rrhis invention relate6 -to thermosetting powder
coating cornpositionG.
With ever increasing severity of pollution of
r~ir, wa-ter and the lile~ powcler coating composi.tions are
introduced into use whic~l are a~nost unli!sely to cause
pollution problems.
Presently, epoxy resin or v:inyl chloride resin
is chiefly used as the resin component of powder coa-ting
compositions. Because of poor resistance to weather,
however, powder coating compositions o~ the epoxy resin
type are not usable out-of-doors, whilst those of -the
vinyl chloride resin type which are thermoplastic are inferior
in their resistance to heat and to solven-ts and there~ore
have limited usefulness,
In order to overcome these problems~ various
powder coating compositions of the acrylic resin type
have been recently proposed which contain glycidyl group
a3 a functional group.
With such acrylic resin type powder coating
composition containing functional glycidyl groups, efforts
are made to ingeniously maintain the thermal flowability,
~cross-lin~ing reaction velocity and softening point of
the resin in balance with one another BO that the composition
exhibits good storage stabi~ity and gives ~mooth COatingG
having high resistance to solvents,
- 2 ~
~LQ14~6~
To ~nsure such balance, there arises the necessity
-to accurat~ly determine the kind of the acrylate or meth-
acrylate to be used, the amount thereof) the polymerization
degree and the amount of the monomer containing the
fuctional group to be used. However, even with the optimum
combination of these factors, the coating composition is
prone to blocking when applied or stored in an environment
in which the ambient temperature is likely to exceed 35 C~
The term "blocking" means the phenomenon in which particles
of the coating composition cohere one another during
storage~ This objection is avoidable when the composition
is adapted to have an elevated softening point at the
sacrifice of the smoothness of the coating to be prepared
therefrom or, otherwise, by providing cooling means for
the containers for storing and recovering the coating
composition. In the former case~ the powd0r coating com- -
position of the thormosetting acr~lic resin type is no
~. longer applicable to decorative surface fini~h for which
- the coating composition i~ chiefly intended to use~
whereas the latter case entails hlgher equipment ~ost
and operation cost ~nd is unfavorable~
Furthermore, powder coating compositions of
the acrylic resin type r~quire baking at high temperatures
of at least 180 C~ if it is d~sired to obtain a coating
which is ~uperior in me¢hanical propert~e~ such as resist~nce
. . ,
9~
to impact, Erich.en te~t and flexural streng-th, besause
lower bakin~ -temperatures not only impair -the mechanical
prop~r-ties of the coa-ting but also reduce its resistance
-to weather, solvents and hea-t,
For uæe in decorative surface finishing, powder
coating compositions, like usual solvent--type coating
compositions, should be applicable to a small thickness
of about 25 to 50 microns for the sake of economy, but
conventional thermosetting powder coating compo~itions of
the acrylic resin type involve difficultles in giving
thin coatings, because they exhibit a hi~h melt viscosity
when applie.d for coating and display. low flowability
when heated for fusion. Although such coating compositions
may be adapted to form thin coatings by reducing their
curability to render them more flowable in molten state,
thls is not desirable since the resulting coatings will
be inferior in physical properties7 solvent resistance,
etc, On the other hand, the coating composition can be
made to form thin coatings when reduced in its softening
point and thereby lowered in its melt viscosity~ but the
composition will then have the disadvantage that the
particles cohere together durin~ storage~ resulting in
reduced resi~tance to blocking. Such composition is
therefore si~ilarly unde~irable~
: 25 Accordingly, an object of this invention is to
, '
.
:' '' """ '
provide an improved powder coating composi-tion which is
free of the foregoing drawbacks of kno~m acrylic powder
coa-ting compositions.
Ano-ther object of -this invention i6 to provide
a powcler coating composition capable of giving coatings
which are excellent in mechanical strength and in physical
properties even when baked at low temperatures.
Another object of this invention is to provide
a powder coating composition capable of giving smooth
glossy coatings for decorative pu~poses ~ree from undesired
blocking, even when applied or stored in a hot environment~.
Still another object of this invention is to
provide a powder coating composition which has a low melt
viscosity and good flowability and which is therefore
capable of readily forming smooth1 glo~sy and yet thin
coatings.
The present invention provides a thermosetting
powder coating composition which comprises:
(A) A graft copolymer of
a) 10 to 40 percent by weight of a linear polyester
having a number average molecular weight of 600 to
3~000 and containing one ethylenically un~aturated
double bond only at one end of the molecule,
b) 5 to 30 percent by weight of a glycidyl ester
having the ~ormula
-- 5 --
1~9196~
1 1 0
CH2 _ C-COOCH2 - CH - CH2
wherein Rl is hydrogen or methyl, and
c) 10 to 85 percent by weight of an acrylic compound
having the formula
l2
CH2 = C-COOR3
wherein R2 is hydrogen or methyl and I~3 is alkyl
having 1 to 14 carbon atoms, cyclohexyl or hydroxyalkyl
l4
represented by -CH2-CHOH wherein RL~ ~s hydrogen or
alkyl having 1 to 2 carbon atoms,
said graft copolymer having a softening point of
70 to 110 C and a number average molecular weight of
2~000 to 30,000; and
(B) at least one of polycarboxylic acids and anhydrides
thereof in an amount of 0.6 ko 1.2 moles in terms of
carboxyl group per mole of the glycidyl group contained
in the graft copolymer.
~ he first advantaga of the coating compo~i~ion o~
this invention i8 that when baked for 30 minutes at a
temperature of 150 C which is much lower than is the cas~
with conve~tional acrylic powder coating composition~
the composition gives a coating having mechanical propertie~
- 6 -
,
. ~ .
~g6~4
such a5 impact resistance, Erichsen test and flexuralstrength, which are comparable to those resulting from.
epoxy resin.powder coati~lg compositions which are the most
excellent of presently avai.lable powder coating compositions.
Moreover~ coatings prepared from the present composition
are in no way inferior to usual powder coating compositions
of the thermosetting acrylic resin type in respect of
resistance to weather~ solvents and heat.
The second advantage of the present coating
composition is tha-t the above-mentioned unique graft
copolymer of polyester and acrylic resin used therein
enables the composition to remain in the form of fine
particles free of blocking 60 as to be applicable to
electrostatic coating or fluidi~d bed coating even under
a eevere operation condition of 35 to 40 C as when it is
used during eummerJ with the result that the compoeitlon
can give smooth and gloæsy eurface finish coatingsO
It ie indeed surprieing that the above-specified
graft copolymer o~ linear polyeetor and acrylic polymer~
although containing 10 to L~0 percent by weight o~ polyester
grafted on to the polymer~ hae almoet as high a softenlng
point as ungrafted acrylic polymers and possesse~ a greatly
reduced melt viscosity when heated.
The high softenlng point make~ it less likely
~or the coaLing composit~o ~o undergo blockin6 during
.. ..
.,,
613~L :
storage or coating operation, 50 -that the composi-tion
has high resistance -to blocl~ing and goo~ ~nenability to
coating operation~
On the other hand, the low melt viscosity of
the composition when it is applied for coating en~ures
good thermal flowabillty to give a smooth surface finishO
The third advantage of the coating composition
of this invention is that because of its low melt viscosity
and good thermal f~owability during the formation of
coating, the composition is capable of giving s~ooth and
glossy coatings having small thicknesses of 25 to 50 ~
while retaining the desired curability and blocking resistance.
Thus these various advantages of the invention
are attributable to the use of the specified graft copolymer
f acrylic polymer and linear polyesterO
With thi~ invention, the polye~ter constituting
the above-identified copolymer must havea number average
molecular weight oP 600 to 3,000 and contain one ethyleni-
cally unsaturated ~ouble bond only at one end of the
molecule. With a number average molecular weight of less
than 600, the polye~ter ha~ an poor pla~tioizing ability
and is inef~ective in greatly reducing the melt viscosity~
impa~ring the smoothnes~ and ph~ical properties of the
resulting coatingO Wlth a number avera~e m~lecular weight
f more than 3~000~ the coating compo~ition ha~ a markedly
~04~8~L
reduced so~tening point and poor blocking resistance.
Preferable number average molecular weight is in the
range of 1,000 -to 2,000.
The method of preparing the linear polyester
having one ethylenically unsaturated double bond at one
end o~ the molecule is in no way limitative in this
invention but merely has a secondary significance in this
invention. Most ~dvantageously, however, it is prepared
by condensing a monohydroxymonocarboxylic acid or a mixture
of the acid and monocarboxylic acid to obtain a linear
polyester having one free terminal carboxyl group and
reacting glycidyl acrylate and/or glycidyl methacrylate
with the polyester. Useful monohydroxymonocarboxylic
acids having one carboxyl group a-t the end of the molecule
and one hydroxyl group in the molecule are aliphatic mono-
hydroxymonocarboxylic acids having 2 to 18 carbon atoms.
Preferable examples are 12-hydroxystearic acid9 ricinoleic
acid~ lactic acid~ etc., among which especially preferable
are 12-hydroxystearic acid and ricinoleic acid. The
monohydroxymonocarboxylic aicds can be used alone or in
admixture with one another. Monocarboxylic acids can be
employed in admixture with the monohydroxymonocarboxylic
acid, if desired, in order to adjust a molecular weight
of the resultant linear polyester~ Usable monocarboxylic
acids are aliphatic monocarboxylic acids having 1 to 18
. ~ .
.
':
carbon atoms and aromatic monocarboxylic acids represented
by -the formula
(R5)
~ COO~I
wherein ~ is al~l having 1 -to L~ carbon atoms and n is
0 or an in-teger of 1 or 2. Preferable examples of the
former are acetic acid, caproic acid, caprylic acid, capric
acid, lauric acid, myris~ic acid, palmitic acid, stearic
acid~ etc. Preferable examples of the latter are benzoic
acid, p-tert-butyl benzoic aci~ etc. Especially preferable
monocarboxylic acids are palmitic acid~ stearic acid and
p-tert-butyl benzoic acid. One or more of -the monocarboxylic
acids can be used. The hydroxymonocarboxylic acid is
subjected~ singly or as admixed with -the monocarboxylic
acid9 to condensation reaction. When the monocarboxylic
acid is used, the amount thereof is up to 20 mole %,
preferably 10 to 20 mole %, based on the hydroxymonocarboxylic
acid.
The condensation reaction is conduc-ted in a
conventional manner in the presence or absence of catalyst
and with heating~ Suitable catalysts are; for example,
sulfuric acid, dimethyl sulfuric acid, methanesulfonic
acid, etcO Generally, the condensation temperature is
about 130 to about 170 C. The condensation reaction yields
a linear polyester having one carboxyl group at the end
-- 10 --
.:
of the molecule.
In order to introduce.an ethylenically unsaturated
double bond in-to the polyester at the end of the molecule,
the polyester is then reacted with glycidyl acrylate and/or
glycidyl me-thacrylate. For this reaction, an equivalent
or excess of glycidyl acrylate and/or methacrylate is
used based on the carboxyl group of the polyester. The
excess glycidyl ester serves as another rnonomer component
A-(b) to ultimately obtain the desired graft copolymer.
Advantageously, the reaction is conducted in the presence
; of catalyst such as trimethylamine~ triethylamine, dimethyl-
. aminoethanol, dimethyl coconut amine or like tertiary amine,
or tetraethyl ammonium bromide, trimethylbenzyl ammonium
chloride or like quaternary ammoni~m salt~ Usually, the
reaction is carried out at a temperature of 110 to 150 C,
preferably until the acid value of the product reduces
to a level not higher than 5.
Another component A-(b) o~ the gra~t copolymer
is a glycidyl ester represented by the formula
Rl 0 ...
CH2 = C-COOCH2 - CH - CH2
- wherein Rl is hydrogen or methyl. Such esters are glycidyl
acrylate and glycidyl methacrylate.
Another component A-(c) of the graft copolymer
is an acrylic compound represented by the formula
-- 11 --
: . .
.
~96&14
R2
C~2 = C-COOR3
wherein R~ is hydrogen or methyl, R~ is alkyl havingr 1 to
~ L~
lL~ carbon atoms, cyclohexyl or -CH2-C~IOH wherein Rl is
hydrogen or alkyl having 1 to 2 carbon atoms. ~xamples
of such compounds are esters of acrylic acid and meth-
acrylic acid. The esters include methyl acrylate, ethyl
acrylate, propyl acrylate, n-butyl acrylate, iæo-butyl
acrylate, t-butyl acrylateg 2-ethylhexyl acrylate, lauryl
acrylate, methyl methacrylate, ethyl methacrylate, propyl
methacrylate, n-butyl methacrylate, iso-butyl methacrylate,
t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl
methacrylate, and like alkyl esters; cyclohexyl acrylate
and cyclohexyl methacrylate; and 2-hydroxyethyl acrylate,
2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
2-hydroxypropyl methacrylate and like hydroxyalkyl esters.
Preferable acrylic compounds are methyl acrylate, ethyl
acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl
methacrylate, n-butyl methacrylate, iso-butyl methacrylate,
2-ethylhexyl methacrylate~ 2;hydroxyethyl methacrylate
~nd lauryl methacrylate. They may be uæed alone or in
admixture with one ano-tJier.
The graft copolymer to be used in this invention
is obtained by subjecting to gra~-t copolymerization the
- 12 -
~9~
above three components, namely linear polyester A-(a)
having one ethylenically un,saturated double bond at the
end of the molecule, glycidyl ester A-(b) and acrylic
compound A-(c). The graft copolymer must have a softening
point of 70 to 110 C and a number average molecular
weight of 2,000 to 30,000. If the softening point is
below 70 C~ the resistance to blocking of the resulting
coating composition will be poor. When the softening
point is higher than 110 C9 the resulting coating will
be poor in surface smoothness. With less than 2,000 number
average molecular weight of the graft copolymer~ the
coating obtained has low mechanical strength and solvent
resis-tance while the coating composition has inferior
resistance to blocking. On the other hand~ a molecular
weight higher than 30,000 gives no additional effect on
the properties of the coating composition as well as of
the coating but increases the melt viscosity of the coating
composition, making it impossible to obtain a smooth coatingO
Preferable number average molecular weight of the graft
copolymer is 4,000 to 20,000~ "'
The proportions of the components A-(a), A-(b)
,and A(c) to be copolymerized into the graft copolymer
are critical and must be 10 to 40 % by weight of linear
polyester A (a), 5 to 30 % by weight of glycidyl ester
A~(b) and 10 to 85 % by weight of acrylic compound A-(c).
- 13 -
~ 04~
If the amoun-t of -the linear polyester is less -than 10 %
by weight9 i-t is impossible to fully ensure the effect
con-templated by this invention~
More specifically, as will be apparent from Composition
No. 6 in the example ~iven later, a graft copolymer (GP-6)
containing about 5 % by weight of the polyester is not
particularly distinguishable from ungrafted copolymers~
whereas those containing at least 10 % by weight of polyester
have an outstanding effect.
This will be seen from Table 1 given below which
shows the softening poin-ts and melt viscosities at 140 C
of copolymers containing varying amounts of polyester.
Table 1
Proportion of
polyester in Melt Viscosity Soften~ng
the copolymer (Poises) point( C)
(wt. %)
82
5,~00 87
1,500 89
1,300 82
1,250 66
. .' -- - - - . , _
Note: The copolymers are prepared in the same manner as
graft copolymer-4 given later, except that the amount
of polyester-4 is varied.
- lL~ _
; . ~ .
, ~
4~68~
Evidently3 the table shows that use of 10 to
40 % by weight of polyester for graft copolymerization
remarl~ably reduces -the melt viscosity without perlllitting
a noticeable reduction in the softening point. The table
further reveals that use of more than 40 % by weight of
polyester is not noticeably effective in reducing the
melt viscosity, while markedly lowering the softening
point to reduce the resistance to blocking of the coati.ng
composition (see Composition No. 10 in the example given
later). Preferably the proportion of polyester to be co-
polymerized is about 15 to 30 % by weight. `~
When the proportion of glycidyl ester A-(b) is
less than 5 % by weight, insufficient cross linking will
resul~.~ failing to impart satisfactory solvent resistance
and mechanical strength to the coating formed (see Composition
No. 13 in the example below), whereas proportions more
than 30 % by weight permit the cross-linking reaction to
proceed to excess during the coating forming step, resulting
in a lower flowability during that step and rendering the
coating no longer smooth-surfaced (see Composition No. 14 in
the example below), Preferably? 10 to 25 % by weight of
glycidyl ester is copolymerized,
The acrylic compound A-(c)~ another component
of the graft copolymer and represented by the ~ormula
- 15 -
R2
CH2=C-COOR3 (wherein R2 and X3 are as defined above)
should be used in a proportion of at least 10 % by weight
to ensure the adhesion of the resulting coating to the
substrate (see Composition No. 22 in the example given below)~
In addition to the foregoing three components,
the graft copolymer usable in this invention may further
contain, as a copolymerizable monomer A-(d), up to 40 %
by weight of at least one of acrylonitrile, methacrylonitrile,
and styrenes represented by the formula
~g~ cx =CH2
R6
wherein R6 is hydrogen or alkyl having 1 to 4 carbon atoms.
The styrenes of the above formula include styrene, vinyl-
toluene, etc. They are used singly or in admixture with
one another.
When containing the above monomer, the coating
composition obtained exhibits better resistance to blocking.
The proportion of the additional monomer must be up to L~0 %
by weight and is usually 5 to 30 % by weight. With more
than 40 % by weight of the additional monomer, the resulting
coating will be poor in surface smoothness.
The graft copolymer is prepared by block
polymerization, solution polymerization, suspension poly
merization, emulsion polymerization, etc., among which most
preferable is solution polymerization~
_ 16 -
,. : " , ~ ,,
6~
In the solution polymerization are employable
various organic solvents such aas aliphatic hydrocarbons,
aromatic hydrocarbons, etc. The solution polymerization
can be conducted in the presence of polymerization initiators.
Examples thereof are organic peroxides such as benzoyl
peroxide, lauroyl peroxide, tert-butylhydroperoxide, tert-
butyl peroxyoctate, isobutanoyl peroxide, etc. and azo
eompounds such as azobisisobutyronitrile, azobisisovalero-
nitrile, etc. The solution polymerization reaction i9
usually carried out under reflux temperature.
The powder coating composition of this i~vention
incorporates the graft copolymer described above and
at least one of polycarboxylic acids and anhydrides
thereof. Useful polycarboxylic acids are aliphatic,alicyclic
and aromatic polycarboxylic acids which are known as
curing agents for acrylic resins con-taining a functional
glycidyl group. More specific examples of polycarboxylic
acids are aliphatic polycarboxylic acids such as adipic
acid, azelaic acid, sebacic acid~ dodecanedicarbox~lic
acid, fumaric acid, male~c acid, succinic acid, tricarballylic
acid, etc~; alicyclic polycarboxylic acids such as
tetrahydrophthalic acid, hexahydrophthalic acid, etc; and
aromatic polycarboxylic acids such as phthalic acida
isophthalic acid, terephthalic acid, trimellitic acid,
pyromellitic acid, etc. The anhydrides of such polycarboxylic
- 17 -
~9~4
acids ar~ similarly usable. The polycarboxylic acids and
anhyclri~es thereof are used singly or at least two of
them are usable in admixture.
To prepare the powder coating composition of
this invention, at least one o~ the above polycarboxylic
acids and anhydrides thereof is used in an amount of o.6
to 1~2 moles in terms of carboxyl group per mole of the
glycidyl group contained in the graft copolymer~ Lesser
amounts lead to insufficient curing and there~ore to
lower mechanical strength and solvent resistance of the
resulting coating (see Composition No. 19 in the example
given below), while excess amounts result in reduced
surface smoothness and poor physical properties of the
coating (see Composition No. 20 in the example).
The powder coating composition of this invention
may further incorporate organic and inorganic pigments,
flowing agent, curing catalyst, antistatic agent, etc.
which are generally used for coating compositions.
Employable as the curing catalysts are, for example,
tert-amine, quaternary ammonium salt,organic tin compound
such as triphenyl tin chloride and dibutyl tin laurate
~nd titanium compounds such as tetra-isopropyl titanate.
~ he powder coating composition can be prepared
by any conventional method, for example, by blending the
ingredients in molten state or by formulating the
ingredients into a solution and thereafter removing the solvent.
18 -
,
For a better understanding of the inventlon
examples for preparing linear polye~ters (A)-a, graft
copolymers (A) and coatlng composltions are glven below.
<Preparation of polyester>
1. Polyester-l (PE- 1)
A 3,000 g quantity of 12-hydroxystearic acid,
150 g of toluene and 5 g of meth~nesulfonic acid
serving as a catalyst are placed into a 5-liter reactor
equipped with a thermometer, a water separator and a
stirrer, and the mixture is subjected to dehydration
conden3ation at 150 C for 4 hours to prepare a polyester
in the form of a viscous liquid and having an acid value of
32 and a molecular weight of about 1,750. The
polyester will be hereinafter referred to as "poly~ster-l"'
or "PE- 1"'.
A 1,000 g portion of the polyester- li, 140 g
of glycidyl methacrylate, 0.5 g of hydroquinone and
1,000 g of toluene are placed into a 5-liter reactor
equipped with a countercurrent conden~er, a thermometer
and a stirrer, and the mixture is reacted at 1~0 C under
reflux for 10 hour~ to ~ive a polyester (hereinafter
referred to as "pclyester- 1" or "PE- 1") havin~ an acid
value of 0.2 and a molecular w~i~ht of about 1,890.
2. Pol~estar- 2 (PE- 2)
Exactly the came procedure as in the case of
19
9~i8~
polyester- 1' is followed except that the dehydration
condensation is effected for 1.5 hours to obtain a
polyester (hereinaf er referred to as "polyester- 2"'
or "PE- 2"') in the form of a viscous liquid and having
an acid value of 56 and a molecular weight of about
1, 000 ~
The polyester- 2' and the compound listed in
Table 2 below in the listed amount, are reacted
in the same manner as in the case of polyester- 1 to
prepare a polyester (hereinafter referred to as
"polyester- 2" or "PE- 2") having the properties given
in the same table.
3. Polyester- 3 (PE- 3)
Exactly the same procedure as in the case
of polyester- 1' is followed except that the dehydration
condensation is effected for 10 hours to obtain a
polyester (hereinafter referred to a~ "polyester- 3 "' or
"PE- 3"') in the form of a vi~cous liquid and having an
acid ~alue of 20 and a moleculer weight of about 2,800
The polyester- 3~ and the compound listed in
Table 2 below in the li~ted amount, are reacted in
the ~ame manner a~ in the case of polyester- 1 to prepare
a polye~ter (hereinafte~ referred to as "polyester- 3"
or "P~- 3") havin~ the properties given in the same
t~ble.
- 20 _
':
,....... .
.
. . ~ .' . . ~ ' , , ~ ,
- .
.
. . ~ . ' .
4. Polyester- 4 (PE~
Exac-tly the same procedure as in the case of
polyester- 1' is followed except -that the dehydration
condensation is effec-ted for 3 hours using 2,800 g of
ricinoleic acid and 200 g of t-butylbenzoic acid in
place of 3,000 g of 12-hydroxystearic acid to obtain
a polyester (hereinaftèr referred to as "polyester- 4~ tl
or "PE- 4"') in the form of a viscous liquid and having
an acid value of 37.4 and a molecular weig~t of about
1,500.
~he polyester- 4' and the compound listed in
~able 2 below in the listed amount, are reacted
in the same manner as in the case of polyester- 1 to
prepare a polyester (here~inafter referred to as
"polyester- 4" or "PE- 4") having the properties given
in the sa~e table.
5. Polyester- 5 (PE_ 5)
~xactly the ~a~e procedure as in the case of
polyester- 1' is followed except that the dehydration
condensation is effected for 2 hours using 2,500 ~ of
: 12-hydrox~stearic acid and 500 g of lactic acid to
obtain a polyester (hereinafter referred to as "polyester-
5"' or "PE- 5"') having an acid value of 80 and a molecular
weight of ~bout 700.
- 21 -
The polyester- 5' and the compound listed in
Table 2 below in the listed amount, ara reacted in
the same manner as in the case of polyester- 1 to prepare
a polyester (hereinafter referred to as "polye~ter- 5"
or "PE- 5") having the properties given in the same
table.
6. Polye~er- 6 (PE- 6)
Exactly the same procedure as in the ca~e of
polyester- 1' i8 followed except that the dehydration
condensation is effected for 3.5 hours using 2,500 g
of 12-hydroxystearic acid and 400 g of coconut oil fatty
acid to obtain a polyester (hereinafter referred to as
"polyester- 6 "' or "PE- 6 "') in the form of a viscous
liquid and having an acid value of 35 and a molecular
weight of about 1,600.
~he poly~ter- 6' snd the compound listed in
~able 2 below in the li~ted amount, are reacted
in the same manner as in the case of polyester- 1 to
prepare a polyestar (hereinafter referred to as "polye~ter-
6" or "PE-6") having the properties given in the ~ame
table.
.7 A Pol~e~ter- 7 (PE_ 7)
E~actly the same procedure as in the Case of
polyester- 1' is ~ollowed except that the dehy~ration
condensation is effected for 1.5 hours uqing 1,500 g of
- 22 -
.
.
~t4~
12-hydrox~stearic acid and 1,500 g of lactic acid to
obtain a polyes-ter (hereinafter referred to as "polyester-
7"'or "PE- 7 "') in -the form of a ~iscous liquid and
havin~ an acid value of 150 and a molecular weight of
about 375.
'~he polyester- 7' and the compounds listed in
~able 2 below, each in the listed amOUnt, are reac-ted in
the same manner as in the case of polyester- 1 to prepare
a polyester (hereinafter referred to as "polyester- 7"
or "PE- 7") having the properties given in the same
table.
8. Yolyester- 8 (PE- 8)
Exactly the same procedure as in the case of
polyester- 1' is followed except -that the dehydration
- 15 condensation is effected for 15 hours to obtain a
polyester (hereinafter referred to as "polyester- 8 "'
or "PE- 8"') in the form of a viscous liquid and having
an acid value of 15 and a molecular wsight of about
3,740.
The pol~ester- 8' and the compound listed in
~able 2 b~low. in the li~ted amount, are reactèd
in the same manner as in the ca~e of poiyester- 1 to
prepare a polyeater (hereinafter referred to as
"polyester- 8" or "P~- 8") having the properties ~iven
in the same table.
- 23 -
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g "
h
C > .~ ~ O ,0~, ~0
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rl
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.rl r~ ~~ rl h rJ
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0 ,1 ~ ~o h40 ~0 P~O
E~ o ~ ^ ,~
CQ 'I ~ ~ E~ 'I ~ C) ~I
ah)
~ ~ - O
01 O ~0 ~ o U\O
,~ ~ ~ ^ ~ O ~ O ~ o
~ ~
CI bD I I O
~ . . .
:~ bD O O O
~ ~ O I ~ 00
(~
a
a
1~ R
a) r~ ~ ~ u
?~
o ~ ~ F4
-- 24 --
.
'
6i~1~
o U~ o
.~ ~
a),~ ,~
o
o o
a
h u~ r- a:)
~ ,E3
~;
Q~
~ ~ d
h a ~o ~ . : = t
? ~ -~ ~
.,, l
~n
~ o ~
~ ~ bD ~ ~ . ~O
a~ a ~ - S - ~ .
,~ P~
C~ h E! h
E~ ~ t> +~
:~ ~ ~ o o ~
G~r~ dO dO dO ~ h
~ W ~0 ~0 ~0
,~ ~0 ~0 ~0 t~
O
U~ o~l o,lo~
~ ~ P~
h P~
_ _ _
u~ ~ O O C' o co o b0 ~1
1~ O h
~ ~ ~ ~1 o
O ~
bO l l ~ 0
U~
~: ~ O ~D ~n
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.
. h~
u~ R
-rl ~ ..
~.0 l l l ~ .
o ~ ~ F~ 1
~o
-- 25 --
,
<Prepar~tion of gr~f-t copol~mer>
1. Graft copolymer~l
A 1,000 g quantity of toluene is placed into
a 5-liter, four-necked flask equipped with a reflux
condenser, a s-tirrer and a dropping funnel and is heated
to reflux temperature in nitrogen atmosphere. A
mixture of 700 g of the polyester-l, 150 g of methyl
methacrylate, 150 g of n-butyl methacrylate, 200 g of
styrene, 150 g of glycidyl methacrylate and 30 g of
azobisisobut~ronitrile placed in a dropping funnel i~
added dropwise over a period of 3 hours to the toluene
maintained at the same temperature. Further at the
same temperature, a mixture of ~ g of azobisisobutyro-
nitrile and 30 g of ethyl acetate is added dropwise to
the resulting solution three times at an interval of
1 hour. (The catalyst thus added is hereinafter referred
to as an "additional ca~alyst"). After maintaining the
mixture under reflux for 2 hours, the condenser i9
changed to a concurrent condenser, and the mixture is
slowly heated to 150 C while permitting the solvent and
unreacted monomers to run off from the flask. After
about 60% of the ~olvent charged in has been drawn off,
the interior of the flask is maintained at 170 C at a
reduced pressure of 30 ~m Hg for 20 minutes, and then, the
contents are placed into a stainless steel vat and
- 26 -
, . . .... .
.
. .
L~
solidified by cooling to prepare a graft copolymer-l
(GP-l).
2 - 19. Graft copolymeræ- 2 to - 19.
In exactly the same manner as above, graft
copolymers-2 to-19 (GP-2 to GP-19) are prepared using
the specified amounts of materials li4ted in ~able 3.
Table 4 shows the compositions and properties of the
graft copolymers obtained.
- 27 -
.
., ~ .
.
a~ a~
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I~ r-~ ~D N O ~ I!J O
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a
r~ ~ ~:
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h a~-- ~ r~ P~ r~
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r
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4 ~. .
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a) ~ a> Q) O)
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r~ r~ r~ r~
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h c) O P~ t~ O~1 c) O r-l C~ O t.) O P~ 0 O
0 ~-- hD rd r-l 0 L~,C r~ O 0 C~ p~ 0 Lr\ ~ 4 r~ U~
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-- 28 --
r - ~
r~
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o ~ bD r~ r~ 011~rl 0 ~~1 ~a o ,1 ~O o
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-- 29 --
. . .
~4~3~
tt,
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t~o . ',
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- 3O --
.. . . .
.
.
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o~-- bD c) ,4 N o ,~ Nrl 0 N .rl 0 N
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-- 32 --
9~
bD
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U~ p~ ~1
OOOOOOOOOO
OOOOOOOOOU~
~ ~ ~ r r ~ ~. ~. r
rd~ ~1
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p~ l ~ c` ~ u~ ~ o o o o
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o ~ ~ ~J ~ ~ ~ ~ O O 00
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-- 33 --
~o
rl ~
C>
V ao ~ ~ t` O ~ ~ C'
.~'_ ~ ~1
O O
O OO O O O O O O
~ 1 ~ oo U~ o o o u~ o
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:
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0 _~
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P~ I ~ O O ~I o o o o o o ..
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- 34 -
161~
<Preparation of powder coating compositions>
Powder coating compositions are prepared,
using the ingredients given in Table 5 below in the
listed amounts.
Compositions Nos. 1 to 5, 7 to 9 and 21 are
prepared according to this invention. The other
compositions areprepared for comparison.
The ingredients are kneaded with hot rolls
at 110 C for 20 minutes, and -the mixture i5 solidified
by cooling, roughly crushed, then pulverized and
screened to obtain fine particles passing 150-mesh
sieves. ~he fine powder is then electrostaticall~
applied to a 0.8-mm thick mild steel sheet treated with
zinc phosphate and the coated sheet is heated at 150 C
for ~0 minutes for curing to prepare a test panel~
~he coating has a thickness of 40 ~ 5 ~.
' ;
- 35 -
-- .. . .... .. .. . . .. . .
. , . - . . . .
.
. :
~J4~
1~ ~rl ~:1
El bO r~
~ .~ ~ O i~
.~ 1 ~ r~
Pl p~ ~ ~ r
* I ~
O 0 0 0 1 I I ~1 ~1 0 rl r-l O
bO N ~ h
~:1` ~1 ~ o U~ ,~ ~ r-l
æ 0,~ 0,~
~: m
a ~ d
~rl rl rl
h~
h O r~rv r~ rl u~ r
1 h .~ a) h
~a bD Pl O P~ O P~ O E~ N O O
~ ~ rl ~~1 rl ~1 r
t:> ~~h .5:1 h ,q h ,~ h ~ E I
IJ~ ~ $
r-¦ r-l r-J 0
~D h h h oo o O Lr\ O O
~ ?~rd r- ~1 ~ D Ci~
E~ o.,l h
r~ rO 0 O r~l O O O O
h hr-l
0 r-l o
~ '
C~ ~ ~ ~ ~1
~rl ~ ~ rl rl rl O
r-l ~rl~rl ro r;) c.) rl
h ~ o 0 0 0 rd
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O bD 00O C) ~I C.) 0~ 0 ~D
,~ C~ ~D ~ ~\ rl ~ r~ r
h ~rlrl v c) r~ ~1 c) r-
0 ~ P1 P~ 0 0 ~
~ rl ro ~ ~ O a) ~1) O ~
Fl 0 ~ J2 CQ U2 R 0
h
:- ~ ~h r-l Or~l 8 ~8 ~ g ~8 ~ 8
4~ 0 bD I OI O I O I O I O I O
h O ~ r-l ~ r~
~,
O O r~
~i
__ _ _ ____ _~
;
.. . .
6~3~
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r~~ O ~ ~rl O r ~ rl O
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1~~ r~ r~tq ~ r~ r~
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~J r t t
o 3 3
r-l r-l r-l r~ r~ r-l `
~r~ t~ ~1 U~ O ~1 0 ~1 0 q I O ~ O ~,
,_ ~ ~ 0 r ~ l 0 r
~_ r~
r,
_ ,
I a a a a
~ ~r~ ~ r~ r~
U~ ,~ 1 0 ~1 0
~'~ h Lr~ t t hrh ~ C p~rh ~rp~
bD ~ C~ o o ~ h ~ h :~ h ~ h
rl ~ ~3 r~
t~ h O ~ ~ ~rl tl) rl 0 r-l 0 ~ 0
C:) ~E 1 ~ 0 C.) ~ rl 1--1 r~ r~l 1--1 r-l i
O ,.
r~ r~ C~ O O
~h'P~ h0 ?
0 r~l rO
C' E3
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r~ r~ r~ rl
r-l r ~ ~ 0 0
~ a~ D O Q~
O ba ~ ~ ~ ~ C) ~ O C) r~
0 r-l 0 r-l rl rrl C) r~rl r-l rl r-l
h C) 0 0 rl C) ~ I
0 ~ O ~ Q~ d r-l Q~ 0 0
O-rl rd rl d ~ ~) rl
rl t,) O V O t)
F~ ~ ~ 0 ~ 0 ~ ~ U~ ln
h
h C~ O O O O r-l O ~
r-l ~ C 000 00~ 0 r-l O r-l O ~
~ O ~D p,p,C~ p~O p,O p~O p~O,,
~h O c~ r-l~ r~ ~ r-l ~ ~ c!~ r~
O O I ~ ~ r I r-l
5z r-l r-l
- 37 -
:
, ~ .
. .
968~
~ ~--~ r1 0
~ o
~ rl ~ rl rl
~ ¢i I~
=
O
~r~ ~ O ~ = -- = ~ = = = ~ = = = .:~
rl bD ~ ~l
~_~ O
a
~ rl ~D
~ ~ +~
U~ r ~
~PI~ ~ h~ = = = _ = = = = = = = =
bD ~ h
~,
t'd ~rl 0
o F~ ~1
r1 p~ ~ > O 00
O ~ rl
,~ o h ~1 0 0 0 0 0 0
h
to ,
~rl ~ rl ~ rl ~r~
ta ~o ta 0 ta
O bO C) ~ $
h t> o O t) t) o c
~d ~ ~ ~ ~ td ~a
a~
M~ ~g U~O ~DO C~O COO O
~ ,,8 ~ ~l o ~ o ~ o ~ o ,~o
p.!, , ,~, pl p~, ~ ~ ~
~0 ~ r~
- 3~ -
: . -
.
. ... ~ ...
,
~n :
~ ~' a ~ o ~ ,~
. ,~c>
~ ~o ~ z - _ o
P'~ ~ r~ ~ :
C)
.~1 3: ~ r~l
~ bD r~ S~ ~ ~ .
r ~ 1' ci
à
~o
a' ~ t ,
U~ r~ ~
~ ~ C` : _ ~ o
m ~ ~ 0 ~rl
.. ) F~ b~ U7
o à h
r-l r~ +~ ~r
~ P~ 0 (~ O O , .
X ~ h ~ t` ~ ,~ o
O ~ rl ~ ~ 4~
h :~ 0 ~ O O
0 ,~ ,~ ~ .
C~ ~ O h h
c) 0 ns
o ,~ d ~ E 3
ri C) .~ ~d
X bD C)u~ a ~C~'D 0 0
h ~rl rl 11~ rl ~1 i~ E~
0 Q) r~
C) ~ rl rl~ r~ ~ rl Q) . ~ . .
~rl ~) ~ O C.) N
CQ ~ 0 ~ r~
h t~l O
a~
El r~ 1 ~rl
~ ~ o ~8 ~o ~ F~
t~ o bD I O I O I O
O C~ r^l ~ r-lC~ r-l * *
..
~ a)
g ~i 0~ r I (~J~0
- 39 --
`
.. - .
.
: . ' '
i~9~
Coating compositions are tested with the
results given in ~ables 6 and 7.
q`able 6
Blocking resistance Resistance
No. _ 30 a 40 C to gasoline
Good Good 2H > HB
Partially Blocked H B
blocked
12 " " H ~ 2B
Blocked " H 2B
17 " " HB ~ 6B
~ he r~sults indicate that whereas the composition
of this invention (Composition No. 5) exhibits good
blocking resistance, Compositions Nos. 10, 12, 15 and 17
ha~e very low blocking resistance because of excess
polyester content (No. 10), hi~h molecular weight of
polyester (No. 12), exce~dingly small molecular weight
of the graft copolymer (No. 15) and exceptionally low
softening point (No. 17). The latter four compositions
are also inferior in resistance to gasoline.
- 40 -
'. :
,
â~
4,
c~ ~
I t' O
~u o ~ = ~ = =
~rl ~ r C~
~ a) C~
t.) ~rl
o a~ o
~ a)o
m h~
a~
a
r~
c~ .--1 ~ o o
0 ~ O ~ 1 0 0 - -
~" o ~ b~
o .r~
r~
u~ a~ u~
r
h b[)~ h ~d
~ a~ o o o
o h o = : r O O
~1 4C~
14 a~
R .
a~
rl a~, A
C~ h
~ o
E/ ~ ~
rl O O O O O O O O O
~ ~rlA A
a~o~
~ a~o~
H h
h
~ a~
c~ a~
o a) o
O p~ r-~
~ o ~
p:~ bO ~ N (~J N N (U
E3
O O r~ 01 ~ ~ Lr~ ~D ~ 00
V~ . ,.
-- 4~.
.
'
'
.
,
,
U~ .,
r`.
. ri ~ ,. 'U F-l o
U~ ~ ~
t) rl
O u~
~1 a~ o
m h ~
U~
U~
OOOOO OOO
4-~ 0 O O O O O ~ 0 ~0 0
U~ ~
0 ~
O _ O ~ ~ Q
1~4 u~
U~, ~ O U~O u~ O U~
~ E~ N r; ~ I C` N ~i r;
~1
h
tO X ~
u~ O ~ O o æ U~ O O
~l rl ~ H H 1~ N Lr~ 1--I N 11
Pi O~ O t~l
~ ~0
H h ~O H
h
~ Uu~ I I I I I I I 1 00
C- Q)
O
~D U~ bt)
m
~ P~ i N
5 0 3
N ~ N
_ 1~2 --
~ ~4g6~4~
Coatings are tested with the results given
in Table 8 below.
~able 8
CompositionFlexural strength Adhesion
No. _ _
9 Good Good
22 Poor Poor
__ _ _
<Test methods>
1. Blocking resistance:
~he eomposition is maintained at 40 t 0. 5 C
or 30 + 0.5 C for 7 days while being subjected to a
load of 30 g/cm2 and is thereafter inspected. When
found unchanged and free of blocking, the specimen is
evaluated as "good".
2. Resistance to gasoline:
The test panel is immersed in gasoline
ttrade mark: '!Silver Gasoline", product of Nippon Oil
Co., ~td., Japan) at 20 C for 24 hours, and the immersed
portion i8 thereafter tested for pencil hardness
according to the methodof JIS K 5400, 6, 14. ~he result
iB indicated in terms of the change from the hardness
'b~fore immersion to the hardness after immersion, for
example as "2H ~ HB". The smaller the change, the
better is the resi~tance to gasoline.
- 43 -
. . . . . . ~ , , ,
. . . . :' . . : ' .
: : .
,. :
' . ~
3. Specular gloss:
Determined according to JIS K 5400, 6, 7.
4. Flexural strength:
~he test panel is ben-t, coated surface up,
over a 10-mm diameter round bar through an angle of
90 in 1 second, and the coating is inspected for
cracking. When the coating cracks, the specimen is
evaluated as "poor". The test is conducted at 20 C.
5. Adhesion:
~he test panel is immersed in boiling water
for 2 hours, thén allowed to stand in air at 20 C
for 1 hour and the coating is cross-cut to the surface
of the substrate. A cellophane tape is adhered to the
cross-cut portion and then peeled off quickl~. If the
coating i~ peeled off, the composition is evaluated as
"poor",
6. Softening point:
D~terminéd according to ring-and-ball method
(JIS K 251~).
7. Impact resistance:
After lea~ing a coated plate to qtand in a
'constant temperature and constant humidity chamber
at a temperature Or 20 + 1 D C and a humidity Or 75%
for 1 hour, th2 following te~t i8 conducted in the same
chamber. A bearer and a center of impact of prescribed
_ l~4 -
96~L
size~ (1/2 inch in diame-ter) sre fitted to a Du Pont
impsct tester and the plate is put between them,
turning the coated surface of the plate upward. The
preqcribed weight (500 g) is dropped on the center of
impact from the prescribed height and the plate i9
-taken out, and after having been left for an hour in
the room, the damage of surface is observed. ~he
largest height ~cm) of -the weight entailing no cracking
in the coating is determined.
8. Erichsen test:
The coated plate is placed in a constant
temperature and humidity chamber kept at 20 C and a
humidity of 75~/0 for one hour. Thereafter, the plate
i5 set on Erichsen test~ng machine with the coating
po~itioned outside. A punch having a radius of 10 mm
is pu~hed outward predctermined distances in contact
wibh the rear face of the plate at as uniform speed as
possible of about 0.1 mm/sec~ ~he pushed out portion
of the plate is checked by the naked eye for cracking
or peeling immediately after pushing out to determine
ths maximum distance (mm) of stroke of the punch causing
,no changes on the coatingO
9. Surfàce smoth~ess:
Determin~d wibh the n~ked e~
5 -
'
