Note: Descriptions are shown in the official language in which they were submitted.
! .
1048684
The present invention relates to a photo-curable
coatlnR composition. More particularly, it relates to a
photo-curable coatinR composition _ which provides a coating
film having a high hiding power.
As photo-curable compositions,there are kno~m a
transparent composition (clear) comprising an unsaturated poly-
ester resin, a monomer polymerizable therewith and a photo-sensi-
tizer and a translucent composition comprising the said trans-
parent composition and an extender pigment having a high ultra-
~iolet ray transmittance, if necessary, together with a smallamount o~ a coloring agent such as a dye or a pigment. These
compositions are generally used as a transparent topcoat finish-
ing or a translucent undercoat finishing on ~-oods, papers, plas-
- tics or other substrates. However, they are poor in hiding
power. When a paint ~enamel) prepared by admixing one of these
. .
compositions with a ccloring agent havir.~ æ lo~ ultraviolet ray
transmittance is applied on a substrate and irradiated by ultra-
violet rays, only a very small amount of the rays cæn reach the
lowest part of the coating layer of the paint because of the
reflection and the absorption of the rays due to the coloring
agent, so that a large difference in curing is caused between
the surface and the lowest part of the said coating layer.
Conseguently, the surface of the coating layer is not smooth
but has a crepe-like appearance or becomes roughly wrinkled.
T~erefore, the coloring agent to be admixed is requircd to have
a high ultraviolet ray transmittance, and so the use of the ob-
tained paint is restricted.
For overcoming such drawback, there has been proposed
the use of a polymeri,.ation initiator such as ~m organic peroxide
and/or a polymerization promot~r such a5 a metal salt together
- 2 -
'~' . . , ~
., .
" .~ .
.
8684
with the photo-sensitizer. Howeve~? these proposals are also
not practlcal, because these agents introduce new problems such
as lowering of stability on storage and the need of using a
paint of the two liquid component type.
There has now successfully been produced a polymer
which can afford, together with a usual photo-sensitizer alone
and without any polymerization initiator and/or a polymerization
promoter, a coating film having a high hiding power, by com- `
bining a compound containing a polymerizable double bond such as
10 maleic anhydride, acrylates and methacrylates, with a polymer,
preferably at its side chain, so as to increase the radical
polymerizability. The present invention is based on the
successful production of such polymer.
According to the present invention, there is provided
; a photo-curable coating composition which comprises (a) a polymer
having a ratio of molecular weight to number of polymerizable
double bonds of 200 to 10,000, obtained from the reaction of an
isocyanate compound containing a polymerizable doùble bond with
a polymer containing an active hydrogen atom, (b) a monomer
polymerizable therewith, (c) a photo-sensitizer, and (d) a
coloring agent, the proportion of the polymer, the monomer and
the photo-sensitizer being 20 - 99 : 80 - 1 : 0.01 - 20 by weight,
and the amount of the coloring agent being 3 to 50 parrs by weight
; to 100 parts by weight of the combined amount of the polymer,
the monomer and the photo-sensitizer.
The term "monomer" as hereinabove used in connection
with the component (2) and also as hereinafter employed in
; connection with the preparation of the component (1) is intended
to mean any compound bearing a polymerizable double bond and
includes not only a monomer in the strict sense but also an
oligomer which may be formed from two or more molecules of the
monomer in the strict sense.
The polymer as the component (1) can be prepared by
-- 3 --
-
1~48684
reacting a monomer contairling a polymerizable double bond and
an active hydrogen atom with a polyfunctional isocyanate and
then reacting the resulting isocyanate compound containing a
- polymerizable double bond wi~h a polymer or pre-polymer contain-
. ing an active hydrogen atom.
- In the preparation of the isocyanate compourld~
the reaction is usually executed at a teMperature of 30 to 130C
(preferably 30 to 70C), if necessary, in the presence of 100 to
5,000 ppm (preferably 500 to 2,000 ppm) of a conventional poly-
merization inhibitor (e.g. hydroquinone, hydroquinone monomethyl
ether, benzoquinone, nitrobenzene, diphenylpicrylhydrazyl, galva-
noxyl) and of 100 to 5,000 ppm (preferably 500 to 2,000 ppm) of a
conventional urethanation (i.e. uretharie-formation) catalyst such
as a tertiary amine (e.g. triethylamine, triethylenediamine, N-
methylmorpholine) or an organotin compound (e.g. stannous octa-
noate, dibutyltin dilaurate, distannoxane) until one iSGCyanate
group remains in each molecule of the produced isocyanate compo-
und in average. The presence of the isocyanate group may be con-
firmed by a conventional amine.back titration procedure or by the
absorption at around 2,200 cm 1 in the IR absorption spectrum.
Sometimes, a part of the starting polyfunctional isocyanate may
remain unreacted, or arly compound containing no isocyanate group
may be by-produced in the reaction. The product containing
these contaminants may be as such subjected to the s~lbsequent
reaction with the polymer containing an ac~ive hydrogen atom.
However, ~hen an acrylic polymer is used as the said polymer,
.. :' ' .
.. . . . .
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..
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~4~684
. . ~
the elimination of these contaminants by a conventional proce-
dure (e.g. extraction, distillation, adsorption) i~ often desir-
ed.
The subsequent reaction of the thus obtained isocyanate
compound with the polymer containing an active hydrogen atom is
cont~d until the r~tio o~ the molecular weight to the nu~ber
of polymerizable double bonds of the produced poly~er becomes
200 to 10,000 (preferably.5C0 to 5,000). ~hen the said ratio is
smaller than 200, the coating film produced by the resulting
polymer has a poor flexibility. When the ratio is larger th2n
10,000, the film is hardly cured. As the case may be, the re-
action may be performed in the presence of a polymerization
inhibitor and an urethanation catalyst as mentioned above.
The reaction temperature is usually 30 to 1~0C, preferably 60
. .
to 120C. The isocyanate group can be detected by the method
as above mentioned. If necessary, a polymerizable monomer con-
taining no active hydrogen atom sensitive to the isocyanate
group (e.g. methyl methacrylate) may be incorporated into the
reaction system.
As the said monomer containing a polymerizable double
bond and an active hydrogen atom, the use of the one havin~ only
; one active hydrogen atom in the molecule is favorable. ~xamples
o~ 8uch monomer are a~ follows (wherein the term "(meth)acrylate"
means acrylate and methacrylate)~
(1) Compound~ containing a hydroxyl group such as
allyl alcohol, 2-hydroxyethyl ~meth)acrylate, polyethyieneelycol
mono(meth)aorylate and polypropyleneglycol mono(meth)acrylate;
(2) Compounds containinS an amino group such ~s mono-
methylaminoethyl (meth)acrylate and monoethylaminoethyl (meth)-
acrylate;
., .
- 5 -
,
,:, - , .
1~)48684
- (3) Products obtained from the reaction between
acrylic acid or mebhacrylic acid and a monoepoxy compound (e.g.
glycidyl (meth)acrylate, glycidyl tertiary alkanoates ("Cardura
- ~" trademark of Shell Chemical Corp.), n-butyl glycidyl
ether, allyl glycidyl ether);
(4) Products obtained from the reaction between
glycidyl (meth)acrylate and a monocarboxylic acid (e.g. acetic
P acid, butyric acid, ber.zoic acid) or a secondary monoamine
(e.g. dimethylamine, diethylamine, piperidine, methylaniline),
0 etc.
As the polyfunctional isocyanate, there may be employed
any conventional one, but the use of a diisocyanate or a triiso-
- cyanate is favorable. ~xamples of them are (1) ethylene diiso-
.. . . . .
cyanate, propylene diisocyanate, tetramethylene diisocyanate,
hexamethylene diisocyanate, l-methyl-2,4-diiso~yanatocyclohexane,
l-methyl-2,6-diisocyanatocyclohexane,~ ~-diisocyanatodiethyl-
benzene, ~,u~-diisocyanatodimethyltoluene, ~,u~-diisocyanato-
dimethylxylene, ~,~'-diisocyanatodiethylY.ylene, lysine diiso-
oyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 4,4'-ethylene-
bis(cyclohexyl isocyanate), ~,~'-diisocyanato-1,3-dimethylbenzene
diisocyanato-1,4-dimethylbenzene, isophorone diisocyanate,
2,4-tolylene diisocyanate, 2,6~tolylene diisocyanate, 1,5-
naphthylcne diisocyanate, 4,4'-methylenebis(phenylisocyanate),
triphenylmethane triisGcyanate, etc. and their polymers such as
dimers and trimers; (2) products obtained from the addition of
; excess of them to low molecular wei~ht polyols (e.g. ethylene-
glycol, propyleneglycol, 1,3-butylglycol, neopentylglycol, 2,2,4-
:: ,
trimethyl-1,3-pentanediol, hexamethyleneglycol, cyclohexansdi-
- methanol, trimethylolpropane, hexanetriol, glycerol, sorbitol,
30 ~orbitan, sucrose, pentaerythritol); and (3) polyisocyanates
- 6 -
,. .
-
' '~ "
~ ! , , ' .
'. ~
1~)48684
having a biuret structure or an allophanate structure. The~e
polyfunctional isocyanates may be used alone or in combination.
~he partial urethanation reaction of the diisocyanate or tri- -
icocyanate with the low molecular weight polyol may be effected
in the presence of an ureth~ation catalyst as employed in the
5imilar manner to the preparation of the isocyanate compound
containing a polymerizable double bond described above.
; As the poly:ner containing an active hydrogen atom, there
may be used the one usually employed in the preparation of a poly-
urethane compound by the reaction with an isocyanate. Therc may
be also used the one in which a polymerizable double bond has
been already introduced by a conventional procedure. Ex~mples -~ -
of such polymer containing an active hydrogen atom are as follows:
(1) Polyetherpolyols (preferably having a molecular
; weight of about 500 to 10,000) obtained by the addition of an -
alkylene oxide (e.g. ethylene oxide, propylerAe oxide, tetrahydro-
iuran) to a polyol (e.g. ethyleneglycol, diethyleneglycol, pro-
pylene~lycol, dipropyleneglycol, glycerol, trimethylolpropane,
; 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,2,6-hexanetriol,
pentaerythritol, sorbitol, sorbitan, sucrose).
(2) Polyesterpolyols (preferably having a molecular
... ...
weight of about 500 to 10,000) obtained by the reaction of the
above mentioned polyol with an epoxy comp~ourd (e.g. "Cardura E",
n-butyl glycidyl ether, allyl glycidyl ether, di(methylglycidyl)
esters of dicarboxylic acids and their derivatives ("~piclon"
trademark of Dainippon Ink & Chemicals Inc.)) ar.d a polycar-
boxylic acid or its anhydride or ester (e.g. adipic acid, suc-
cinic ~hydride, maleic ~nhydride, phthalic anhydride, tetra-
hydrophthalic anhydride, terephthalic acid, itaconic acid) or
the reaction of the above mentioned polyol or epoxy compound
. . .
- ~ 7 -
.. .
. .
,
- . .- ,: . .. . .: ' . '~ '
- , , . . . ., : .
b
' ' ' , . .
1048684
with the polycarboxylic acid or its anhydride or ester. The-
8aid polyols, epoxy compounds and polycarboxylic acids mzy
be used alone or in combin~tion, res~ectively.
(3) Polyesterpolyols containin~ a polymerizable
double bond (prefer~bly having a molecular weight of about
500 to 10,000) obtained by the reaction of a polyesterpolyol
containing a carboxyl group with a polymerizable ur~saturated
epoxy ccmpound (e.g. glycidyl methacrylate, allyl glycidyl
ether) or the reaction of a polyesterpolyol containing a gly-
cidyl group with a polymerizable unsaturated carboxylic acid
(e.g. acrylic acid, methacrylic acid).
(4) ~olymers obtained by the ring opening of cyclic
esters having a molecular weight of about 500 to 4,000 (e.g.
polycaprolactone, polybutyrolactone).
(5) Esters (pre~erably having a molecular weight of
about 500 to 4~000) obtained by the esterification of a polyol
with a higher fat~y acid (e.g. mono, di or triethyleneglycol
mono or diricinoleate, 1,2,6-hexanetriol mono, di or triricino-
leate, trimethylolpropane mono, di or triricinoleate, penta-
erythritol mono, di, tri or tetraricinoleate, castor oil, hydro-
genated castor oil, castor oil fatty acid mono or diglyceride,hydrogenated castor oil fatty acid mono or diglyceride).
(6) Acrylic polyols (preferably having a molecular
; weight of about 500 to 30,000) such as homopolymers of alkylene-
glycol monoacrylate or .~ono.nethacrylate and copolymers of them
~ith poly~erizable ~ono~ers (e.g. styrene, dibutyl fumarate,
acrylic acid, methacrylic acid, ~crylic ester, methacrylic ester,
elyc~dyl methacrylate, ethylene, propylene, vinyl chloride,
~inylidene chlor~dc, butadiene, isoprene, vinyl acetate)
(7) Acrylic polyols (preferæbly having a molecular
-- 8
: - ~- . . . .
;
- ~48684
~eight of about 500 to 30,000) containing a polymerizable dnuble
bond obtaincd by t~le half esterification of an acrylic polyol
~th an unsaturated polycarboxylic anhydride (e.g. maleic an- -
hydride, it~conic anhydride).
(8) Acrylic polyols (preferably having a molecular
- weight of sbout 500 to 30,000) cont~ining a polymerizable double ~ --
bond obt~ined by thc esterification of t~e carboxyl group at the
~ide chain of an acrylic polyol with ~ polymerizable unsaturated
epoxy compound (e.g. glycidyl methacrylate, allyl glycidyl
ether),
(9) Acrylic polyols (preferably having a molecular
~eight of about 500 to 30,000) containing a polymerizable double
- bo~d obtained by the esterification of the glycidyl group at the
side chain of an acrylic polyol with a polymerizable unsaturated
carboxylic Acid (e.g. acrylic acid, methacrylic acid).
(10) Polyurethanepolyols obtained by the urethanation
oi the above mentioned polyetherpolyol, polyesterpolyol or the
like with a polyisocyanate.
(11) hnion poly~eri7.ation products (preferably having
a molecular weight of about 500 to 10,000) substituted with a
functior.al ~roup having an active hydrogen atom at the er.d of
the ~olecule (e.g. polyethylenediol~ polybutadienediol, poly-
styrenediol, diols of copolymers of the monomeric constituents
o~ the above polymers).
(l?) Saponification products of copoly~ers of vinyl
esters (e.g. vinyl acetate) with vinylpyrrolidone, polyamido-
polyamine ~nd polyethylQneimine.
Amone the ~bove mentioned poly~ers cont~inin~ an ~
active hydro~en atom, the polyesterpolyols .Ind the acrylic polyols
are particularly favorable.
_ g _
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~048684
Examples of the monomer as the component (2) are as
. follo~r~ (wherein the term "(meth)acrylnte" means acrylate ~nd
methacryl~te):
- . (1) Styrene compounds such as styrene, vinyltoluene, .
t-butylstyrene, monochlorostyrene, ~-rnethylstyrene and divinyl-
: benzene;
(2) Vinyl esters such as vinyl acetate, vinyl
propionate, vinyl butyrate and vinyl benzoate;
(3) (Meth)acrylate compounds such as methyl (meth)-
. 10 acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, cyclo-
hexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, methoxy-
b~tyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate and tri-
methylolpropane tri(meth)acrylate;
(4~ Allyl compounds such as allyl methacrylate and
triallyl isocyanurate;
- (5) Unsaturated nitrile~ such as acrylonitrile;
: ... . ~ .
~ . . . (6) a,B-Unsaturated amides such as acrylamide and
- N-butoxymethylacrylamide; .
(7) Diesters of unsaturated polycarbo~ylic acids such
, .. ........ . . ...... .
a8 diethyl itaconate, dibutyl itaconate, diethyl fumarate, di-
butyl ~umarate, dimethyl maleate and dibutyl maleate.
These monomers are employed alone or in combination
depending on the purpose of the use of the coating composition
to be prepared, since the properties of the coating film are
~aried by the combination of these monomers with the said polymers.
: As the photo-sensitizer, there may be used a con~en-
tional one sueh as benzoin, benzoin ethers, benzophenone, benzil,
2,4-dichlorobenzaldehyde or disulfides.
In the composi.tion of the invention, the proportion :~
of the polymer, the monomer and the photo-sen~itizer may be
- -- 10 --
1048684
20 - 99 : 80 - 1 : 0.01 - 20 by weight, preferably 40 -
90 :- 60 - 10: 0.1 - 10 by weight. When the proportion
of the polymer is smaller than the said lower limit, the
coating composition becomes hardly cured and the proper-
ties of the coating film are deteriorated. The use of
the monomer in a larger amount is desirable for increas-
ing the curing property. When the phot-sensitizer is
smaller than the said lower limit, the curing proceeds
with difficulty. Even if the amount exceeds the said
upper limit, any change in the curing property is not
expected, and the use of such a large amount of the agent
is not economical.
The composition of the invention may be diluted with
an organic solvent inert to ultraviolet rays. It can be
used not only for a clear coating but also for a colored
coating by incorporating various coloring agents therein.
Any kind of coloring agents can be used for the purpose
of colored coating, but there is a tendency that, when a
coloring agent having a high ultraviolet ray transmitta~e
(e.g. prussian blue, ultramarine, cadmium pigment) is
employed, it can be incorporated in a high concentration
and when a coloring agent having a low~ultraviolet ray
transmittance e.g. phthalocyanine blue, phthalocyanine
green~ is employed, it can be incorporated only in a low
concentration. Although the amount of the coloring agent
depends on the kind of the coloring agent or the film
thickness, it is preferred to be in a range of 3 to 50
parts by weight to 100 parts by weight of the composition
i.e. the combined amount of the three essential compon-
ents (1), (2) and (3), in order to assure a sufficient
hiding. When the amount of the coloring agen* is smaller
than the said lower limit, the coating film necessitated
for hiding is made thicker. When the amount exceed
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~0~8684
the said upper limit, the curing property at the film
thickness necessary for assurance of good film properties
is lowered and the film appearance is very poor. In
case of requiring a thin coating film, however, the color-
ing agent may be used in an amount larger than the said
upper limit.
The preparation of the coating composition of the
invention may be carried out by mixing of the polymer,
the monomer and the photo-sensitizer, when used, with
the coloring agent by the aid of a conventional dispersing
machine such as ball mill or three roll mill. The coat-
ing composition may be applied on a substrate by a conven-
tional procedure and then irradiated by ultraviolet rays
for curing. If necessary, the substrate receiving the
composition may be allowed to stand prior to the irradia-
tion so as to evaporate the inert solvent which may be
present in the composition. Practically, the irradiation
may be performed by exposing the substrate applied the
composition to the sun shine or an artificial light of
250 and 500 m~ , preferably 300 to 400 m , in wave
length. As the light source, there may be used a carbon ~ -
arc lamp, an ultra-high pressure mercury lamp,
a low pressure mercury lamp, a metal
halide lamp, a xenone lamp, a chemical lamp or the like.
The composition of the invention can be used not
only in the field of paints b~t also in any other field
such as inks.
Practical and presently preferred embodiments of the --
invention are illustratively shown in the following
Examples wherein parts are by weight.
.. . .
Reference Example 1
In a flask equipped with a stirrer, there are
charged xylylene diisocyanate (a mixture of w,w'-diisocy-
anat~
: - 12 -
.~', .
. . - , - . . .
' '' . l~g8684
1,3-dimethylbenzene and ~,~'-diisocyanato-1,4-dimethylbenzene)
(180 parts)~and hydroquinone (0.16 part), and the contents
are 8tirred while cooling with water to keep below 70C.
mixture of 2-hydroxyethyl methacrylate (130 parts), dibutyltin
dilaurate (0.63 part) and hydroquinone (0.16 part) is dropwise
added thereto over about 1.5 hours. After the addition, the
resultant mixture i~ aged for about 30 minutes to obtain an
isocyanate compound having a polymerizable double bond.
R~eference Example 2
; In a flask equipped with a stirrer, there are
charged glycidyl methacr~late (156 parts), dibutyltin dilaurate
(0.12 part) and hydroquinone (0.24 part). ~o the mixture,
methacrylic acid (86 parts) is dropwise added at 100 to 115C
over about 2 hours under nitrogen atmosphere. l'he reaction is
effected at the same temperature until the acid value becomes
2 or less. ~he reaction mixture i9 cooled to room temperature,
and dibutyltin dilaurate (0.63 part) and hydroquinone (0.23
part) are added thereto. The obtained mixture is dropwise added
to a flask equipped with a stirrer which contains isophorone
dii~ocyanate (222.3 parts) and hydroquinone (0.23 part), and
the re~ulting mixturc is aged as in Reference Example 1 to ob- -
tain an isocyanate compound having a polymerizable double bond.
eference Example 3
In a flask equipped with a stirrer, there are
¢harged phthalic anhydride (296 parts), tetrahydrophthalic
anhydride (304 parts), adipic acid (292 parts). ethylene
glycol (62 parts), "Cardura E" (490 parts), "Epiclon" (mole-
cular wei~ht 360; epoxy equiv~lent, 180) (720 parts) and toluene
~73.4 p~rts), and the contents are reacted ~t 150C under nitrogen
atmosphere until the acid v~lue bccomes 58 or less to o~tain
.
: .
1~48684
a polyester polyol. After the tempcrature i~ lowered to 130~C,
glycidyl methacrylate (284 parts), triphenyl phosphite (12 part3)
, and hydroquinone (1.2 parts) are added thereto, and the reaction
.i8 effected at 130C until the acid value becomes 10 or les~ to
obtain an unsaturated polyester prepolymer.
. . .
- Reference Example 4
.~ .
In a flask equipped with a stirrer, the unsaturated
polyester prepolymer (2534.6 parts) p~epared in Reference '
~xample 3 is charged and stirred at 110C under nitrogen at-
mosphere. ~he isocyanate compound obtained in Reference Example
1 (311 p~,rts) is dropwise added thereto over about 1 hour, and
the reaction is effected for 3 to 10 hours to give a polymer
which shows a ratio of the molecular weight to the nu~ber of
~ .
polymerizable double bonds of 919. A~ter confirming the com- ~,'
plete reaction of the isocyanate group, methyl methacrylate (638
parts) and hydroquin,one (1.4 parts) are added to the reaction
mixture to obtain an urethane-modi~ied polymer composition
containing the polymer. '
Reference Example 5
The unsaturated polyester prepolymer (2534.6 parts)
prepared in Reference Example 3 and the isocyanate compound
(622 parts) obtained in Reference Example 1 are reacted as in ~ ;
Reference Example 4 to give a polymer which shows a ratio of
the molecular wei~ht to the number of polymerizable double bonds
of 767. Methyl methacrylate (716 parts) and hydroquinone (1.5
parts) are ~dded to the re:~ction mixture to obtain an urethane-
modified polymer composition containing the polymer.
Reference Exam~le 6
The unsaturated polyester prepolymer (2534.6 parts)
prepared in Reference Example 3 and the i~ocyanate compound
, ~ ~
. - 14 - ,
~, .
. . ~ .
- . . .
1048684
(933 parts) obtained in Reference Example 1 are reacted
as in Reference Examp]e 4 to give a polymer which shows
a ratio of the molecular weight to the number of poly-
merizable double bonds of 676. Methyl methacrylate
(793.6 parts) and hydroquinone (1.7 parts) are added to
the reaction mixture to obtain an urethane modified,
polymer composition containing the polymer.
ReferenceExample 7
The unsaturated polyester prepolymer (2534.6 parts)
prepared in Reference Example 3 and the isocyanate com-
pound(1244 parts) obtained in Reference Example 1 are
reacted as in Reference Example 4 to give a polymer which
shows a ratio of the molecular weight to the mumber of
polymerizable double bonds of 615. Methyl methacrylate
(850 parts) and hydroquinone (1.7 parts) are added to the
reaction mixture to obtain an urethanemodified polymer
composition contaning the polymer.
Reference Example 8
The unsaturated polyester prepolymer (2534.6 parts)
prepared in Reference Example 3 and the isocyanate com-
pound(1555 parts) obtained in Reference Example 1 are
reacted as in Reference Example 4 to give a polymer which
shows a ratio of the molecular weight to the number of
polymerizable double bonds of 571. Methyl methacrylate
(908 parts) and hydroquinone (2.0 parts) are ad~ed to
the reaction mixture to obtain an urethane-modifie~ ~oly
mer composition containing the polymer.
Reference Example 9
The unsaturated polyester prepolymer (2534.6 parts) ~-
prepared in Reference Example 3 and the isocyanate com-
- 15 -
''
1048684
pound (931.5 parts) obtained in Reference Example 2
are reacted as in Reference Example 4 to give a poly-
mer which shows a ratio of the molecular weight to 1
the number of polymerizable double
- 15a -
.
' .:'' . , ' ' ' : '. . ' ' ~ ' . ~:
1~4~684
bond~ of 558. ~lethyl methacrylate (72~ parts) and hydro~uinone
(1.5 parts) are added to the rcaction mixture to obtain an
urethane-modified polymer composition containing the polymer.
'? Reference XxamPle 10
In a flask equipped with a stirrer, there are
charged tetrahydrophthalic anhydride (152 part~), 2-hydroxy-
ethyl methacrylate (143 parts) and hydroquinone (0.28 part),
and the contents are stirred at 120C. A mixture of glycidyl
! methacrylate (142 parts), hydroquinone (0.14 part) and triethyl-
amine (2.11 parts) is dropwise added thereto over about 1 hour,
and the resultant mixture is reacted at the same temperature
until the acid vaiue becomes 9 or less. The reaction mixture
i8 cooled to room temperature, and dibutyltin dilaurate (0.6
part) and hydroquinone (0.3 part) are added thereto. The
obtained mixture is reacted with xylylene diisocyanate (180
-; parts) and hydroquinone (0.3 part) in a flas~ equipped with a
8tirrer as in Reference ~xample 1 to obtain an isocyanate com-
pound.
Reference Exam~le 11
In a flask equipped with a stirrer, there are
charged methyl methacrylate (340 parts), styrene (100 parts),
~-butyi acrylate (50 parts), 2-hydroxyethyl methacrylate (10
part~), laurylmercaptan (1 part) and toluene (350 parts), and
the contents are stirred at 100 to 110C in nitrogen atmosphere.
A mixture of 2,2'-azobisisobutyronitrile (5 parts) and toluene
~150 parts) is dropwise added thereto o-~er about 3 hours. The
resultant mixture is aged at the same temperature for 2 hours
to obtain ~n acrylic polyol having a number a~crage molecular
wei~ht of 17,000. To the thus obtained acrylic polyol, meth~l
methacryl~tc (129 part3) and hydroquinone (0.26 part) are added,
.~ .
.
i~ - 16 -
.
.
1048684
and the mixture is reacted with the isocyanate compound
(15.9 parts) prepared in Reference Example lO in the
same manner as in Reference Example 4 to give an urethane ~;
modified polymer composition containing a polymer which -
shows a ratio of the molecular weight to the number of
polymerizable double bonds of 9521.
Example l
The polymer composition obtained in Reference Exa~
mple (125 parts), triallyl isocyanurate (25 parts),
benzoin methyl ether (2.5 parts) a~d titanium oxide
("Tioxide R-CR 3" trade mark of British Titan Products
Corp.) (12.5 parts) are dispersed to obtain a coating
composition. The thus prepared composition is applied
on a clean polished plate of steel. After allowed to
stand for lO minutes, the plate is subjected to irradia-
tion by a high pressure mercury lamp (2 KW, one lamp)
for 3 minutes at a distance of 15 cm to form a coating
film.
Example 2
As in Example 1, the polymer composition obtained
in Reference Example 7 (125 parts), triallyl isocyanu-
rate (50 parts), benzoin methyl ether (3 parts), and '
"Tioxide R-CR 3" (15 parts) are dispersed to make a
coating composition, from which a coating film is pre-
,~! pared ~
Example 3
As in Example l, the polymer composition obtained iin Reference Example 7 (125 parts), trimethylolpropane
trimethacrylate ~Z5 parts), benzoin methyl ether (2.5
- 17 -
.
.
. ~ ~ . ,
- . . ~ . -
.: . ~
1048684
parts) and "Tioxide R-CR 3" (12.5 parts) are dis-
persed to make a coating composition, from which a ::
coating film is prepared.
ExamEle 4
As in E~ample l, the polymer composition obtained
.
.
I
. I
~ ,
''
~ 17a _
:' :
~)4~684
.. . .
in Reference Example 7 (125 parts), trimethylolpropane tri-
methacrylate (50 parts), ben7.0in methyl ether (~ parts) and
nTioxide R-CR 3" (15 parts) are dispersed to make a coating com-
po~ition, from which a coating film i9 prepared. -
xam~le 5
A8 in Example 1, the polymer composition obtained
in Reference Example 4 (125 parts), trimethylolpropane tri-
methacrylate (50 parts), benzoin methyl ether (2.5 parts)
and "Tioxide R-CR 3" (10 parts) are dispersed to-make a coæting
composition, fro~ which a coating film is prepared. Up to a
thickness of the film being 80 ~, curing is effected without
any undesirable change on the surface. The pencil hardness is B.
. Example 6
. ~8 in Example 1, tke polymer composition obtained
- in Reference ~xample 5 (125 parts), tri~ethylolpropane tri- --
. .
methacrylate (50 parts), benzoin methyl ether (2.5 parts) and ~-
nTioxide R-CR 3" (10 parts) are dispersed to make a coating
. , .
composition, from which a coating film is prepared. Up to a
thickness of the film being 85 ~, curing is effected without
any undesirable change on the surface. The pencil hardness ïs H.
Example 7
As in Example 1, the polymer composition obtained
~n Reference Example 6 (125 parts), trimethylolpropane tri-
methacrylate (50 parts), benzoin methyl ether (2.5 parts~ and
"Tioxide n-CR 3" (10 parts) are dispersed to makc a coating com-
;~ po8ition, from which a coating film is prepared. Up to a
thickness of the film being 100 ~, curir.g is effected without
any undesirable chanee on the ~urface. The pencil hardness is H.
. Exa~ple 8
-~ 30 Ao in Ex~mple 1, the polymer composition obtained
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:', ., , ,. ~' .
1048~i84
in Reference Example 11 (222 parts), N-butoxymethylacrylamide
(~5 parts)j benzoin methyl ether (2.5 parts) and cobalt blue
(60 parts) are dispersed to make a coating composition, from
which a coatin~ film i3 pre~ared. Up to a thickness of the
film being 110 ~, curing is effected without an~ unde~irable
change on the surface. The pencil hardness is H. The thickness
of the film required for hiding is 100 ~, when calculated from
the value determined by the aid of a cryptometer.
-ExamPle 9 ' -
As in ~xample 1, the polymer composition obtained ~-~
in Reference Example 8 (125 parts), trimethylolpropane tri-
methacrylate (25 parts), methyl methacrylate (25 parts), benzoin
methyl ether (2.5 parts) and an organic red pigment ("Colofine
-Red 236" trademark of Dainippon Ink & ~hemicals Inc.) (20
parts) are dispersed to make a coating composition, from which
a coating film is prepared. Up to a thickness of the film being
. 100 ~, curing is effected without any undesirable change on the
~ur~ace. The pencil hardness is H. The thickness of the film
required for hiding is 90 ~, when calculated from the value
determined by the aid of a cryptometer.
Example 10
As in Example 1, the polymer composition obtained
in Reference Example 7 (125 parts), trimethylolpropane tri-
methacrylate (25 parts), benzoin methyl ether (2.5 parts) and
- an or~anic orange pi~ment ("Chlorol Orange Y ~0-789-D~ trade-
mark of DuPont) ~20 parts3 are dispersed to m~ke a coatin~
composition, from which a coating film is prep~.red; Up to a
thickness of the film being 90 ~, curing is effected without any
unde~ir~le chanF,e on the surface. The pencil h~rdness is 2EI.
The thickness of the film required for hidin6 is 50 ~, when
.
.
1048684
calculated from the value determined by the ~aid of
a cryptometer.
Example 11
As in Example 1, the polymer composition obtained
in Reference Example 7 (125 parts), tetrahydrofurfryl
methacrylate (25 parts), styrene (25 parts), benzoin
isopropyl ether-(2.5 parts) and-an inorganic black pig-
ment ("Cobalt Black XD-3~J4" trademark of Kyokujitsu
Sangyo Co., Ltd.) (40 parts) are dispersed to make a
coating composition, from which a coatfilm is prepared.
Up to a thickness of the film being 100 , curing is
effected without any undesirable change on the surface.
The pencil hardness is H. The thickness of the film
required for hiding is 80 , when calaulated from the
: .
value determined by the air of a cryptometer.
E~ample 12.
As in Example 1, the polym~r composition obtained
in Reference Example 9 (125 parts), -trimethylpropane tri-
methacrylate (25 parts), methyl methacrylate (25 parts)
benzoin methyl ether (2.5 parts) and red iron oxide
("~eny Bengara No. 501" trademark of the Tone Sangyo
Co., Ltd.) (10 parts) are dispersed to make a coating
composition, from which a coating film is prepared. Up
to a thickness of the film being 80~ , curing is ~
effected without any undesirable change on the surface.
The pencil hardness is H. rlhe thickness of the film
required for hiding is 40~ , when calculated from the
value determined by the aid of a cryptometer.
; Control Example 1
Unsaturated polyester resin ("Goaelack 750" trade-
mark of Nippon Synthetic Chemical Industry Co., Ltd.) `-
(solid content, 100 parts), styrene (25 parts), benzoine
methyl ether ((2.5 parts)
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104868~
and "Tioxide R-CR-3" (12.5 parts) are dispersed as in
Example 1 to make a coating composition.
Control Example 2
"Goselack 750" (solid content, 100 parts), triallyl
isocyanurate (50 parts), benzoin methyl ether (3 parts)
and "Tioxide R-CR 3" (-15 parts) are dispersed as in
Example 1 to make a coating composition.
Control Example 3
"Goselack 750" (solid content, 100 parts), trimethyl-
lolpropane trimethacrylate (25 parts), benzoin methyl
ether (2.5 parts) and "Tioxide R-CR 3 (12.5 parts) are
dispersed as in Example 1 to make a coating compo~ition
The propert~es of the coating films formed by the
use of Example 1 to 4 and Control Examples 1 to 3 are
shown in Table 1
Table 1
,: . _ . ,
Properties Ex ~mple No. ~ 1 Example No.
coating film 1 2 3 4- ¦ 1 ~ 3
Maximum
thickness *)5060 70 90 1 28 r 20
; Pencil
hardness **)H 2B H HB j ~5B 1 2B I H
,: , _
Note: *) Maxdmum thickne,ss of ~e coatin~ film not
, pro uclng any aonormallty ~ucn às crepe-
like appearance or wrinkle formation
(macroscopically observed).
**) Hardness of the coating film having the
maximum thickness
'.:
. : .
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