymerizable unsaturated monomer (g) or a copolymer of
such monomer (g) and another polymerizable unsaturated
monomer (b).
Silane-containing polymerizable unsaturated monomer (g)~
Monomer (g) is a compound containing at least
one silane group and radically polymerizable unsaturated
group in the molecule. Examples of the radically : :
polymerizable unsaturated group are those represented by
the formulas
R 6
C H2 = C--C O O -
53 _2~2f~985~
R6 : -:
C H 2 = C
R 6
'-
C H 2 = C ~
C H2 = C H O--
C H2 --C H C H2 ~--
.
wherein R6 is as defined above.
Examples of the silane group-containing
polymerizable unsaturated monomer (g) having radically
polymerizable unsaturated group CH2=C(R6)-COO- include the
compounds represented by the formula (62) ~:
R6 y
CH2=C-COO-R1l-Si-Y ~ '
I (62)
Y
wherein R6 and Rll are as defined above, groups Y are the
same or different and each represent a hydrogen atom, a
hydroxyl group, a hydrolyzable group, a Cl_8 alkyl group, :~
an ~ryl group or an aralkyl group, and at least one of
groups Y is a hydrogen atom, a hydroxyl group or a
hydrolyzable group.
,.~
2~2298,~
Examples of the compounds of the formula (62)
are y-(meth)acryloxypropyltrimethoxysilane,
y-(meth)acryloxypropyltriethoxysilane,
y-(meth)acryloxypropyltripropoxysilane,
y-(meth)acryloxypropylmethyldimethoxysilane,
y-(meth)acryloxypropylmethyldiethoxysilane,
y-(meth)acryloxypropylmethyldipropoxysilane,
y-(meth)acryloxybutylphenyldimethoxysilane,
y (meth)acryloxybutylphenyldiethoxysilane,
y-(meth)acryloxybutylphenyldipropoxysilane,
y-(meth)acryloxypropyldimethylmethoxysilane,
y-(meth)acryloxypropyldimethylethoxysilane, ,:
y-(meth)acryloxypropylphenylmethylmethoxysilane,
y-(meth)acryloxypropylphenylmethylethoxysilane,
y-(meth)acryloxypropyltrisilanol,
y-(meth)acryloxypropylmethyldihydroxysilane~ -~
y-(meth)acryloxybutylphenyldihydroxysilane~
y-(meth)acryloxypropyldimethylhydroxysilane,
y-(meth)acryloxypropylphenylmethylhydroxysilane, and
compounds represented by the following formulas.
~2~5
- 5s - ;
CH3 O
11
CHz=C (CH3)COO(CHz)3-Si-OCCH3
1 ~
OCCH3
CH3 C2Hs
CH 2 = CH - COO~CH 2 ) 4-Si-O-N
CH3 C2Hs
Examples of silane group-containing
polymerizable unsaturated monomer (g) having radically
polymerizable unsaturated group CH2=C(R6) ~ include
the compounds represented by the formulas (63) to (65)
- ,
~ CH2=C ~ R~ Y (63~
y
CH2=C ~ i Y (64) ~ ;
.'
CH2=C ~ O-R~ Y
y (65)
X
, :
2~229~
- 56 -
In the foregoing formulas, R6, Rll and Y are as
defined above, the groups Y are the same or different, and
at least one of the groups Y is a hydrogen atom, a
hydroxyl group or a hydrolyzable group.
Specific examples of the compounds of the
formulas (631 to (65) include the compounds represented by
the following formulas.
CH2=C (CH33~C2H~-- S i(OCHa)~ '
CH2=C ~CH3 ~ C2H~-Si(CHl)20CH,
C H2- C H ~C2H4- S i (OH)3 :
CH2-C (CH3~C2H4- Si(CH3)20H
:
o
CH2=CH ~C3H6--S i(OCC H~) 3
C H2--C (C H3~S i(O C H3) 3
2~22~8~
- 57 ~
CH2=CH --~S i (CH3)2N(CH3)2
CH2=C (CH3)~30--C2H4--S i (OC2Hs)2
',
Examples of silane-containing polymerizable
unsaturated monomer (g) containing radically polymerizable
unsaturated group of the formula CH2=C(R6)- include the
compounds of the formulas ( 66 ) to ( 67 ) .
R 6 y
I i (66)
CH 2 = C--S i--Y
;' . '; :'
R6 y
CHz=C-R1~-Si-Y (67)
Y
In the formulas (66) and ( 67 ), R6, Rll and Y are :
as defined above, the groups Y may be the same or
different and at least one of Y is a hydrogen atom, a
hydroxyl group or a hydrolyzable group.
Specific examples of the compounds of the
~ 21229~5
- 58 -
formulas (66) and (67) are those represented by the
following formulas.
CH2 = CH- Si(OCH3 ) 3
CH2 = CH- Si (OC 2 H 5 ~ 3
CH2 =CH - Si (OCH3 ) 2 CH3
CH2 = CH- Si (CH3 ) 2 OCH3 :~ ~
CH2 = CH - CH2 Si (OCH3 ) 3 :~::
CH2 = CH- Si(OCOCH3 ) 3
CH2 - CH- CH2 Si (OCOCH3 ) 3
CH2 = CH- Si (CH3 ) 2 N (CH3 ) 2
CH~ CH3 0
11
CH2=CH Si~ ~ ~H3
CH2=CH Si (~ ) 20N (CH3) 2
2~ 2~9~5
- 59 -
Examples of silane-containing polymerizable
unsaturated monomer (g) having radically polymerizable
unsaturated group of the formula CH2=CHO- include the
compounds represented by the formulas (68) and (69).
CH2=CHO-R1~-Si-Y (68)
y
Y
CH2=CHO-Si-Y (69)
Y
In the foregoing formulas, Rll and Y are as
defined above, the groups Y may be the same or different
and at least one of the groups Y is a hydrogen atom, a
hydroxyl group or a hydrolyzable group.
Specific examples of the compounds represented
by the formulas (68) and (69) are following compounds.
CH3 O
11
CH2=CHO-(CH2)3Si--NCCH3
CH3 H
CH3
I
CH2=CHO-(CHz)zSi-OCH3
OCH3
~22985
~ 60 ~
CH3 CH3
CH2=CHO-Si-O-N -
CH3 CH3
CH3 C2Hs
CH2=CHO-Si-ON
CH3 C2Hs
Examples of silane-containing polymerizable
unsaturated monomer (g) having radically polymerizable
unsaturated group of the formula CH2=CHCH20- include the
., compounds of the following formulas (70) and (71).
~ CH2=CHCH20-Si-Y (10~
~,
~-.
,'' ''. -:
2 ;~ 2 9 ~
CHz =CHCH20-R~- Si -Y (71)
Y ',,
In the foregoing formulas (70) and (71), Rll and
Y are as defiend above, the groups Y may be the same or
different and at least one of the groups Y is a hydrogen
atom, a hydroxyl group or a hydrolyzable group.
Specific examples of the compounds of the-
formulas (70) and (71) include those represented by the
following formulas.
C2Hs CH3
CH2=CHCH20-Si-N
~ CH3
r
CH2=CHCH20-Si-NCC2Hs
~ H
2 1 ~ 2 9 ~ a ~ ~
~ 62 -
OCH3 0
11
CHz=CHCH20~(CH2~3~Si--~CCzHs
OCCH3
o
OC2Hs
CHz=CHCH20- (CH2) z-Si-OC2Hs
CH3
In addition to the silane group-containing poly-
merizable unsaturated monomer (9), a polysiloxane
unsaturated monomer containing silane group and
polymerlzable unsaturated group and prepared by reacting
the silane group-containing polymerizable unsaturated
monomer (9) with, for example, a polysilane compound (e.g.
compounds represented by the formulas (59) to (61)). ~-~
Representative of the polysiloxane unsaturated
monomer is a polysiloxane macromonomer produced by
reacting about 30 to about 0.001 mole% of a compound of;~
the formula (62) and about 70 to about 99.999 mole~ of at
least one of the compounds of the formulas (59) to (61)
(for example those disclosed in Japanese Unexamined Patent
Publication No. 275132/1987). Also useful as the
polysiloxane unsaturated monomer are the compounds
represented by the following formulas.
2~ 2298~
- 63 - -
CH3 OCH3
CH2=C (CH3!-COOC3H6-Si-O-Si-OCH3
CH3 OCH3
CH3 OCH3
CH2=CH COOC3H6Si-O-Si-OCH3
CH3 OCH3
CH3 OCH3 O
11 , '
CH2-C ~CH33Coo-CH2-~Si-O).~ Si -OCCH3 - :
1 0
CH3 1 .
OCCH3
CH,=C (CH, ~ I -Ot,-o-~i_N<
¦ CH,=CH~ O~ -O~i-O-N<
CH3 ~ 1~
CH2=cHcH~ O ~ ~i-OCCH~
CH3 11
' OCCH3
'e
2~2~ ~
~ 64 --
CH3 ICH3 C2Hs
CH2=CHO~7 i--~7~1 i--ON<
CH3 CH3 C2Hs
00
CH2=CHCH20~'- i -O~S i--NHCC2H~
~) ~
O C2Hs O C2Hs : ~ -~
CH2=CHCH20-C2H.~ O~I i--OC2Hs
CH3 CH3
3) A reaction product prepared by reacting the
foregoing hydroxyl-containing compound (A-l) with a
compound containing isocyanato group and silane group in
the molecule such that the resulting reaction product will ~ ;
have no isocyanato group.
Examples of the compound containing isocyanato
group and silane group (i.e., isocyanato-containing silane
compound) are represented by the formulas (72) and (73).
2~9~'~
- 65 -
OCN-R8-Si Y (72)
y
Y ,, -.
OCN-Si-Y (73)
Y
In the foregoing formulas, R6 and Y are as
defined above and the groups Y are the same or different,
and at least one of the groups Y is a hydrogen atom, a
hydroxyl group or a hydrolyzable group.
Examples of the compounds of the formula (72)
and (73) are those represented by the following formulas.
OCNClH6Si (OCzHs) 3
OCNCzH~Si rOCH3) 3
OCNC3H6Si (OC2Hs) z
CH3
OCNCzH~Si lOCH3) 2
I
CH3
,
.,
2~229~
- 66-
OCNCH2Si(OC2Hs)3
OCNCHzSi(OCH3)3
OCNCH2Si(OC2Hs)2
CH3
OCNCH2Si(OCH3)3 -~ ;
OCNCH2Si(OC2Hs)2
'
~ . ';
OCNCH2Si(OCH3)
CH3
OCN-C3H6-SiN-(C2Hs) 2
CH3 :
CH3 C3H~
OCN-C3H6 - SiN~
~ C2~s
'~
- 67 2~29~'
CH3 C2Hs
OCN-C3H 6 -Si -O-N
CH3 CzHs
CH3
I
OCN-C3H6-SiON(C3H7)~
CH3
OCN-C3H6-Si(OCCH3)3
CH3 O
1 11
OCN~C~Hs~Si~OCCH3
~3
OCN-Si(OCH3) 3
o
OCN-SilOCCH3) 3
OCCH3
11
OCN Si OCC4Hs
l O
O-CCH3
2 ~ ~ ~ Q ,~ ~3
-- 6 8 --
.
Also usable as the isocyanato-containing silane
compound is a compound preparecl by reacting a hydroxyl-
containing silane compound to be described later with the
foregoing polyisocyanate compound.
Examples of such isocyanato-containing silane
compound include a reaction product of such a hydroxyl-
containing silane compound and hexamethylene diisocyanate
or tolylene diisocyanate, such as products represented by
the following formulas.
~ CH3
OCN~CH2~NHCO-C3Hc-~i-NCCH3 ~-
'~ ~
O CN~NHCO--C4Ho--~i--ON<
ON~ -
CH3
,- .~
Useful isocyanato-containing silane compounds
further include a condensation product of the above
isocyanato-containing silane compound with, e.g. the
foregoing polysilane compound, such as one represeted by
the following formula.
., .
21229~5
- 69 -
~ CH3 OCCH3 O
OCN-C3H6-~Si-O ~ Si-O ~Sl OCCH3
~ OCCH3
(ii) Fluorine-containing silane compound (C)
Examples of silane group-containing compound (C3
that contains fluorine are those described below.
1) A reaction product of the foregoing hydroxyl-
containing compound (A-2~ ~ith the above polysilane
compound.
2) A reaction product of the foregoing hydroxyl-
containing compound (A-2) with the above isocyanato-
containing silane compound.
3) A reaction product of a hydroxyl-containing silane
compound with a copolymer comprising as monomer components
a fluorine-containing polymerizable unsaturated monomer
(c), an isocyanato group-containing polymerizable
unsaturated monomer (e) and if desired another
polymerizable unsaturated monomer (b).
Examples of such hydroxyl-containing silane
compound are those represented by the formulas (74) to
(76).
2l2298~
- 70 ~
Y .
H o - R 3 - S i - Y ( 7 ~
Y ';,,' ', ~
O O Y -~: ~
Ho-R8-oC-NH-R~1-NH-C-NH-R11-$i-Y (75)
O Y
HO-R3-co-R8-si-y (76)
In the formulas, R8, Rll and Y are as defined
above; the groups R8 are the same or different, the groups
Rll are the same or different, and the groups Y are the ~ ::
same or different, provided that at least one of the :~
groups Y is a hydrogen atom, a hydroxyl group or a
hydrolyzable group.
Specific examples of the compounds of the ~
formulas (74) to (76) are those represented by the :::
followin~ formulas.
OCH3
HO-(CHz~3-Si-OCH3
OCH3
2l2~985
O H O H CH3 CH3
Il H I O I I /
HO-(CH2)z-OC-N-(CH2)6-N-C-N-(CH2)3-Si-ON=C
C~3 CH3
O CH3
Il I o
HO-(CH2)z-O-(CHz)z-C-O-(CHz)3-Si-OCCH3
OCCH3
o
4) A copolymer comprising as monomer components the
foregoing fluorine-containing polymerizable unsaturated
monomer (c), silane group-containing polymerizable
unsaturated monomer (g) and when required another
polymerizable unsaturated monomer (b).
s) A reaction product prepared by reacting a mercapto-
containing silane compound with a copolymer comprising as -~
monomer components fluorine-containing polymerizable
unsaturated monomer (c), epoxy-containing polymerizable
~i ,
unsaturated monomer (f) and if required another -~
polymerizable unsaturated monomer (b) such that the
resulting reaction product will have no epoxy group.
Examples of the above mercapto-containing silane
compound are those represented by the following formulas.
:
r
.
i,~,
i~
. . ,,.~, .. .
7~22~
~C2H5
HS-C3H6-''i-0C4Hg
OC2H5
O
Hs-c3H6-li(OccH3)2
CH3
CH3
HS-C4H8-'-i-ON ~ 2 5
C2H5
Invention 2
The epoxy- and silane group-containing compound
(D) for use in Invention 2 of the present invention has in
the molecule at least two, preferably 2 to 300, epoxy
groups on the average and at least one silane group on the
average. Compounds having epoxy groups or silane groups
less than the above range in number are undersirable since -~
lower curability (gel fraction ratio) will then result.
On the other hand, with an increase in the number of
silane groups as already stated, epoxy groups are
consumed, decreasing the amount of epoxy groups needed for
the curing reaction with hydroxyl groups and impairing the
curability of the resin composition. It is therefore
desired that up to 2,500 silane groups be present in the
molecule on the average. The compound (D) is preferably
21229~
- 73 -
1,000 to 200,000, more preferably 3,000 to 80,000, in
number average molecular weight. If the molecular weight
is less than 1,000, the resulting coating is inferior in
curability, weather resistance, etc., whereas if it is
over 200,000, the compound is less compatible with other
components and is therefore undesirable.
(i) Fluorine-free compound (D)
Examples of fluorine-free compound (D) include
the compounds as described in the following items 1) to
3).
1) Copolymers comprising as monomer components
thereof silane group-containing polymerizable unsaturated
monomer (9), epoxy-containing polymerizable unsaturated
monomer (f) and, when required, another polymerizable
unsaturated monomer (b).
2) Reaction products of hydroxyl-containing
compound (A-l), the aforementioned isocyanato-containing
epoxy compound and the aforementioned isocyanato-
containing silane compound.
3) Compounds represented by the formula (77) or
(78).
2122~
74
(:: H 2 ~
O
R6 --C
C H2
O (77)
R 1l
Y ~--S i --R 9
R 9
(~ (78)
R ~l
Y~ S i --R 9
R9
wherein R6, R9, Rll and Yrare each as defined above, and
the two groups R9 may be the same or different.
Examples of compounds represented by the above
formulae are y-glycidoxypropyltrimethoxysilane,
glycidoxypropyltriethoxysilane, y-glycidoxypropyl-
triacetoxysilane, glycidoxyethyltrimethoxysilane, B-
glycidoxyethyltriethoxysilane, B-(3,4-epoxycyclohexyl)-
ethyltrimethoxysilane, B-(3l4-epoxycyclohexyl)eth
~ triethoxysilane, B-(3,4-epoxycyclohexyl)ethyltriacetoxy-
silane, y-(3,4-epoxycyclohexyl)propyltriethoxysilane and
:.
, .
. .,
.. , :
2l229~
- 75 -
the like.
(ii) Fluorine-containing compound (D)
Examples of fluorine-containing compounds (D)
include the compounds of the following items 1) and 2).
1) Copolymers comprising as monomer components
thereof silane group-containing polymerizable unsaturated
monomer (g), epoxy-containing polymerizable unsaturated
monomer (f), fluorine-containing polymerizable unsaturated
monomer (c), and, when required, other polymerizable
unsaturated monomer (b).
2) Reaction products of hydroxyl-containing
compound (A-2), the aforementioned isocyanato-containing
epoxy compound and the aforementioned isocyanato-
containing silane compound.
Examples of hydroxyl group-containing compounds
(A) which can be used are the same as those of fluorine-
free hydroxyl-containing compounds (A-l) and fluorine- and
hydroxyl-containing compounds (A-2) already mentioned.
Invention 3
The hydroxyl- and silane group-containing
compound (E~ for use in Invention 3 of the present
invention has in the molecule at least two hydroxyl groups
on the average and at least one silane group on the
average. Compounds having hydroxyl groups of silane
groups less than the above range in number are undesirable
, r;
ff;~ ;.,' r.~ "~." ,
~2~
- 76 -
since lower curability (gel fraction ratio) will then
result. From the viewpoint of weather resistance, water
resistance, etc., up to 400 hydroxyl groups are preferably
present in the molecule. Further up to 2,500 silane
groups are preferably present in the molecule in view of
curability (gel fraction ratio). The compound (E)
preferably has a number average molecular weight of 1,000
to 200,000, more preferably 3,000 to 80,000. If the
molecular weight is less than 1,000, the resulting coating
is inferior in weather resistance, whereas if it is over
200,000, the compound (E) i5 less compatible with other
components and therefore undesirable.
(i) Fluorine-free compound (E)
Examples of fluorine-free compounds (E) include
.~
the following compounds.
1) Copolymers comprising as monomer components
thereof hydroxyl-containing polymerizable unsaturated
monomer (a), silane group-containing polymerizable
unsaturated monomer (g) and, when required, other
polymerizable unsaturated monomer (b).
2) Products obtained by reacting hydroxyl-
containing compound (A-l) with the isocyanato-containing
silane compound described hereinbefore so that the product
contains in the molecule at least two hydroxyl groups and
at least one silane group on the average.
. , .
- 2122~8~
- 77 -
.
(ii) Fluorine-containing compound (E)
Examples of fluorine-containing compounds (E)
include the following compounds.
1) Copolymers comprising as monomer components
thereof hydroxyl-containing polymerizable unsaturated
monomer ta), silane group-containing polymerizable
unsaturated monomer (9), fluorine-containing polymerizable
unsaturated monomer Ic~ and, when required, other
polymerizable unsaturated monomer ~b).
2) Products obtained by reacting hydroxyl-
containing compound (A-2) with the isocyanato-containing
silane compound described above so that the product ~
contains in the molecule at least two hydroxyl groups and -
at least one silane group on the average.
Examples of compounds ~B) usable are the same as ~ -
those already mentioned.
Invention 4
The hydroxyl- and epoxy-containing compound (F)
for use in Invention 4 of the present invention has in the
molecule at least 2 hydroxyl groups on the average and at
least 2, preferably 2 to 300, epoxy groups on the
average. Compounds having hydroxyl groups and silane
groups less than the above range in number are undesirable
since lower curability (gel fraction ratio) will then
result. In view of weather resistance, water resistance,
2f 22~8~
etc., it is desirable that up to 2,500 hydroxyl groups be
present in the molecule. The compound (F) has a number
average molecular weight of 1,000 to 200,000, preferably
3,000 to 80,000. If the molecular weight is less than
1,000, the resulting coating is inferior in weather
resistance, whereas if it is over 200,000, the compound
(F) is less compatible with other components and therefore
undesirable.
(i) Fluorine-free compound (F)
Examples of fluorine-free compounds (F) include
the following compounds.
1) Copolymers comprising as monomer components
thereof hydroxyl-containing polymerizable unsaturated
monomer (a), epoxy-containing polymerizable unsaturated
monomer (f) and, when required, other polymerizable
unsaturated monomer (b).
2) Products obtained by reacting hydroxyl-
containing compound (A-13 with the aforementioned
isocyanato-containing epoxy compound so that the product
contains in the molecule at least 2 hydroxyl groups and at
least 2 epoxy groups on the average.
(ii) Fluorine-containing compound (F)
Examples of fluorine-containing compounds (F)
include the following compounds.
1) Copolymers comprising as monomer components
212298~
- 79 -
hydroxyl-containing polymerizable unsaturated monomer (a),
epoxy-containing polymerizable unsaturated monomer (f),
fluorine-containing polymerizable unsaturated monomer tc)
and, when required, other polymerizable unsaturated -
monomer (b).
2) Products obtained by reacting hydroxyl-
containing compound (A-2) with the aforementioned
isocyanato-containing epoxy compound so that the product
has in the molecule at least 2 hydroxyl groups and at
least 2 epoxy groups on the average.
With Invention 4, compound ~C) are those already
described above with respect to Invention 1.
The components described hereinbefore can be
prepared by conventional methods. More specifically the
reaction between hydroxyl and isocyanato groups,
condensation reaction of silane group, copolymerization
reaction and the like can be conducted in conventional
manner. For example, the reaction between isocyanato
group and hydroxyl groups can be effected at a temperature
between room temperature and 130~C for about 30 to about
360 minutes. The condensation reaction of silane group is
conducted in the presence of an acid catalyst (for
example, hydrochloric acid, sulfuric acid, formic acid,
acetic acid or the like) with heating at a temperature of
about 40 to about 150~C for about 1 to about 24 hours. ~ ~
' :
''~
.~ ..
" 2l 2298~ ':
- 80 -
The copolymerization reaction is carried out in the same
manner under the same condictions as the reaction for
synthesis of acrylic or vinyl resins. Such synthetic
reaction can be carried out, for example, by dissloving or
dispersing the monomer components in an organic solvent
and heating the solution or dispersion in the presence of
a radical polymerization initiator at a tempera~ure of
about 40 to about 180~C with stirring. The reaction time
usually ranges from about 1 to about 24 hours. Useful
organic solvents include those conventionally used and
inactive to the monomer or the compound used, such as
ether solvents, ester solvents or hydrocarbon solvents.
The hydrocarbon solvent is preferably used in combination
with a different solvent in view of its dissolving
ability. The radical polymerization initiator can be any
of polymerization initiators conventionally employed and
including peroxides such as benzoyl peroxide and t-butyl
peroxy-2-ethylhexanoate and the like and azo compounds
such as azobisisobutyronitrile,
azobisdimethylvaleronitrile and the like.
In the resin compositions of the invention,
components having introduced therein alicyclic epoxy group
accelerate the addition reaction of the epoxy group with
hydroxyl group, giving a coating with improved curability.
In preparation of resin compositions, the use of
- 8~122~
the monomer of the formula (5) as the fluorine-containing
polymerizable unsaturated monomer (c) provides a polymer
with fluorine atoms attached to the main chain, giving a
coating enhanced in resistance to weather, acid resistance
and other properties. The use of the monomer of the
formula (6) affords a polymer with the fluorine atoms
attached to the side chain which atoms serve to exhibit
remarkable water repellency and resistance to staining.
As to the fluorine content, each of the resin
compositions of the invent on (Inventions 1 to 4) may
contain fluorine-containing polymerizable unsaturated
monomer (c) as monomer component in an amount of about 1
to about 70% by weight, preferably about 5 to about 60% by
weight, based on the total weight of the components of the
composition (i.e., based on the non-volatile content).
The resin composition with a fluorine content less than
said range gives a coating having low resistance to
scratching, staining, weather and acids. On the other
hand, the resin composition with a fluorine content ~ ~
exceeding said range incurs a higher production cost and ~ ;
is difficult to manufacture.
The resin compositions of the invention are
usually used as dissolved or dispersed in a solvent
including hydrocarbon solvent such as toluene and xylene,
ketone solvent such as methyl ethyl ketone and methyl
'
- 822l?29~
isobutyl ketone, ester solvent such as ethyl acetate and '
butyl acetate, ether solvent such as dioxane and ethylene
glycol diethyl ether, alcohol solvent such as butanol and
propanol, etc.
The curable composition of the invention
comprises each of the resin compositions (Inventions 1-4)
of the invention and a metal chelate compound as a curing
catalyst.
Useful metal chelate compounds include, for
example, aluminum chelate compounds, titanium chelate
compounds and zirconium chelate compounds. Among these
chelate compounds, those containing, as a ligand for
forming a stable chelate ring, a compound capable of
forming a keto-enol tautomer.
Examples of the compound capable of forming a
keto-enol tautomer are B-diketones (such as acetyl
acetone), esters of acetoacetic acids (such as methyl
acetoacetate), esters of malonic acids (such as ethyl
malonate), ketones having hydroxyl group in the ~-position
(such as diacetone alcohol), aldehydes having hydroxyl
group in the B-position ~such as salicylaldehyde), esters
having hydroxyl group in the ~-position (such as methyl
salicylate), etc. The use of esters of acetoacetic acids
or esters of ~-diketones can achieve desirable results.
The aluminum chelate compound can be suitably
, Y&:,,.,.-, ~,, , ", ,~ ,",, ~ "~ ,"" ~ , "~,"; ;,~ " ,~ ,,, " ", ~ ," ~ , "~
::' 2122~5 ~:
- 83
prepared for example by admixing the comound capable of
forming a keto-enol tautomer with an aluminum alkoxide
represented by the formula
o R12
(79)
R 12 0 - A Q ~ O R 12
wherein the groups Rl2 are the same or different and each
represent an alkyl having l to 20 carbon atoms or alkenyl
group usually in a ratio of about l to 3 moles of the
former per mole of the latter, followed by heating the
mixture when so required.
Examples of the alkyl group having l to 20
carbon atoms are undecyl, dodecyl, tridecyl, tetradecyl,
octadecyl and the like as well as the above alkyl groups
having l to lO carbon atoms. Examples of the alkenyl
group are vinyl, allyl and the like. ~-
Examples of the aluminum alcoholate having the
formula (79) are aluminum trimethoxide, aluminum
triethoxide, aluminum tri-n-propoxide, aluminum -
triisopropoxide, aluminum tri-n-butoxide, aluminum
triisobutoxide, aluminum tri-sec-butoxide, aluminum tri-
tert-butoxide and the like. Among them, preferable are
aluminum triisopropoxide, aluminum tri-sec-butoxide,
aluminum tri-n-butoxide, etc. -~
The titanium chelate compound can be suitably
"~ ~ ,,,", , ~,,",""~ "; ,~ , :"
~ 2~22~8~
. - 8~ -
'r prepared, for example, by mixing the compound capable of
forming a keto-enol tautomer with a titanate represented
by the formula
/0 Rl2 \ O R12
R 12 o-- ¦ i --O -- T i --O R 12 ( 8 o
~O R 12 /w O R 12
wherein w is an integer of 0 to 10, and R12 is as defined
above, usually in a ratio of about 1 to 4 moles of the
former per mole of the Ti in the titanate, followed by
. heating when so required.
Examples of the titanate of the formula (80)
wherein w is 0 are tetramethyl titanate, tetraethyl
titanate, tetra-n-propyl titanate, tetraisopropyl
titanate, tetra-n-butyl titanate, tetraisobutyl titanate,
tetra-tert-butyl titanate, tetra-n-pentyl titanate, tetra~
n-hexyl titanate, tetraisooctyl titanate, tetra-n-lauryl
titanate, etc. Suitable results can be achieved by use of
tetraisopropyl titanate, tetra-n-butyl titanate, tetra-
isobutyl titanate, tetra-tert-butyl titanate and the
like. Of the titanates wherein w is 1 or more, those
which can achieve good results are dimers to hendecamers
~w = 1 to 10 in the formula ~80)) of tetraisopropyl
' titanate, tetra-n-butyl titanate, tetraisobutyl titanate,
' i~5
.
,~1229~
- 85 -
tetra-tert-butyl titanate and the like.
The zirconium chelate compound can be suitably
prepared, for example, by mixing the compound capable of
forming a keto-enol tautomer with a zirconate represented
by the formula
/0 R~2 \ O R12
R12 C)--Z r --O -- Z r --O Rl2 (8 1 )
\0 R 12 /W O R 12
wherein w and Rl2 are as defined above usually in a ratio
of about l to 4 moles of the former per mole of the Zr in
the zirconate, followed by heating when so required.
Examples of the zirconate represented by the ~;
formula (81) are tetraethyl zirconate, tetra-n-propyl
zirconate, tetraisopropyl zirconate, tetra-n-butyl
zirconate, tetra-sec-butyl zirconate, tetra-tert-butyl
zirconate, tetra-n-pentyl zirconate, tetra-tert-pentyl
zirconate, tetra-tert-hexyl zirconate, tetra-n-heptyl ~-~
zirconate, tetra-n-octyl zirconate, tetra-n-stearyl ~;~
zirconate and the like. Desirable results can be obtained
:
by tetraisopropyl zirconate, tetra-n-propyl zirconate, '
tetraisobutyl zirconate, tetra-n-butyl zirconate, tetra-
1~ ' ' - ~
sec-butyl zircoante, tetra-tert-butyl zirconate or the
like. Of the zirconates wherein w is l or more, those
which can produce desirable results are dimers to
;:::
~ .
'~ ~
- 86 -
hendecamers (w = 1 to 10 in the formula (81)) of
tetraisopropyl zirconate, tetra-n-propyl zirconate, tetra-
n-butyl zirconate, tetraisobutyl zirconate, tetra-sec-
butyl zirconate, tetra-tert-butyl zirconate and the
like. The chelate compound may contain structural units
wherein such zirconates are associated with each other.
Examples of preferred chelate compounds for use
in the invention are aluminum chelate compounds such as
tris(ethylacetoacetate)aluminum, tris(n-propyl-
a-etoacetate)aluminum, tris(isopropylacetoacetate)-
aluminum, tris(n-butylacetoacetate)aluminum,
isopropoxybis(ethylacetoacetate)aluminum, diisopropoxy-
ethylacetoacetate aluminum, tris(acetylacetonato)aluminum,
tris(propionylacetonato)aluminum, diisopropoxypropionyl-
acetonato aluminum, acetylacetonato-bis(propionyl-
acetonato)aluminum, monoethylacetoacetate-bis(acetyl-
acetonato)aluminum, tris(acetylacetonato)aluminum and the
like; titanium chelate compounds such as diisopropoxy-
bis(ethylacetoacetate)titanate, diisopropoxy-bis(acetyl-
acetonato)titanate, diisopropoxy-bis(acetylacetonato)-
titanate and the like; and zirconium chelate compounds
such as tetrakis(acetylacetonato)zirconium, tetrakis(n-
propylacetoacetate)zirconium, tetrakis(acetyl-
acetonato)zirconium, tetrakis(ethylacetoacetate)zirconium
and the like.
27~-?~
~ he aluminum chelate compounds, zirconium
chelate compounds or titanium chelate compounds can be
used singly or at least two of them are usable in mixture.
With respect to the resin composition according
to Invention 1, hydroxyl group-containing compound (A) is
used in an amount of 5 to 95% by weight, preferably 20 to ~-
80% by weight, and epoxy group-containing compound (B) is
used in an amount of 95 to 5% by weight, preferably 80 to
20% by weight, each based on the total amount of hydroxyl
group-containing compound (A) and epoxy group-containing
compound (B) combined. If the proportions of these
components are outside the above respective ranges,
curability at low temperature tends to be impaired. -~
Silane group-containing compound (C) is used in an amount
of 0.1 to 150 parts by weight, preferably 1 to 100 parts
by weight, based on 100 parts by weight of the total
amount of hydroxyl group-containing compound (A) and epoxy
group-containing compound (B) combined. If the amount of
silane compound (C) is less than 0.1 part by weight,
curability of the resulting composition tends to
drastically decrease. If the amount of silane compound
(C) is more than 150 parts by weight, excess silane -;~
compound (C) that remains in the resulting composition ~-
tends to reduce the solvent resistance of the resulting ~-
coating. In the curable composition containing the above
~2~98~
- 88 -
resin composition, the amount of the metal chelate compound
is about O.01 to 30 parts by weight, preferably O.1 to 5
parts by weight, per 100 parts by weight of the total amount
of hydroxyl group-containing compound (A), epoxy group-
containing compound (B) and a compound (C) containing
hydrolyzable group directly attached to silicon atom and/or
silanol group. If the amount of the metal chelate compound
is less than 0.01 part by weight, curability of the
resulting composition is reduced. If the amount is more
than 30 parts by weight, the resulting coating tends to have
insufficient water resistance.
With respect to the resin composition according
to Invention 2, the amount of hydroxyl group-containing
compound (A) is 5 to 95% by weight, preferably 20 to 80%
by weight, and the amount of epoxy group- and silane
group-containing compound (D) is 95 to 5~ by weight,
preferably 80 to 20% by weight, each based on the total
amount of hydroxyl group-containing compound (A) and
epoxy group- and silane group-containing compound (D)
combined. If the proportions of these components are
outside the above respective ranges, the resulting
composition tends to have reduced curability, especially
at low temperature. In the curable composition containing
the above resin composition, the amount of the metal
chelate compound is about 0.01 to 30 parts by weight,
preferably 0.1 to 5 parts by weight, per 100 parts by
21 22 9 ~ ~ ~
- 89 -
weight of the total amount of hydroxyl group-containing ~ -
compound (A) and epoxy group- and silane group-containing
compound (D) combined. If the amount of the metal chelate
compound is less than 0.01 part by weight, curability of
the resulting composition is reduced. If the amount is
more than 30 parts by weight, the resulting coating tends
to have insufficient water resistance.
With respect to the resin composition according
to Invention 3, the amount of hydroxyl group- and silane
group-containing compound (E) is 5 to 95% by weight,
preferably 20 to 80~ by weight, and the amount of epoxy
group-containing compound (B) is 95 to 5% by weight,
preferably 80 to 20% by weight, each based on the total
amount of hydroxyl group- and silane group-containing
compound (E) and epoxy group-containing compound (B)
combined. If the proportions of these components are
outside the above respective ranges, the resulting -
composition tends to have reduced curability, especially
at low temperature. In the curable composition containing
the above resin composition, the amount of the metal
chelate compound is about 0.01 to 30 parts by weight, -
preferably 0.1 to 5 parts by weight, per 100 parts by
weight of the total amount of hydroxyl group- and silane -
group-containing compound (E) and epoxy group- containing
compound (B) combined. If the amount of the metal chelate
~ ..
:
2~22~8~
- 9o -
compound is less than 0.01 part by weight, curability of
the resulting composition is reduced. If the amount is
more than 30 parts by weight, the resulting coating tends
to have insufficient water resistance.
With respect to the resin composition according
to Invention 4, the amount of hydroxyl group- and epoxy
group-containing compound tF) is 5 to 95% by weight,
preferably 20 to 80% by weight, and the amount of silane
group-containing compound (C) is 95 to 5~ by weight,
preferably 80 to 20% by weight, each based on the total
amount of hydroxyl group- and epoxy group-containing
compound (F) and silane group-containing compound ~C)
combined. If the proportions of these components are
outside the above resp~ctive ranges, the resulting
composition tends to have reduced curability, especially
at low temperature. In the curable composition containing
the above resin composition, the amount of the metal
chelate compound is about 0.01 to 30 parts by weight,
preferably 0.1 to 5 parts by weight, per 100 parts by
weight of the total amount of hydroxyl group- and epoxy
group-containing compound (F) and silane group-containing
compound ~C) combined. If the amount of the metal chelate
compound is less than 0.01 part by weight, curability of
the resulting composition is reduced. If the amount is
more than 30 parts by weight, the resulting coating tends
'~
~;
- 91 _ 2~229~
to have insufficient water resistance.
The curable composition of the present invention -~
may contain the above-mentioned chelating agent,
preferably an ester of acetoacetic acid, B-diketone or
like compounds to improve the storage stability.
The coating composition of the invention as
mixed with known additives selected as required are usable
as a topsoat and/or intercoat composition for coating
automotive body panels.
When the coating composition of the invention is
used as a topcoat composition, for example as a topcoat
solid-color composition, a clear topcoat composition in
two-coat one-bake coating methods or a topcoat composition
in three-coat two-bake coating methods, suitable
proportions of the components are about 100 parts by
weight of a base resin ti-e., resin composition according
to Invention 1, 2, 3 or 4), about 0.1 to about 30 parts by
weight of a metal chelate compound and 0 to about 100
parts by weight of a coloring pigment. Useful coloring
pigments can be an inorganic or organic coloring pigment
of high weatherability conventionally used in topcoat
compositions for coating automotive body panels. Among
useful coloring pigment are inorganic pigments such as
rutile-type titanium oxide, carbon black and the like and
organic pigments such as ~uinacridone red pigment or like -
. .. . . . . . . . . . . . . . . . . . . . .. . . . . . . .
21~
- 92 -
quinacridone-type pigments, pigment red and like azo-type
pigments, phthalocyanine blue, phthalocyanine green and
like phthalocyanine pigments, etc. When used as a clear
coating co~position in two-coat one-bake coating methods,
the coating composition of the invention may be used
without a coloring pigment.
When the coating composition of the invention is
used as a base coat composition in two-coat one-bake
method or as a metallic coating composition in one-coat
one-bake coating method, suitable proportions of the
components are about 100 parts by weight of a base resin,
about 0.1 to about 30 parts by weight of a metal chelate
compound, about 2 to about 36 parts by weight of a
metallic pigment and 0 to about 40 parts by weight of a
coloring pigment. Useful metallic pigments can be
conventional ones including flaky metallic powders such as
powders of aluminum, copper, micaceous iron oxide, bronze,
stainless steel or the like. The coloring pigment for use
herein can be any of those exemplified hereinbefore.
Further, the coating composition may contain up to about
20 parts by weight of an acrylic dispersion having the
core crosslinked by heterogeneous polymerization and
obtained by known methods or cellulose acetate butylate as
a modified resin for rheology control useful for improving
the metallic effect by adjusting the arrangement of
.. . .
'.,' / ' ' ' . ~ '.' ' ' '
2l22~8~ -
- 93 -
~.
metallic pigment.
For use as an intercoat composition for coating
automotive body panels, suitable proportions of the
components in the coating composition of the invention are
about lO0 parts by weight of a base resin, about 0.1 to
about 30 parts by weight of a metal chelate compound, and
about 5 to about 150 parts by weight of a pigment. Useful
pigments are titanium oxide, barium sulfate, calcium
carbonate, clay and like inorganic pigments and organic
pigments for coloration.
When required, the coating composition of the
invention, especially the coating composition comprising
the resin composition of Invention 2 or 4, may incorporate
a low-molecular weight compound of up to 2,000 in number
average molecular weight which contains at least two
alicyclic epoxy groups per molecule. Such low-molecular
weight compound acts as a reactive diluent. When mixed
with the coating composition, the compound can lo~er the
viscosity of the composition, thus increasing the solids
content thereof. Further the composition forms small
quantities of by-products during curing. Therefore, there
can be provided a high solid coating composition which is
uniformly curable and excellent in other properties.
Moreover, the resulting coat is less susceptible to
shrinkage during curing and outstanding in surface
2.a22~
- 94 -
smoothness.
Useful compounds having at least two alicyclic
epoxy groups per molecule and a number average molecular
weight of up to 2000 can be sellected from epoxy group-
containing compound ~B).
It is important that the low-molecular weight
compound having at least two epoxy groups per molecule
have a number average molecular weight of less than 2,000,
preferably 160 to 1,000. The compounds of more than 2000
in number average molecular weight have a low
compatibility with the base resin used, consequently
failing to give a coat excellent in finishing properties
and film properties.
A suitable amount of the low-molecular weight
compound is 0 to about 100 parts by weight, preferably
about 10 to about 60 parts by weight, per 100 parts by
weight of the non-volatile content of the coating
composition.
The coating composition of the invention can be
applied as by electrostatic coating (bell type, REA type ~:
or the like), air spraying or other coating methods, using
conventional coaters or coating equipment conventionally
employed. Before use, the coating composition of the
invention is adjusted to a suitable viscosity of about 15
to about 35 seconds (Ford cup No. 4, at 20~C) for use as :
21 22 9 8 r~
- 95 -
~ .
intercoat, or about 12 to about 30 seconds (Ford cup No.
4, at 20~C) for use as topcoat. The viscosity of the
composition is suitably variable depending on the coater,
the kind of the solvent, coating conditions and the like.
The solvent for diluting the coating composition
can be any of those used for conventional coating
compositions of the acrylic resin/melamine resin type.
Specific examples of such solvent are toluene, xylene and
like hydrocarbon solvents; methyl ethyl ketone, methyl
isobutyl ketone and like ketone solvents; ethyl acetate,
butyl acetate and like ester solvents; dioxane, ethylene
glycol diethyl ether and like ether solvents; and butanol,
propanol and like alcohol solvents. While these solvents
may be used alone or in a suitable combination, alcohol
solvents are preferably used in mixture with other
solvents in view of solubility of the resin. To enhance
the curing rate, an organic solvent having a boiling point ; ;
of about 150~C or below is preferred to which, however,
useful solvents are not limited in the invention.
The coating composition of the invention is
useful as an intercoat composition and/or a topcoat
composition for example in a coating method comprising ~
electrophoretically applying a primer to a steel panel -
treated by chemical conversion, and coating the steel
panel with an intercoat composition (optionally omissible)
,."' ,
:'
~', :
'- 21229~
- 96 -
and a topcoat composition, or in a coating method
comprising applying to a substrate a primer suitable for a
plastics material, drying the coating, and applying an
intercoat composition (optionally omissible) and a topcoat
composition in this sequence.
In formation of intercoat, the coating
composition of the invention is applied to a dry film
thickness of about 25 to about 60 ~m. In formation of
topcoat, the coating composition of the invention is
applied to a dry film thickness of about 20 to about
60 ~m, preferably about 30 to about 40 ~m when used as a
solid-color coating composition in the one-coat one-bake
coating method, a metallic coating composition in the one-
coat one-bake method, a clear topcoat composition in the
two-coat one-bake method or a clear topcoat composition in
the three-coat two-bake method. The coating composition
of the invention is applied to a dry film thickness of
about 10 to about 25 ~m, preferably about 10 to about
20 ~m when used as a metallic base coat composition in the
two-coat one-bake coating method. ~ -~
The coating composition of the invention can
readily undergo curing reaction by crosslinking at a low
temperature of 140~C or lower. For example, when the
coating composition of the invention is cured at room
temperature without any heating, it can be sufficiently
2t229~5~
- 97 -
cured in about 8 hours to 7 days after application. When
the coating composition of the invention is cured by
heating at about 40 to 100~C, it can be fully cured in S
minutes to 3 hours after application.
The reason why the curable composition of the
invention has excellent curability at low temperature
would presumably be as follows. In the first step
reaction, the metal chelate compound reacts with silane
groups to form bonds of the formula
, A Q --O--Si--
,~
and the bonds are coordinated with other silanol groups
(alkoxysilane group acyloxysilane group and the like are -
converted to silanol group by the action of moisture in
the air) to form bonds of the following formula ~-
-Si- O - H
, A Q - O -Si~
and thereby to polarize the silanol groups. The polarized
silanol groups then react with epoxy groups to form a
structure of the formula
I e
- si - o - c - c -
\O
H
2~2~98~
- 98 -
and this structure reacts with hydroxyl groups to form a
structure of the formula
I
- C - O - C - C -
O H
and this reaction between the above structure and hydroxyl
group proceeds at a relatively low temperature.
It is presumed that since the curable
composition of the invention contains a hydroxyl group
containing compound as one of the essential components and
further contains epoxy groups, silane groups and a metal
chelate compound, the above reactions quickly proceed,
whereby the resin composition of the invention has
excellent curability at low temperatures. ;~
The fluorine component used in the curable ~-
composition of the inventio~ is poor in compatibility with
the alkoxy- and epoxy-containing components, and is
unlikely to inhibit the reaction between alkoxy and epoxy
groups, hence effective in exhibiting a high curability.
Further, the fluorine atoms chemically attached to the
cured product are chemically stable to extraneous attack
as by light, heat, water, or the like, and serve to give a
cured product which is low in surface energy.
The composition of the invention can achieve the
following remarkable results.
2~22~
- 99 -
(1) The composition of the invention gives a coat
excellent in surface smoothness and distinctness-of-image
gloss. The ionic polymerization reaction and addition
reaction predominantly takes place during the curing
reaction of the composition and only a significantly small
amount of by-products are formed. In addition, the
coating composition of the invention undergoes a low
degree of volumetric shrinkage during curing and thus can
form a coat having a surface without fine irregularities,
namely a high grade of surface smoothness, hence excellent
in distinctness-of-image gloss.
(2~ The composition of the invention is of the one-
package type and has an excellent low temperature
curability. The composition of the invention is
satisfactorily crosslinkable at a temperature of about
80~C when baked for 30 to 40 minutes.
(3) The composition of the invention which is of the
one-package type is stable as a coating material and low
in toxicity.
(4) The coat formed from the composition of the
invention is excellent in acid resistance by the fluorine
component and polysiloxane bond in the base resin.
(5) The coat formed from the composition of the
invention have an excellent resistance to staining. Thus,
the coating formed from the composition of the invention
2~22~
- 100 --
is highly resistant to pollutants due to various factors
including a high density of crosslinking and high water
repellency caused by the polysiloxane bonds and fluorine
component present in the base resin.
(6) The coat formed from the composition of the
invention is outstanding in water repellency. Because of
the polysiloxane bonds and the fluorine component present
in the base resin, the resin has a high hydrophobicity and
a good water repellency. In particular, the fluorine
component present at the side chain of the base resin
reduces the surface energy of the coat, thereby providing
the coating with a high water repellency over an
automotive body panel.
(7) The coat formed from the composition of the
invention is outstanding in scratching resistance. The
coat of the composition of the invention has a high
scratching resistance because of the synergistic effect ~-
produced by high density of crosslinking and the reduction
of frictional resistance attributable to polysiloxane -
bonds and C-F bonds present in the base resin.
~8) The coat formed from the composition of the
invention has a high resistance to weather (namely free of
loss of gloss, cracking, chalking, blistering, etc.). The
coating composition applied is cured with little
difference in the degree of curing in the surface and the
i
~ ,:
- lol -2~9~
interior of the coat, leaving substantially no portion
uncured. This advantage is due to the presence of C-F
bonds excellent in chemical stability, and due to the fact
that small amounts of by-products are produced during
curing because of the concurrent occurrence of three types
j of crosslinking reactions, i.e., the ion polymerization -
reaction of epoxy groups, the addition reaction of epoxy
groups to silanol and hydroxyl groups and the condensation
reaction of silanol groups. The coat thus uniformly cured
exhibits excellent resistance to weather.
Example
For a better understanding of the present
invention, examples are given below.
First, copolymer preparation examples are given.
Preparation Example 1
Preparation of Copolymer (1)
The following monomers were placed into a 400-ml
stainless steel autoclave equipped with a stirrer.
CH2=CHO(CH2)4OH 15 parts by weight
CH2=CHO ~ 30 parts by weight
CH2=CHoc2H5 5 parts by weight
Also placed into the autoclave were the following -
compounds.
Methyl isobutyl ketone 200 parts by weight
Azobisisobutyronitrile 2 parts by weight
~: '
. 2l229~ :
- 102 -
Sodium borate 0.5 part by weight
The air in the autoclave was then replaced by nitrogen,
the contents were cooled for solidification, and the
autoclave was evacuated. Into the autoclave was
thereafter placed 50 parts by weight of CF2=CFCl, and the
autoclave was gradually heated until the internal
temperature reached 60~C. The mixture was thereafter
reacted with stirring for at least 16 hours. When the
internal pressure of the autoclave dropped to not higher
than 1 kg/cm2, the autoclave was cooled with ice to
terminate the reaction. The resulting resin solution was
placed into an excessive amount of heptane to cause a
resin to separate out, followed by washing and drying to
obtain 939 of resin. Yield 93%. The resin was 5,000 in
number average molecular weight as determined by GPC (gel
permeation chromatography). The resin obtained was
dissolved in the same amount of xylene as the resin to
obtain a resin solution containing 50% by weight of
nonvolatile component. -~
Preparation Examples 2-5
Copolymers (2) to (5) were prepared in the same
manner as in Preparation Example 1. ~able 1 shows the
amounts (parts by weight) of the monomers used, and the
number average molecular weight (Mn) of each copolymer as
determined by GPC.
-- , -
; ' ~ ~ ' . -~'
~"
- : i
:- ;~:. .
Table
~ . - ~:. ~:
'. Copolymor
( 1 ) ( 2 ~ ( 3 ) ( 4 ) ( 5 )
CHz =CHO (CH2 ) 4 OH 15
r' C H 2 = C H C H 2 O ( C H 2 ) 2 O H 10
C Hz = C H O C H2 ~o 35
C H 2 = C H C H 2 O C H z ~o 20
CH2 =CHS i (OH) (OCH3 ) z 20 o
CH2 =CHCH2 O (CHz ) 3 S i (OCOCH3 ) 3 20 ' 2~:~
' ~ '' ~' ~''I' ' ' CH2 =CEO (CH2 ) 3 S i (OCH3 ) 3 30
CHz =CHO~ 30 20 10 5
CHz =CHOCz H5 5 15
o 10
CH2 =CHOCC3 H7 10 10
: ~ . C F2 = C F C Q - 50 45 45 40 45
C F 2 = C F 2 10
M n 5000 4200 6800 5000 10500
..: .
: :~. . . :
- 104 _ ~ 22 9~ ~
Preparation Examples 6-15
Acrylic copolymer varnishes (copolymers (6) to
(15~) of the compositions listed in Table 2 below were
prepared by the usual procedure for preparing acrylic
cGpolymer varnishes. These varnishes are each in the form
of a xylene solution having a nonvolatile content of 50
wt. %. Table 2 also shows the number average molecular
weight of each varnish as determined by GPC.
- 105 - 21 ~238
Table 2
Copolymer
~6) (7) (8)
CH2 = CHCOO(CHz ) 2 OH 30
F M - 3 30
CH2 = C(CH3 )COOCHz ~ o 55
CH2 = CHCOOCH 2 ~ o
OH
1 40
~H2 - ~H~uu~H 2 - ~H ~ o
CH2 = CHCOOC2 H 4 OCONH ~ NHCOCH2 ~ o
CH2 = C(CH3 )COOCH2 CH -~CH2
o
Macromonomer B
CH2 = C(CH3 )COOC 3 H 6 - Si(OCH3 ) 3 ~ -
CH2 = CHCOOC3 H 6 - Si(N(CH 3 ) 2 ) 3 :
CH2 = CH ~ C 3 H 6 - SiON(CH 3 ) 2
(CH3 ) 2
CHz = CHCOOC3 H 6 - Si(ON(CH3 ) 2 ) 3
Styrene 15 30
n-Butyl methacrylate 10 20 40
CH2 = CHCOOCz H 4 C 8 F 17 20 10
CHz = C(CH3 )COOC 2 H 4 C 8 F ~7
M n 5000 5000 6000
~ 21229~
- 106 -
Table 2 (continued)
Copolymer
(9) (10) (11)
CH2 = CHCOO(CH2 ) 2 OH
F M - 3
CH2 = C(CH3 )COOCH2 ~ o
CH2 = CHCOOCH 2 ~ o
OH
CH2 = CHCOOCH 2 - CH ~ O
CH2 = CHCOOC2 H ~ OCONH ~ NHCOCH2 ~ O 60
CH2 = C(CH3 )COOCN2 C\H -&H2
Macromonomer B 40
CH2 = C(CH3 )COOC 3 H 6 --Si(OCH3 ) 3 20
7 ' CH2 = CHCOOC3 H 6 - Si(N(CH 3 ) 2 )
CH2 = CH--~ )-- C 3 H 6 --SiON(CH 3 ) z
(CH3 ) 2
CH2 = CHCOOC3 H 6 --Si(ON(CH3 ) 2 ) 3
Styrene 20 lD 30
; n-Butyl methacrylate 20 50 50 ~ :~
'~ CH2 = CHCOOC2 H ,I C 8 F 17 :~
CH2 = C(CH3 )COOC 2 H 4 C 8l~17
M n 5000 5500 6500 ~ -
;.' ~
', :
- 107 _ 2~ 2
Table 2 tcontinued)
Copolymer
(12) (13) (14) --:
CH2 = CHCOO(CH2 ) z OH 20
~ M - 3
CH2 = C(CH3 )COOCH2 ~ o
CH2 = CHCOOCH 2 ~ o
OH
CH2 = CHCOOCH 2 - CH - ~ O
CH2 = CHCOOC2 H 4 OCONH ~ NHCOCH2 ~ o
CH2 = C(CH3 )COOCH2 C~H - CH2 40
Macromonomer B
CH2 = C(CH3 )COOC 3 H 6 --Si(OCH3 ) 3
CHz --CHCOOC3 H 6 --Si(N(CH 3 ) 2 ) 3 20
CH2 = CH ~ C 3 H 6 --SiON(CH 3 ) 2 20
(CH3 ) 2
CH2 = CHCOOC3 H 6 --Si(ON(CH3 ) 2 ) 3 20
Styrene 2010 20
n-Butyl methacrylate 6030 40
CH2 = CHCOOC2 H 4 C 8 F 17
CH2 = C(CH3 )COOC 2 H 4 C 8 F 17
M n G500 10000 6300
- 108 - 2~ 22~5
Table 2 (continued)
Copolymer
(15~
CH2 = CHCOO(CH2 ) 2 OH -
F M - 3 40
CH2 = C(CH3 )COOCH2
CH2 = CHCOOCH 2 ~ o 40
OH : :
CH2 z CHCOOCH 2 - CH
CH2 = CHCOOC2 H ~ OCONH ~ NHCOCH2 ~ O
CH2 = C(CH3 )COOCH2 CH -/CH2 . -~
O :, -
Macromonomer B -~
CH2 = C(CH3 )COOC 3 H 6 --Si(OCH3 ) 3
~ CH2 = CHCOOC3 H 6 --Si(N(CH 3 ) 2 ) 3 ~ :~
CH2 = CH ~ C 3 H 6 - Si - ON(CH 3 ) 2
(CH3 ) 2
CH2 = CHCOOC3 H 6 --Si(ON(CH3 ) 2 ) 3 ~ -:
Styrene
n-Butyl methacrylate 20
CH2 = CHCOOC2 H 4 C 8 F 17
Cll2 = C(CH3 )COOC 2 H 4 C 8 F ~
M n 4700
. ~:
.', ,
... .
~ Z ~ r
log- ~229~
"FM-3 monomer" listed in Table 2 is a hydroxyl-
cont~ining caprolactone-modified methacrylic acid ester
(product of Daicel Ltd.), which is 472 in average
molecular weight and 119 KOH mg/g in theoretical hydroxyl
value.
As to "macromonomer B" used for preparing
Copolymer (10) in Table 2, it was prepared as follows.
Synthesis Example of Macromonomer B
Phenyltrisilanol 7800 g
~ Si(OH)3 (50 moles)
y-Acryloxypropyltrisilanol 200 9
CH2=CHCOOC3H6si(OcH3)3 ( 1 mole)
Toluene 4500 9
The mixture of above compounds was reacted at
117~C for 3 hours, and the reaction mixture was
dehydrated, giving a polysiloxane macromonomer, which was
7,000 in number average molecular weight and had one vinyl
group and 5 to 10 silanol groups per molecule on the
average.
The amount listed in Table 2 is the amount of
component effective as the macromonomer.
Preparation Example 16
Preparation of Copolymer (16)
A polyester polyol was prepared by the following
method.
* Trade-mark
- llo - 2~229~
The compounds given below were placed into a
glass flask equipped with a stirrer and a water separator.
Phthalic anhydride192 parts by weight
Hexahydrophthalic anhydride 256 parts by weight
Adipic acid 107 parts by weight ~-
Neopentyl glycol 357 parts by weight
Trimethylolpropane88 parts by weight
The mixture was heated to raise the temperature from 160~C
to 230~C over a period of 3 hours and thereafter
maintained at 230~C for 1 hour. With addition of 50 g of
xylol, the mixture was further reacted until the acid
value thereof became 8. The reaction mixture was cooled ;
and then diluted with a solvent mixture of xylene/n~
butanol (4/1) to a solids concentration of 50 wt. %. The
resin obtained was about 3,500 in number average molecular
weight as determined by GPC.
Preparation Example 17
Preparation of Copolymer (17)
Preparation of Copolymer (i)
The same procedure as in Preparation Example~ 8
was repeated except that CH2=CHCOOC2H4O~ was replaced by
the same amount of CH2=C(CH3)COOC2H4NCO to obtain
copolymer ti) (50% xylene solution, Mn = 6,000).
~ he following solution and compounds were placed
into a 400-ml glass flask equipped with a stirrer.
lll- 212298~
Solution of copolymer (i) 200 parts by weight
(CH3o)3sic3H6-oH 35 parts by weight
Xylene 35 parts by weight
The mixture was heated at 90~C with stirring for 5 hours
to effect an addition reaction between -OH group and -NCO
group.
IR absorption spectrum indicated disappearance
of absorption of -NCO group and -OH group. This revealed
that Si(OCH3)3 group and -OH group. This revealed that
-Si(OCH3)3 group had been introduced into copolymer (i).
Preparation Example 18
Preparation of Copolymer (18)
The following solution and compounds were placed
into a 400-ml glass flask equipped with a stirrer.
Solution of copolymer (1) 200 parts by weight
(50% nonvolatile content)
(CH3O)3SiC3H6NCo 13.3 parts by weight
C H3
C 2 H 4 O C O N H ~ C H3 23.5 parts by weight
H3 C C Hz N C O
Xylene 36.8 parts by wéight
The mixture was heated at 90~C with stirring for 5 hours
to effect an addition reaction between -CH group and -NCO
group.
IR absorption spectrum indicated disappearance
"
,- :
.
- 112 _ 21 229 8S ~;
of absorption of -OH group at 3530 cm~l. This revealed
that -Si(OCH3)3 group and ~ O group had been
introduced into copolymer (1) of Preparation Example 1.
Preparation Example 19
Preparation of Copolymer (19
The materials given below were placed into a
400-ml glass flask equipped with a stirrer.
Solution of copolymer (2) 200 parts by weight
(50% nonvolatile content)
(H3Co)3sic3H6sH 45 parts by weight
Xylene 45 parts by weight
The mixture was heated at 90~C with stirring for 7 hours
to effect an addition reaction between ~ O group and
-SH group.
IR absorption spectrum indicated complete ~ ;
disappearance of absorption of epoxy group, revealing
that -Si(oCH3)3 group had been introduced into copolymer
(2) of Preparation Example 2.
Preparation Example 20
Preparation of Copolymer (20)
The materials given below were placed into a
400-ml glass flask equipped with a stirrer.
Solution of copolymer (i) 200 parts by weight
~ CH2OH 25 parts by weight
Xylene 25 parts by weight
- 113 - 2~ 2~9 3~
The mixture was heated at 100~C with stirring for 4 hours
to effect an addition reaction between -OH group and -NCO
group.
IR absorption spectrum indicated complete
disappearance of absorption of -NCO group and -OH group,
revealing that ~ O group had been introduced into
copolymer (i).
Preparation of Base Coat A
The base coat composition to be used in
ccmbination with a two-coat one-bake clear coat
composition was prepared by the following procedure.
Prepatation of Siloxane Macromonomer
Methyltrimethoxysilane 2720 g
(20 moles)
y-Methacryloxypropyltri- 256 9
methoxysilane (1 mole)
Deionized water 1134 9 ;~
30~ HCl 2 9
Hydroquinone 1 9
~he mixture of above ingredients was reacted at ~ :
80~C for 5 hours to obtain a polysiloxane macromonomer,
which was 2,000 in number average molecular weight and had
1 vinyl group (polymerizable unsaturated group) and 4
silanol groups per molecule on the average.
A copolymer was prepared using the macromonomer
obtained.
. ?~
c' '~
- 114 - 212298~
Polysiloxane macromonomer 150 g
2-Hydroxyethyl acrylate 100 g
C H3 O
C Hz = C - C - O - C Hz ~ O 150 g
n-Butyl acrylate 500 9
Styrene 100 9
Azobisisobutyronitrile 10 g
The above mixture was added dropwise to 1,000 9 of mixture
of butanol and xylene in equal amounts by weight at 120~C
to effect polymerization and obtain a transparent
copolymer, which was about 30,000 in number average
molecular weight.
Using the obtained copolymer, a metallic base
coating composition of the following components useful in
the two-coat one-bake method was prepared using the
components in the amounts listed below (calculated as
solids)~
Above copolymer 95 parts by weight
Cellulose acetate butyrate 5 parts by weight
Aluminum paste #55-519 13 parts by weight
(product of Toyo Aluminum Co., Ltd.)
Aluminum trisacetylacetone 1 part by weight
The above mixture was adjusted to a viscosity of
13 seconds (Ford Cup No.4, 20~C~ with a 80/20 mixture of
toluene/Swasol #1500 (trademark, Cosmo Oil Co., Ltd.) and
, ::
.. :
.
,, ~
- 115 - 2 ~22 98
applied.
Preparation of coating compositions
Using the copolymers obtained in Preparation
Examples described hereinbefore, automotive topcoating
compositions were prepared. The obtained topcoating
compositions were solid color ones (white) and clear ones
useful in the two-coat one-bake method.
Table 3 below shows examples of preparation of
solid color (white) compositions (Nos. S-l to S-6).
Titanium oxide was dispersed in a copolymer solution for 1
hour using a paint shaker. The pigment used in the solid
color composition was used in an amount of 80 parts by
weight per 100 parts by weight of the resin calculated as
solids.
Table 7 below shows preparation examples of
clear coating compositions (Nos. M-l to M-13) useful in
the two-coat one-bake method.
The amount of copolymers shown in Tables 3 and 4
are expressed in % by weight of active ingredients
(resins). Tables 3 and 4 also shows the amount of pigment
and metal chelate compound expressed in % by weight of the
resin content (PHR).
The metal chelate compound used are as follows:
:
- 116 ~ 21 229 85
Chelate compound I tris(acetylacetonato)aluminum
Chelate compound II tetrakis(acetylacetonato)
zirconium
Chelate compound III diisopropoxy-bis
(ethylacetoacetato~titanate
Further in Tables 3 and 4, "Oligomer A" and
"TiO2" mean the following.
1) Oligomer A = Alicyclic oxirane group-containing
compound of the formula
~C-O-CH2 ~
O ~J 11 ~ O
:
2) TiO2 = pigment, titanium white, "Titanium oxide JR-602"
(product of Teikoku Kakoh K.K.)
, ~" ,
.' ':
~ * Trade-mark
,'
i,
- 117 - 2 1 2 2 9 3 5
Table 3
Coating compo-
sition No. S-l S-2 S-3 S-4 S-5 S-~
copolymer(1) 5 ~ 2 0
" (2) ~ :
" (3) 4 0 2 0 4 0
" (4)
" (5) 5 ~ :
" ( 6 ) 3 0
( 7 ) -~
" ( 8 )
" (9) 3 0 2 0 2 0 2 0
" ( 1 0 )
(1 1) ' '
" (1 2) 2 0
" (1 3) 3 0
~' (14) 30
(1 5) 30
" (1 6) 2 0
Oligomer A : 1) 0 2 0 3 0 3 0 3 0 2 0 ~ ~ :
Chelate compound I
~ m
Tio2 2) 8 0 8 0 8 0 8 0 8 0 8 0
- 118 -
2~ 22~.5
Table 4
'
Coating compo~
sition No. M-l M-2 M-3 M-4 M-5 M-6 M-7 M-8 M-9 :~ :
copolymer(1) 4 0 2 5 4 0 4 0
(2) 4 0 2 5 4 0
2 0 ~ ~
" (4) 6 0 -
" (5) 50 ~:
" (6) 20 20 -~
" (7) 5 0 1 0
- " (8) 20 40
" (9) 20 30
" (10) 20 30 20
" (11) 30 20
~' (12) 20
(13)
" (14)
~' (15) 1 0
" (16)
Oligomer A 1) 2 0 2 0 2 0 0 2 0 2 0 2 0 2 0 2 0
Chelate compound I 1 1 1 1 1 ~1 1
~ m
- 119 212298~
Table 4 (continued)
,, ,'
Coating compo- :
sition No. M-10 M-ll M-12 M-13
Copolymer ( 1 ) 4 0 5 0
" (2) 4 0
,- " (5) 5 O
(8) 2 O
(9) 2 O
'~ (17) 2 O
(18) 5 ~
(19) 2 O
" (20) 30
~o
- Oligomer A : 1) 2 O O 2 O 2 O
Chelate compound I 1 1 1 1 :
..
',,
I :
', :
-. .
"~.' '., ':'
,, .
.,.' :
;.,
, . ~, , .
,......................................................................... . .
- 120 ~ 29~
Performance Test I
To a dull-finished steel panel treated by
chemical conversion was applied an epoxy resin-type
cationic electrodeposition coating composition to a film
thickness of about 25 ~m and cured with heating at 170~C
for 30 minutes. Lugabake AM as an intercoating
composition (tradename for an automotive polyester
resin/melanine resin coating composition manufactured by
Kansai Paint Co., Ltd.) was applied to the panel to a dry
film thickness of about 30 ~m and baked at 140~C for 30
minutes. The coating surface was subjected to wet-
grinding with #400 sandpaper, dried and wiped with a piece
of cloth saturated with petroleum benzine to give a
substrate specimen.
The solid color topcoating compositions prepared
above were adjusted to a viscosity of 22 seconds (Ford Cup
No.4, 20~C) with Swasol #1000 (trademark for a product of
Cosmo Oil Co., Ltd., a mixture of petroleum type
solvents). The diluted composition was applied to the
substrate specimen to a dry film thickness of 40 to 50 ~m,
set at room temperature for 10 minutes and baked at 140~C
for 30 minutes to give a test coated panel.
Lugabake*AM white (coating composition No. S-7)
was applied in the same manner as above to give a test
coated panel for comparison.
*Trade-mark
- 121 ~ 2 1 2 2 ~
Table 5 shows the test results. In Table 5,
coating Composition No. S-7 is a comparative example.
~ "~
~ :
~ ~ S ~ ~ Y
- 122 - ~ 8~
1~ 0 N
~ ~ t~ ~O 0 -- N X <¦ ~) X
~n ~ O
~D O ~ O ~ O
I ~ ~ ~ ~' ~3 ~ ~ O O ~ O
cn ~ _
o
Ln o o o ~ o In
C/~ ~ o
o a~ ~ _ o
00 ~ -- ~ ~ O ~ O ~ ~ ~
tn ~ _
o
~) O O ~ ~ O N
3 0 ~3 0 ~O (~ ~
~
o
,a ~ O ~ 00 ~
~ ~ O tn ~3 O (~3 ~ oO
O
~ o o o~ _ o
tn ~ _
U ~ X
- 123 21 22 9
~ Performance Test II
A primer, "Soflex No. 2500" (product of Kansai
Paint Co., Ltd., Japan) was applied to a substrate of
polypropylene to a thickness of 15 to 20 ~m and baked at
80~C for 20 minutes. Then the above solid color
topcoating composition was applied to the panel to a
thickness of 90 to 50 ~m, and baked at 80~C for 30
minutes.
For comparison, Retan PG-80 white (trademark for
a product of Kansai Paint Co., Ltd., Coating Composition
No. S-8) was used as a solid color topcoating composition
in the same manner as above.
,'. '. ~,',
' ~ ''' ' '
.., :,. ~
'~''' ' ;' '~
' ':
- 124 -
212~
Table 6
Coating composition Present invention C~n'~ri
S - l S - 5S - 8
Gloss 8 7 9 18 9 ~:
Pencil hardness 3) F F F
DOI gloss 4 ) 8 7 9 18 5
Xylol resistance 5) O O o
Adhesion 6) 100/100 100/100 100/100
Impact resistance 7) 3 0 3 ~ 3 ~ ~ : ~
Acid resistance 8)
Scratching resist. 9) 0 0 ~ ;
Water resistance l0)
Staining resist. ll) O o ~\
Water repellency 12) 8 4 8 6 7 6
Weatherability 13)
Storage stability 14) ~ X
.
-
- 125 -
2122~85
Performance Test III
The base coating composition A was applied to
the substrate specimen used in Performance Test I above to
a dry film thickness of 15 to 20 ~m and was left to stand
for about 5 minutes. Clear topcoating compositions (Nos. -
M-l to M-13) diluted with Swasol #1000 to a viscosity of
22 seconds were applied to the coated specimens to a dry
film thickness of 35 to 45 ~m. After application of the
topcoating compositions, the coated substrates were ''
allowed to stand at room temperature for about 10 minutes
and baked at 100~C or 140~C for 30 minutes.
For comparison, to the substrate specimens were
also applied Magicron #1000 (silver) as a base coating ~ ;;
composition and Magicron #1000 (clear) as a clear
topcoating composition (product of Kansai Paint Co., Ltd., -~
acryl/melamine resin-type coating composition, No. M-
14). The coated substrate was baked in the same manner
but was not cured at 100~C.
Table 7 shows the test results.
* Trade-mark
:',
: ' :
.
Table 7
- .
- -
; : Coating composition M - 1 M - 2 M - 3
' Baking Temp. (~C) 1 0 0 1 4 O 1 O O 1 4 O 1 O O 1 4 O
Gloss 9 2 9 1 9 5 9 4 9 4 9 3
Pencil hardness 3) F H F H F H
DOI gloss 4) 8 7 8 6 8 8 8 7 8 9 9 O
. . ~. .",. .' .- ' . . .~ . . . ~;
~ Xylol resistance 5) O ~ O
'~: Adhesion 6) 100/100 100/100 100/100 100/100 100/lOC 100/100
Impact resistance 7) 3 5 3 o 3 5 3 o 3 5 3 o
Acid resistance 8)
.. Scratching resistance 9) 0 0 0 0 0 - O
' Water resistance 10) ~ ~ ~ c~
Staining resistance Il) O o O O O O
~ '"'2~''.''.'''J~ - Water repellency 12) 8 2 8 3 8 5 8 6 8 5 8 7
Y~ Weatherability 13)
~,''.' ''''''!~~'';': '';~'~, '~,.:-',' " '' ,'' '' " , Storage stability 14)
~ .
.
.
r~ a~
.
~ ; Table 7 (continued)
Coating composition M - 4 M - 5 M - 6
Baking Temp. (~C) 1 0 0 1 4 O 1 O O 1 4 O 1 O O 1 4 O
' Gloss 9 1 9 2 8 9 9 O 9 5 9 6
Pencil hardness 3) F F F H F H
~'';~'''''~''~'~'""~''"~' ~ DOI gloss 4 ) 8 8 8 8 8 4 8 5 8 7 8 6
~ ' Xylol resistance 5) O ~ O ~ O ~ ~
Adhesion 6) 100/100 100/100 100/lOC 100/100 100/lOC 100/100
'................... Impact resistance 7~ 3 O 3 o 3 o 3 o 3 o 3 o
~ Acid resistance 8)
"n~ . Scratching resistance 9~ 0 0 0 0 0 0 ~9
Water resistance 10~
Staining resistance 11) 0 0 0 0 0 0 ~n
~ " J Water repellency 12) ~ o 8 1 8 1 8 2 9 2 9 1
.'J'' Weatherability 13) ~ ~ ~ ~ O O
Storage stability 14) ~ ~ ~
; . ~:: .
~,' ' ' ~
: ' ''~ .
; ' ~ '
Table 7 (continued)
Coating composition M - 7 M - 8 M - 9
Baking Temp. (~C) 1 0 0 1 4 0 1 0 0 1 4 0 1 0 0 1 4 0
Gloss 9 2 9 2 9 1 9 0 8 9 9 1
Pencil hardness 3) F H F H F H
DOI gloss 4) 8 9 9 0 8 8 9 1 9 0 9 2
Xylol resistance 5) O ~ O ~ O ~ I -
Adhesion 6) 100/100 100/100 100/10C 100/100 100¦100 100/100 ~
Impact resistance 7) 3 0 3 0 3 5 3 0 3 5 3 0
Acid resistance 8)
Scratching resistance 9) O O O ~ O
Water resistance 10) ~ ~ ~ ~ ~ ~ c~
Staining resistance 11) ~ ~ o ~ ~ ~ GO
Water repellency 12) 9 5 9 6 9 3 9 2 9 4 9 6
Weatherability 13)
Storage stability 14)
.- :
:
: ' : ':
, ~
Table 7 (continued)
.
Coating composition M - 1 O M - 1 1 M - 1 2
Baking Temp. (~C) 1 0 0 1 4 O 1 O O 1 4 O 1 O O 1 4 O
.. '
~ :; Gloss 9 1 9 0 8 8 8 9 9 1 9 2
~'f'~ Pencil hardness 3) F H F H F H
~ DOI gloss 4 ) 8 9 8 8 9 O 9 O 8 7 8 8
~ . Xylol resistance 5)
. Adhesion 6) 100/100 100/100 100/100 100/100 100/lOC 100/100
Impact resistance 7) 3 o 3 o 3 o 3 o 3 o 3 o
Acid resistance 8)
Scratching resistance 9) 0 0 0 ~ O
' Water resistance 10)
Staining resistance 11) 0 ~ e~n
~ Water repellency 12) 8 8 8 9 8 4 8 4 8 1 8 2
Weatherability 13)
Storage stability 14)
: - ~
.
. ' ! ' , ~ ~ '
: - ''', .,: : ' . : ,.
~ Table 7 (continued)
: - -
. ~ -
~ -- Coating composition M - 1 3 M - 1 4
~i'
S ..... . ~ - Baking Temp. (~C) 1 0 0 1 4 0 1 0 0 1 4 0
~ Gloss 9 0 8 9 9 3
~ Pencil hardness 3) F H F
~ DOI gloss 4) 8 6 8 9 7 5
. .. . ... - ' ~ ' ~
Xylol resistance 5) ~ ~ O
,"r~ ";,~,~' ~,'r.',~ Adhesion 6) 100/100 100/100 100/100
~ Impact resistance 7) 3 o 3 o 2 0
Acid resistance 8). ~ ~ X
~ Scratching resistance 9) O O
~ '''~'':!, j'',-','.~'_~.'~" ''','''''.',: ~.'''' Water resistance 10)
~ ' staining resistance Il) 0 0
~ Water repellency 12) 8 2 8 4 7 6 ~-7
'~' r'~ 'X Weatherability 13) ~ ~ cracking
. ''~'~',i.-'~-, ;,._.''.'~'.'i~;.~.~:~ :.r~ Storage stability 14) ~ ~
- ,: -.- . . - ~,
.
, . . .
- 131 ~ 21229~
3) Pencil hardness: -
Surface of the coat was scratched with a pencil
"Mitsubishi Uni" (trademark for pencils manufactured by
Mitisubishi Pencil Co., Ltd.) while being pressed with the
pencil lead. The degree of pencil hardness was evaluated
and expressed in usual symbols for hardness such as H, 2
or B to represent a maximum hardness of lead which caused
no mar on the surface.
4) Distinctness-of-image gloss (DOI gloss)
The distinctness-of-image gloss was determined
using an image clarity meter (product of Suga Shikenki
Kabushiki Kaisha). The figures in tables are ICM values
of 0 to 100% as determined by the meter. The larger the
value, t~e higher the distinctness-of-image gloss. The
values of more than 80 indicate markedly high
distinctness-of-image gloss.
5) Xylol resistance
Surface of the coat was vigorously rubbed with a
piece of xylol-impregnated gauze pressed with fingers to
achieve 10 reciprocal strokes. The results were evaluated
in terms of the degrees of dissolution, mar and swelling
and rated according to the following criteria.
~ : Gloss not affected
O : Gloss slightly lost
~ : Gloss lost
- 132 -
~ 2 ~ ~ ~
: Swollen
X : Dissolved
6) Adhesion
~ he coat was cut crosswise to the surface of the
substrate with a razor to form 100 squares, 1 mm x 1 mm.
An adhesive cellophane tape was adhered to the coating
surface and then quickly peeled off. The number (N) of
remaining squares was counted and expressed in terms of
N/100.
7) Impact resistance
The impact resistance was determined using a ~u
Pont impact tester (diameter of impact load element 1/2
inch; weight 0.5 kg). The degrees of impact resistance
were assessed in terms of a maximum height at which the
dropping of the weight caused no cracking on the coating -
surface.
8) Acid resistance ~ -~
~ he coated substrate specimen was immersed in
40~ H2S04 at 4Q~C for 5 hours, withdrawn and washed with
water after which the coating surface was observed and
evaluated according to the criteria in which the symbols
to X designate the highest to lowest degrees of acid
resistance.
: Gloss not affected
O : Gloss slightly lost
..... . ,,, ., . ., ,.. '. ., ~, : . . ., :' .
- 133 -
2~22~8~
: Gloss lost
: Slight degree of blushing -~
X : Blushing
9) Scratching resistance
The scratching resistance was determined using a
tester for color fastness of dyed materials against
friction (product of Daiei Chemical Precision Machinery
Mfg., Co.). A polishing powder ("Daruma Cleanser",
trademark) was kneaded with water to give a mass of high
viscosity and the resulting mass was placed on the coating
surface. While being pressed with a terminal element of
the tester, the coating surface was rubbed with the mass
deposited thereon under a load of 0.5 kg to achieve 25
reciprocating strokes. After the coated substrate was
washed with water, the degree of scratching was evaluated
according to the following ratings:
~ : Not scratched
O : Slightly scratched
: Scratched in low degree
: Scratched in high degree
X : Scratched in highest degree ~-
10) Water resistance
The coated substrate specimen was immersed in a ;
thermostatic water bath at 40~C for 240 hours. After
withdrawal, the water resistance of the coating surface
::
- 134 -
2~2~8~
was evaluated in scales of 5 grades represented by symbols
~ to X in which the symbol ~ means the appearance
without change as in gloss or blistering.
11) Staining resistance
A 1 g quantity of stained dust according to JIS
No.15 was placed onto the coated substrate specimen
measuring 5 x 5 cm. The dust was uniformly spread over
the substrate with 20 strokes of a brush and was left to
stand at 20~C for 24 hours. The coated substrate specimen
was washed in running water with a clean brush and checked
for the degree of staining. The results were evaluated
according to the following ratings.
~ : Not stained
O : Slightly stained
: Stained in unacceptable degree
X : Stained in highest degree
12) Water repellency
The water repellency was expressed in terms of
the angle at which the coating surface is in contact with
water. The contact angle was measured with a contact
angle meter (product of Kyowa Kagaku Kabushiki Kaisha) 3
minutes after dropping 0.03 ml of distilled water onto the
coating surface at a temperature of 20~C. The greater the
figure, the higher the water repellency.
13) Weatherability
212298~
Using an accelerated weathering tester
(manufactured by Q Panel Co., Ltd.), a QW acceleratd
exposure test was carried out under the following
conditions:
One cycle:
W irradiation 16 hr/60~C
Water condensation 8 hr/50~C
After conducting 125 cycles of operation (3000-
hour exposure), the degree of weatherability was evaluated
according to the following ratings.
: Retaining substantially the same gloss as in
initial stage
O : Slightly impaired in gloss, but free of flaw
such as cracking, blushing and the like
X : Significantly reduced in gloss and defective in
respect of cracking and blushing (chalking)
14) Storage stability ~ ~
The coating composition diluted to a constant ~-
viscosity (22 seconds/Ford Cup No.4) was placed into a
container. The container was covered with a lid to
prevent exposure to the atmosphere and was stored at 40~C
for l week. The storage stability was rated according to
, the following criteria.
' ~ : Increased in viscosity to up to 5 seconds
: Increased in viscosity to 5 to 10 seconds
:..
.
, .
* Trade-mark
:.
- 136 ~ 21 22~ 8 ~
X : G e l l e d
:: ,
;~ ' '',
~: ,. .. ' ' ,:',
~ ''"'',. "','
:- ~
