CA1048684A - Photo-curable coating composition comprising the reaction product of an isocyanate with a polymer - Google Patents
Photo-curable coating composition comprising the reaction product of an isocyanate with a polymerInfo
- Publication number
- CA1048684A CA1048684A CA74191430A CA191430A CA1048684A CA 1048684 A CA1048684 A CA 1048684A CA 74191430 A CA74191430 A CA 74191430A CA 191430 A CA191430 A CA 191430A CA 1048684 A CA1048684 A CA 1048684A
- Authority
- CA
- Canada
- Prior art keywords
- photo
- polymer
- parts
- isocyanate
- sensitizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
- C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
- C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
Abstract
PHOTO-CURABLE COATING COMPOSITION
Abstract of the Disclosure A photo-curable coating composition is described having high hiding power and being useful in the field of paints, as well as inks. The composition is in the form of a polymer having a ratio of molecular weight to number of polymerizable double bonds of 200 to 10,000. This obtained from the reaction of an isocyanate compound containing a polymerizable double bond with a polymer containing an active hydrogen atom, a monomer polymerizable therewith and a photo-sensitizer.
Abstract of the Disclosure A photo-curable coating composition is described having high hiding power and being useful in the field of paints, as well as inks. The composition is in the form of a polymer having a ratio of molecular weight to number of polymerizable double bonds of 200 to 10,000. This obtained from the reaction of an isocyanate compound containing a polymerizable double bond with a polymer containing an active hydrogen atom, a monomer polymerizable therewith and a photo-sensitizer.
Description
! .
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
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
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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 -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, .. :' ' .
.. . . . .
..
. ::
:
~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;
., .
, ,:, - , .
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 ,. .
-' '~ "
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'. ~
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 ' ' ' , . .
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.
., .
" .~ .
.
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 -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, .. :' ' .
.. . . . .
..
. ::
:
~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;
., .
, ,:, - , .
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 ,. .
-' '~ "
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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 ' ' ' , . .
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).
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 : - ~- . . . .
;
- ~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).
;
- ~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 _ , - :
~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 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 .~ .
.
' ~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 - , ~, .
. . ~ .
- . . .
(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-'' 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 -.
.
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 .
.
. ~ ~ . , - . . ~ . -.: . ~
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 :', ., , ,. ~' .
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 .
.
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) 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 '.:
. : .
(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 _ , - :
~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 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 .~ .
.
' ~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 - , ~, .
. . ~ .
- . . .
(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-'' 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 -.
.
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 .
.
. ~ ~ . , - . . ~ . -.: . ~
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 :', ., , ,. ~' .
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 .
.
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) 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 '.:
. : .
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS;
1. 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 poly-merizable double 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 parts by weight to 100 parts by weight of the combined amount of the polymer, the monomer and the photo-sensitizer.
80 - 1 : 0.01 - 20 by weight, and the amount of the coloring agent being 3 to 50 parts by weight to 100 parts by weight of the combined amount of the polymer, the monomer and the photo-sensitizer.
2. The photo-curable composition according to claim 1, wherein the proportion of the polymer, the monomer and the photo-sensitizer is 40 - 90 : 60 - 10 : 0.1 - 10 by weight.
3. The photo-curable composition according to claim 1, wherein the polymer is the one prepared by reacting a monomer containing 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 with a polymer containing an active hydrogen atom.
4. The photo-curable composition according to claim 1, wherein the isocyanate compound is a diisocyanate or a triisocyanate.
5. The photo-curable composition according to claim 1 wherein the monomer is selected from styrene compounds, vinyl esters, (meth) acrylate compounds, alkyl compounds, unsaturated nitriles, .alpha.,.beta.-unsaturated amides and diesters of unsaturated polycarboxylic acids.
6. The photo-curable composition according to claim 1, wherein the polymer containing an active hydrogen atom is selected from polyesterpolyols and acrylic polyols.
7. A photo-curable composition having a high hiding power which comprises (1) a photo-curable urethane modified polymer having at least one unsaturation of an acrylate or methacrylate moiety in the side chain and in which the ratio of the molecular weight to the number of unsaturated polymerizable bonds is 200 - 10,000, said photo-curable urethane modified polymer being produced by reacting (A) an isocyanate compound having at least one unsat-uration of the acrylate or methacrylate moiety with (B) a polymer having at least one active hydrogen atom, said isocyanate compound (A) being produced by reacting (C) an acrylate or meth-acrylate compound having at least one acrylate or methacrylate moiety and at least one active hydrogen atom with (D) a poly-functional isocyanate having isocyanate groups bonded directly with a carbon atom;
(2) an .alpha.,.beta.-ethylenically unsaturated compound;
(3) a photo-sensitizer; and (4) a coloring agent;
the weight ratio of the photo-curable urethane modified polymer (1) to the .alpha.,.beta.-ethylenically unsaturated compound (2) to the photo-sensitizer (3) being 20 - 99 : 80 - 1 : 0.01 - 20, and the amount of the coloring agent being 3 to 50 parts by weight to 100 parts by weight of the combined amount of the photo-curable urethane modified polymer (1), the .alpha.,.beta.-ethylenically unsaturated compound (2) and the photo-sensitizer (3).
(2) an .alpha.,.beta.-ethylenically unsaturated compound;
(3) a photo-sensitizer; and (4) a coloring agent;
the weight ratio of the photo-curable urethane modified polymer (1) to the .alpha.,.beta.-ethylenically unsaturated compound (2) to the photo-sensitizer (3) being 20 - 99 : 80 - 1 : 0.01 - 20, and the amount of the coloring agent being 3 to 50 parts by weight to 100 parts by weight of the combined amount of the photo-curable urethane modified polymer (1), the .alpha.,.beta.-ethylenically unsaturated compound (2) and the photo-sensitizer (3).
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP48013288A JPS5817237B2 (en) | 1973-02-01 | 1973-02-01 | Photocurable coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1048684A true CA1048684A (en) | 1979-02-13 |
Family
ID=11829001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA74191430A Expired CA1048684A (en) | 1973-02-01 | 1974-01-31 | Photo-curable coating composition comprising the reaction product of an isocyanate with a polymer |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5817237B2 (en) |
| CA (1) | CA1048684A (en) |
| DE (1) | DE2404313B2 (en) |
| FR (1) | FR2216332B1 (en) |
| GB (1) | GB1450244A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS604058B2 (en) * | 1974-10-09 | 1985-02-01 | 吉崎 鴻造 | container lid |
| US4233425A (en) * | 1978-11-15 | 1980-11-11 | The Dow Chemical Company | Addition polymerizable polyethers having pendant ethylenically unsaturated urethane groups |
| JPS5780405A (en) * | 1980-11-10 | 1982-05-20 | Dow Chemical Co | Addition polymerizable polyethers having ethylenically unsaturated urethane branched group |
| JPS624654U (en) * | 1985-06-25 | 1987-01-12 | ||
| JPH03294322A (en) * | 1990-04-13 | 1991-12-25 | Showa Highpolymer Co Ltd | Production of graft polymer |
| US8017664B2 (en) † | 2002-05-22 | 2011-09-13 | Shell Oil Company | Process for preparing polymer polyols |
| CN112266438B (en) * | 2020-11-04 | 2022-11-15 | 三棵树(上海)新材料研究有限公司 | Methyl methacrylate polymer and preparation method and application thereof |
| CN114561002A (en) * | 2022-03-21 | 2022-05-31 | 孝感市易生新材料有限公司 | Preparation method and application of urethane-based modified polyester acrylate |
| CN115671383B (en) * | 2022-11-08 | 2023-09-12 | 杭州拉瓦生物科技有限公司 | Complete denture and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA920296A (en) * | 1970-01-29 | 1973-01-30 | J. Trecker David | Acrylates and coating compositions thereof |
| US3694415A (en) * | 1970-07-15 | 1972-09-26 | Kiyoshi Honda | Coating resinous composition |
| GB1379259A (en) * | 1970-12-07 | 1975-01-02 | Kansai Paint Co Ltd | Photopolymerizable compositions |
| DE2200478B2 (en) * | 1972-04-14 | 1976-09-23 | Inmont Corp., New York, N.Y. (V .StA.) | LIQUID, POLYMERIZING AND DRYING BINDERS MADE OF SYNTHETIC RESIN FOR PRINTING INKS |
| JPS4926061A (en) * | 1972-06-28 | 1974-03-08 |
-
1973
- 1973-02-01 JP JP48013288A patent/JPS5817237B2/en not_active Expired
-
1974
- 1974-01-30 DE DE19742404313 patent/DE2404313B2/en not_active Ceased
- 1974-01-31 GB GB453274A patent/GB1450244A/en not_active Expired
- 1974-01-31 CA CA74191430A patent/CA1048684A/en not_active Expired
- 1974-02-01 FR FR7403513A patent/FR2216332B1/fr not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2216332A1 (en) | 1974-08-30 |
| DE2404313A1 (en) | 1974-08-08 |
| GB1450244A (en) | 1976-09-22 |
| JPS5817237B2 (en) | 1983-04-05 |
| DE2404313B2 (en) | 1981-07-09 |
| FR2216332B1 (en) | 1979-01-26 |
| JPS49103931A (en) | 1974-10-02 |
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