JP2007302735A - Coating material for optical use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating material for optical use usable in spray coating, coating by using a coater, curable by UV and compatible with a curing agent having an isocyanate group in the molecule, free from surface stickiness in coated film, having excellent optical properties such as transparency, etc., exhibiting an excellent adhesion to a polymer film, sheet or molded article containing a highly polar triacetyl cellulose and an alicyclic structured polymer with low polarity. <P>SOLUTION: The invention relates to the coating material for optical use characterized by comprising (A) a thermoplastic elastomer, (B) a copolymerizable monomers comprising a monomer having an α, β-ethylenic unsaturated group and other compolymerizable monomers, and (C) an organic solvent, wherein the copolymerizable monomer (B) comprises at least one of a monomer without a functional group. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an optical coating material comprising a thermoplastic elastomer, a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers, and an organic solvent. More specifically, the present invention relates to an optical coating material that exhibits excellent adhesion to a film, sheet, or molded article having excellent optical properties, high polarity triacetyl cellulose, and low polarity alicyclic structure-containing polymer. .

Conventionally, various displays such as televisions and personal computers have used transparent materials such as plastic and glass that can transmit light. In particular, in the transparent film, triacetyl cellulose (hereinafter abbreviated as TAC) is widely used from the viewpoint of transparency and moisture impermeability, and in recent years, a film made of an alicyclic structure-containing polymer has also been used. Yes.
However, since both films have poor scratch resistance and chemical resistance, various surface treatments are performed to improve performance. Examples of these methods include a method of using an ultraviolet curable resin for the hard coat layer (Patent Document 1).
In general, an optical coating material used for various surface treatments is required to have workability, transparency, and adhesion to a base material.
Further, in recent years, there has been a problem that further enhancement of functionality, in particular, improvement of durability, is required, and there is nothing to adhere to both high polarity triacetyl cellulose and low polarity alicyclic structure-containing polymer. .
Japanese Patent Laid-Open No. 1-105738

  The present invention provides an optical coating material that solves the above-described problems described above. That is, the present invention is an optical coating material that can be applied with a spray or coated with a coater, and further UV-curable, and a curing agent having an isocyanate group in the molecule is used in combination. When the coating film is formed, the coating film surface has no stickiness, has excellent optical properties such as transparency, and has a high polarity triacetyl cellulose and a low polarity alicyclic structure-containing polymer. An object of the present invention is to provide an optical coating material exhibiting excellent adhesion to a film, sheet or molded product.

  As a result of intensive studies and studies to achieve the above-mentioned object, the present inventors have found that the thermoplastic elastomer (A), a monomer having an α, β-monoethylenically unsaturated group, and other copolymers It has been found that an optical coating material comprising a copolymerizable monomer (B) composed of a possible monomer and an organic solvent (C) is extremely useful in solving the above-mentioned problems. It came to be completed.

That is, the present invention relates to a thermoplastic elastomer (A), a copolymerizable monomer (B) comprising a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers, an organic An optical coating material comprising a solvent (C), wherein the copolymerizable monomer (B) contains at least one monomer having no functional group.
Further, an optical coating material containing at least a part of the thermoplastic elastomer (A) modified with a functional group is preferable. The optical coating material further comprises a copolymerizable monomer (D) having a photopolymerizable unsaturated bond and a photopolymerization initiator (E). Furthermore, it is an optical coating material containing a main agent containing an optical coating material having active hydrogen and / or hydroxyl groups, and a curing agent capable of reacting with active hydrogen and / or hydroxyl groups. These are triacetylcellulose and an alicyclic structure-containing polymer molded article coated with the optical coating material described above.

  According to the present invention, it is an optical coating material that can be applied by spraying or coating by a coater, and can be UV-cured, and those having active hydrogen and / or hydroxyl group have an isocyanate group in the molecule. It can also be used together with a curing agent, and when it is made into a coating film, it has no stickiness on the surface of the coating film and has excellent optical properties such as transparency. It has become possible to obtain an optical coating material exhibiting excellent adhesion to a cyclic structure-containing polymer film, sheet, or molded product.

Details of the present invention will be described below.
<Thermoplastic elastomer (A)>
Examples of the thermoplastic elastomer (A) used in the present invention include polyethylene, polypropylene, poly-1-butene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, and poly-4-methyl- 1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, represented by propylene / 1-butene copolymer, ethylene, propylene, 1-butene, 3-methyl-1-butene, 4 Of α-olefin such as methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1-octene, 1-decene and 1-dodecene, or a copolymer of two or more kinds thereof A thermoplastic elastomer is mentioned. Among these, an ethylene-butene copolymer, an ethylene-propylene copolymer, an ethylene-octene copolymer, an ethylene-propylene-butene copolymer, a propylene-butene copolymer, and a propylene-octene copolymer are preferable.
The weight average molecular weight (hereinafter abbreviated as Mw. The weight average molecular weight can be measured by, for example, gel permeation chromatography (GPC) using polystyrene as a standard) is usually 10,000 to 700, 000, preferably 30,000 to 500,000, more preferably 50,000 to 400,000.

Other examples of the thermoplastic elastomer (A) include hydrogenated styrene-conjugated diene block copolymers, hydrogenated styrene-conjugated diene random copolymers, and the like. Examples of the structure of the hydrogenated product include a hydrogenated product of a styrene-conjugated diene diblock copolymer, a hydrogenated product of a styrene-conjugated diene-styrene triblock copolymer, and the like. Examples of the conjugated diene used here include butadiene and isoprene. Among these, a hydrogenated product of a styrene-isoprene-styrene triblock copolymer and a hydrogenated product of a random copolymer of styrene-butadiene are preferable. The thermoplastic elastomer used here has a styrene content of usually 2 to 60% by weight, more preferably 3 to 45% by weight.
The weight average molecular weight is preferably in the range of 10,000 to 700,000. In the case of hydrogenated styrene-isoprene-styrene copolymer, 15,000 to 500,000, and further 20,000 to 400,000. Is preferred. Moreover, in the hydrogenated product of a styrene-butadiene copolymer, 10,000-700,000, Furthermore, 50,000-500,000 are preferable.

The thermoplastic elastomer (A) includes an alicyclic structure-containing polymer, which contains an alicyclic structure in the repeating unit of the polymer, and the alicyclic ring is present in either the main chain or the side chain. It may have a formula structure. Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure, and a cycloalkane structure is preferable from the viewpoint of thermal stability when formed into a film. The number of carbon atoms constituting the alicyclic structure is not limited, but is usually in the range of 4-30, preferably 5-20, more preferably 5-15.
The proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer is appropriately selected according to the purpose of use, but is usually 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight. % Or more. If the proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer is excessively small, the heat resistance is undesirably lowered. In addition, the remainder other than the repeating unit which has an alicyclic structure in an alicyclic structure containing polymer is not limited, According to the intended purpose, it selects suitably.

  Specific examples of the polymer containing an alicyclic structure include (1) norbornene-based polymer, (2) monocyclic olefin-based polymer, (3) cyclic conjugated diene-based polymer, and (4) vinyl fat. Examples thereof include cyclic hydrocarbon polymers and hydrogenated products thereof. Among these, from the viewpoints of dimensional stability, oxygen permeability, moisture permeability, heat resistance, opportunity strength when formed into a film, hydrogenated norbornene polymer, monocyclic olefin polymer, cyclic conjugate A diene polymer, a vinyl alicyclic hydrocarbon polymer and a hydride thereof are preferred.

(1) Norbornene-based polymer Examples of the norbornene-based polymer used in the present invention include, for example, a ring-opening polymer of a norbornene-based monomer, and a ring-opening copolymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization therewith. Examples thereof include polymers, hydrogenated products thereof, addition polymers of norbornene monomers, and addition copolymers of norbornene monomers and other monomers copolymerizable therewith. Among these, from the viewpoint of heat resistance of the film, mechanical strength, and the like, a ring-opening polymer hydrogenated product of norbornene-based monomer, and an addition copolymer of norbornene-based monomer and other monomers copolymerizable therewith are most preferable. .

As the norbornene-based monomer, bicyclo [2.2.1] -hept-2-ene (common name: norbornene), 5-methyl-bicyclo [2.2.1] -hept-2-ene, 5,5- Dimethyl-bicyclo [2.2.1] -hept-2-ene, 5-ethyl-bicyclo [2.2.1] -hept-2-ene, 5-butyl-bicyclo [2.2.1] -hept 2-ene, 5-hexyl-bicyclo [2.2.1] -hept-2-ene, 5-octyl-bicyclo [2.2.1] -hept-2-ene, 5-octadecyl-bicyclo [2] 2.1] -hept-2-ene, 5-ethylidene-bicyclo [2.2.1] -hept-2-ene, 5-methylidene-bicyclo [2.2.1] -hept-2-ene, 5-vinyl-bicyclo [2.2.1] -hept-2-ene, 5- Lopenyl-bicyclo [2.2.1] -hept-2-ene, 5-methoxy-carbonyl-bicyclo [2.2.1] -hept-2-ene, 5-cyano-bicyclo [2.2.1] -Hept-2-ene, 5-methyl-methoxycarbonyl-bicyclo [2.2.1] -hept-2-ene, 5-methoxycarbonyl-bicyclo [2.2.1] -hept-2-ene, 5 -Ethoxycarbonyl-bicyclo [2.2.1] -hept-2-ene, 5-methyl-5-ethoxycarbonyl-bicyclo [2.2.1] -hept-2-ene, bicyclo [2.2.1 ] -Hept-5-enyl-2-methylpropionate, bicyclo [2.2.1] -hept-5-enyl-2-methyloctanoate, bicyclo [2.2.1] -hept-2-ene -5,6-dicarboxylic anhydride 5-hydroxymethyl-bicyclo [2.2.1] -hept-2-ene, 5,6-di (hydroxyethyl) -bicyclo [2.2.1] -hept-2-ene, 5-hydroxy-i -Propyl-bicyclo [2.2.1] -hept-2-ene, 5,6-dicarboxy-bicyclo [2.2.1] -hept-2-ene, bicyclo [2.2.1] -hept 2-ene-5,6-dicarboxylic imide, 5-cyclopentyl-bicyclo [2.2.1] -hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] -hept-2-ene 5-cyclohexenyl-bicyclo [2.2.1] -hept-2-ene, 5-phenyl-bicyclo [2.2.1] -hept-2-ene, tricyclo [4.3.1 ^2,5 . 0 ^1,6 ] -deca-3,7-diene (common name: dicyclopentadiene), tricyclo [4.3.1 ^2,5 . 0 ^1,6 ] -dec-3-ene, tricyclo [4.4.1 ^2,5 . 0 ^1,6 ] -undeca-3,7-diene, tricyclo [4.4.1 ^2,5 . 0 ^1,6 ] -undeca-3,8-diene, tricyclo [4.4.1 ^2,5 . 0 ^1,6 ] -undec-3-ene, tetracyclo [7.4.1 ^10,13 . 0 ^1,9 . 0 ^2,7 ] -trideca-2,4,6-11-tetraene (alias: 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, common name: methanotetrahydrofluorene), tetracyclo [8.4 ^.11,14 . 0 ^1,10 . 0 ^3,8 ] -tetradeca-3,5,7,12-11-tetraene (also known as 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene), tetracyclo [4.4 .1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene (also known as tetracyclododecene), 8-methyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-ethyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-methylidene-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-ethylidene-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-vinyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-propenyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-methoxycarbonyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-hydroxymethyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-carboxy-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-cyclopentyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-cyclohexyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-cyclohexenyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-phenyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, pentacyclo [6.5.1, ^1,8 . 1 ^3,6 . 0 ^2,7 . 0 ^{9, 13]} - pentadeca -3.10- diene, pentacyclo ^{[7.4.1 3,6.} 1 ^10,13 . 0 ^1,9 . 0 ^2,7 ] -pentadeca-4.11-diene, 6-methyl-1,4,5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene and the like. It is done. These norbornene monomers are used alone or in combination of two or more.

A ring-opening polymer of a norbornene-based monomer or a ring-opening copolymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization is obtained by polymerizing the monomer components in the presence of a ring-opening polymerization catalyst. Can do. As the ring-opening polymerization catalyst, for example, a catalyst comprising a metal halide such as ruthenium, rhodium, palladium, osmium, iridium, platinum, a nitrate or an acetylacetone compound, and a reducing agent, or titanium, vanadium, zirconium, tungsten, molybdenum A catalyst comprising a metal halide such as acetylacetone compound or an organoaluminum compound can be used. The polymerization reaction is carried out in a hydrocarbon or without solvent, usually at a polymerization temperature of −50 ° C. to 100 ° C. and a polymerization pressure of 0 to 50 kg / cm ² . Examples of other monomers capable of ring-opening copolymerization with a norbornene monomer include monocyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene.

The hydrogenated ring-opening polymer of the norbornene-based monomer can be usually obtained by adding a hydrogenation catalyst to the polymerization solution of the ring-opening polymer and hydrogenating a carbon-carbon unsaturated bond. Although it does not specifically limit as a hydrogenation catalyst, Usually, a heterogeneous catalyst and a homogeneous catalyst are used. Addition (co) polymer of norbornene-based monomer or norbornene-based monomer and other monomer copolymerizable therewith, for example, monomer component in solvent or without solvent, titanium, zirconium or vanadium compound and organoaluminum compound (Co) polymerization is usually performed at a polymerization temperature of −50 ° C. to 100 ° C. and a polymerization pressure of 0 to 50 kg / cm ² in the presence of a catalyst consisting of

  Examples of other monomers copolymerizable with norbornene-based monomers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 3-ethyl. -1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3 An α-olefin having 2 to 20 carbon atoms such as ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; cyclobutene, cyclopentene, Cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohex Cycloolefins such as cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1, Non-conjugated dienes such as 4-hexadiene and 1,7-octadiene; Of these, α-olefins, particularly ethylene, are desirable.

  These other monomers copolymerizable with the norbornene-based monomer can be used alone or in combination of two or more. In the case of addition copolymerization of a norbornene monomer and another monomer copolymerizable therewith, the ratio of the structural unit derived from the norbornene monomer and the structural unit derived from the other monomer copolymerizable in the addition copolymer However, it is appropriately selected so that the weight ratio is usually 30:70 to 99: 1, preferably 50:50 to 97: 3, and more preferably 70:30 to 95: 5.

(2) Monocyclic Cyclic Olefin Polymers As monocyclic cycloolefin polymers, for example, addition polymers of monocyclic cycloolefin monomers such as cyclohexene, cycloheptene, and cyclooctene can be used. However, it is not limited to these.

(3) Cyclic conjugated diene polymer As the cyclic conjugated diene polymer, for example, a polymer obtained by subjecting a cyclic conjugated diene monomer such as cyclopentadiene or cyclohexadiene to 1,2- or 1,4-addition polymerization, and its Although a hydrogenated substance etc. can be used, it is not limited to these.
The molecular weight of the norbornene-based polymer, monocyclic olefin-based polymer or cyclic conjugated diene-based polymer used in the present invention is appropriately selected according to the purpose of use, but the cyclohexane solution (when the polymer resin does not dissolve) Is a weight average molecular weight of polyisoprene or polystyrene measured by a gel permeation chromatography method of toluene solution), and is usually in the range of 5,000 to 500,000, preferably 8,000 to 200,000, more preferably 10,000 to 100,000. In some cases, the mechanical strength and molding processability of the molded body are highly balanced and often suitable.

(4) Vinyl alicyclic hydrocarbon polymer Examples of the vinyl alicyclic hydrocarbon polymer include polymers of vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane, and hydrogenated products thereof; styrene. , Hydrogenated products of aromatic ring portions of polymers of vinyl aromatic monomers such as α-methylstyrene, and the like can be used. In this case, a copolymer such as a random copolymer or a block copolymer of a vinyl alicyclic hydrocarbon polymer or a vinyl aromatic monomer and another monomer copolymerizable with these monomers. It may be a coalescence and its hydrogenated product. Examples of the block copolymer include diblock, triblock, or more multiblock and gradient block copolymers, and are not particularly limited.

The molecular weight of the vinyl alicyclic hydrocarbon polymer used in the present invention is appropriately selected according to the purpose of use, but gel permeation chromatography of a cyclohexane solution (toluene solution when the polymer resin does not dissolve). When the polyisoprene or polystyrene-equivalent weight average molecular weight measured by a graphic method is usually in the range of 10,000 to 300,000, preferably 15,000 to 250,000, more preferably 20,000 to 200,000. In many cases, mechanical strength and moldability are well balanced.
The glass transition temperature (Tg) in the DSC measurement of the alicyclic structure-containing polymer resin used in the present invention may be appropriately selected according to the purpose of use, but is usually 40 ° C. or higher, preferably 50 ° C. to 200 ° C. ° C, more preferably in the range of 60 ° C to 180 ° C. Within this range, heat resistance and moldability are highly balanced and suitable. The above thermoplastic elastomers can be used alone or in combination of two or more.

<The thermoplastic elastomer (A) is at least partially modified with a functional group>
In the present invention, it is preferable that the thermoplastic elastomer (A) contains at least a part of which is modified with a functional group because compatibility with the polar material is improved.
In the thermoplastic elastomer (A) used in the present invention, at least partly modified with a functional group, the thermoplastic elastomer (A) described above, or a mixture of two or more of these, has the functional group described below. Obtained by reacting a monomer having an α, β-monoethylenically unsaturated group and a copolymerizable monomer (B1) comprising other copolymerizable monomers, but not partially reacting There is no problem even if it contains.

As the copolymerizable monomer (B1) comprising a monomer having an α, β-monoethylenically unsaturated group containing a functional group and other copolymerizable monomers used here, hydroxyethyl acrylate, Hydroxyl-containing vinyls such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, lactone-modified hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, acrylic Carboxyl group-containing vinyls such as acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, ω-carboxy-polycaprolactone monoacrylate, phthalic acid monohydroxyethyl acrylate, acrylamide, methacrylamide, methylolacrylamide, Chi methacrylamide, nitrogen compounds such as dimethylaminoethyl (meth) acrylate, maleic anhydride, include carboxylic anhydrides such as citraconic anhydride, it alone, can be used even more.
The addition amount of the copolymerizable monomer composed of the monomer having an α, β-monoethylenically unsaturated group containing the functional group and the other copolymerizable monomer is usually 0.5 to It is in the range of 20% by weight, more preferably 1 to 15% by weight.

<Copolymerizable monomer (B)>
Examples of the copolymerizable monomer (B) comprising a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers used in the present invention are shown below.
As monomers having α, β-monoethylenically unsaturated groups, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate , Tert-butyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate , Dodecyl (meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, lauroyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, pheny (Meth) acrylic acid such as ru (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate Esters, hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, lactone-modified hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, etc. Hydroxyl group-containing vinyls, acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, ω-carboxy-polycaprolactone monoacrylate, phthalic acid monohydroxy ester Carboxyl group-containing vinyls such as acrylates and their monoesterified products, epoxy group-containing vinyls such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate, isocyanate groups such as vinyl isocyanate and isopropenyl isocyanate Vinyls, aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, amides such as acrylamide, methacrylamide, N-methylolmethacrylamide, N-methylolacrylamide, diacetoneacrylamide, maleic acid amide , Vinyl esters such as vinyl acetate and vinyl propionate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (methacrylate, N, N-dimethylaminopropyl) Aminoalkyl (meth) such as pill (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, N, N-dihydroxyethylaminoethyl (meth) acrylate Acrylates, styrene sulfonic acid, sodium styrene sulfonate, unsaturated sulfonic acids such as 2-acrylamido-2-methylpropane sulfonic acid, mono (2-methacryloyloxyethyl) acid phosphate, mono (2-acryloyloxyethyl) unsaturated phosphoric acids such as acid phosphate, and other acrylonitrile, methacrylonitrile, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, ethylene, _propylene, a C 4 _{-C 20} alpha-olefin, 1,2,2,6,6 -Penta Methyl-4-piperidyl (meth) acrylate, 2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate, 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole Etc. Moreover, the macromonomer etc. which have the said monomer or its copolymer in a segment, and have a vinyl group at the terminal can also be used.

Examples of the copolymerizable monomer comprising other copolymerizable monomers used in the present invention include carboxylic anhydrides such as maleic anhydride and citraconic anhydride.
Moreover, description like the methyl (meth) acrylate described here shows methyl acrylate and methyl methacrylate.
It is preferable to use a monomer having an α, β-monoethylenically unsaturated group as a main component. Further, a monomer having an α, β-monoethylenically unsaturated group as a main component and other copolymerizable monomers can be used in combination.
In the present invention, a copolymerizable monomer (B) comprising a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer to the thermoplastic elastomer (A) used in the present invention. The ratio is preferably (A) / (B) = 90 / 10-20 / 80, more preferably (A) / (B) = 85 / 15-25 / 75, by weight.

  The content of the copolymerizable monomer (B) comprising a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers is reduced. When the amount of the monomer increases, the adhesion to the alicyclic structure-containing polymer decreases, the content of the thermoplastic elastomer (A) increases, or a monomer having an α, β-monoethylenically unsaturated group and other copolymers. When the content of the copolymerizable monomer (B) composed of a polymerizable monomer is decreased, the adhesion to triacetyl cellulose or the adhesion to other coating materials is lowered, and therefore the above range is preferable. Moreover, it is preferable that the copolymerizable monomer (B) contains at least one monomer having no functional group.

<Organic solvent (C)>
The organic solvent (C) used in the present invention is an aromatic hydrocarbon such as xylene, toluene or ethylbenzene, an aliphatic hydrocarbon such as hexane, heptane, octane or decane, or an alicyclic ring such as cyclohexane, cyclohexene or methylcyclohexane. Hydrocarbon organic solvents such as organic hydrocarbons, esters such as ethyl acetate, n-butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3 methoxybutyl acetate, methyl ethyl ketone, methyl isobutyl ketone And polar organic solvents such as ketone solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, etc. A mixture of two or more may be.

<Copolymerizable monomer (D) having a photopolymerizable unsaturated bond>
In this invention, it can be hardened by light, such as UV, by using the copolymerizable monomer (D) which has a photopolymerizable unsaturated bond. The photopolymerizable monomer (D) is a compound having an acrylic group. For example, ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentenyl (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonane Diol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, neopen Diglycol-modified trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, bis ((meth) acryloxyethyl) bisphenol A, tri Methylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane ditri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, ethylene oxide modified glycerol tri (meth) acrylate, propylene Oxide-modified glycerin tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythrine Lithol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, part of these (meth) acrylates substituted with alkyl groups or ε-caprolactone Examples thereof include polyfunctional (meth) acrylate, acryloylmorpholine having an active double bond, triethylene glycol divinyl ether, hydroxyethyl divinyl ether, styrene, divinylbenzene and the like.

  Furthermore, polyester poly (meth) acrylate, epoxy resin (meta) obtained by reaction of polybasic acids such as phthalic acid and adipic acid, polyhydric alcohols such as ethylene glycol and butadiol, and (meth) acrylic acid compounds. ) Epoxy poly (meth) acrylate obtained by reaction with acrylic acid compound, polysiloxane poly (meth) acrylate obtained by reaction of polysiloxane and (meth) acrylic acid compound, polyamide and (meth) acrylic acid compound Examples thereof include polyamide poly (meth) acrylate obtained by the reaction.

  In the present invention, one or more photopolymerizable monomers (D) are applied, but urethane acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, neo Pentyl glycol di (meth) acrylate, ethylene oxide modified trimethylolpropane ditri (meth) acrylate, tripropylene glycol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate are preferably used. .

Urethane acrylate is synthesized by performing polymerization by addition reaction of a diisocyanate compound and a glycol species, and further adding (meth) acrylate having an active hydrogen group such as a hydroxyl group to the remaining isocyanate group.
Examples of the diisocyanate compound include hexamethylene diisocyanate (HDI), 1,3-diisocyanatomethylcyclohexane (H ₆ XDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), and the like.

Examples of the glycol species include polyester polyols such as pivalic acid neopentyl glycol ester and polycaprolactone polyol; polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol; polycarbonate polyols such as polyhexamethylene carbonate glycol; ethylene glycol Propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,6-hexanediol, methylpentanediol, neopentyl glycol, 3,3-dimethylolheptane, carbon number 7-22 alkanediol, diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexanedimethanol Alkane-1,2-diol having 17 to 20 carbon atoms, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, glycerin 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, 1,1,1-tris (hydroxymethyl) propane 2,2-bis (hydroxymethyl) -3-butanol, other aliphatic triols having 8 to 24 carbon atoms, tetramethylolmethane, D-sorbitol, xylitol, D-mannitol, D-mannitol and the like.
Examples of the (meth) acrylate having an active hydrogen group such as a hydroxyl group include hydroxyl group-containing vinyls such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. .

<Photopolymerization initiator (E)>
The photopolymerization initiator (E) of the present invention is a compound capable of generating radicals by ultraviolet rays, electron beams, radiation, etc., and specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl. Ether, benzoin isobutyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4, 4-bis (dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1- (4-isopropylphenyl) -2-hydride Carbonyls such as xyl-2-methylpropan-1-one, sulfides such as diphenyl disulfide, dibenzyl disulfide, tetramethylthiuram disulfide, azo such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, etc. Quinones such as benzoquinone, anthraquinone, chloroanthraquinone, ethylanthraquinone and butylanthraquinone, peroxides such as benzoyl peroxide and ditertiary butyl peroxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6 -Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and other acylphosphine oxides, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone and other thiols Although xanthone etc. can be mentioned, these may be used alone or in combination of two or more. In addition, these include amines such as triethylamine, trimethylamine, triethanolamine, dimethylaminoethanol, pyridine, quinoline, trimethylbenzylammonium chloride, allylphosphines such as triphenylphosphine, thiol ethers such as β-thiodiglycol, etc. May be used in combination.

Among the above, benzophenone, methylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide are preferable, These may be used alone or in combination of two or more.
The amount of the photopolymerization initiator (E) used is a copolymerizable monomer comprising a thermoplastic elastomer (A), a monomer having an α, β-monoethylenically unsaturated group, and other copolymerizable monomers. It is 0.1 to 15 weight% normally with respect to (B), Preferably it is 1 to 10 weight%, More preferably, it is 1 to 8 weight%.

  As a method for obtaining the coating material of the present invention, (1) from a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers to a thermoplastic elastomer (A) in an organic solvent. After polymerization while feeding a copolymerizable monomer (B) and a polymerization initiator, or (2) a monomer having a thermoplastic elastomer (A) and an α, β-monoethylenically unsaturated group in an organic solvent It can be produced by a method in which a copolymer is produced while feeding a polymerization initiator to a copolymerizable monomer (B) composed of a polymer and other copolymerizable monomers, and then a radical is further generated to react. (3) a copolymerizable monomer (B) comprising a thermoplastic elastomer (A) in an organic solvent, a monomer having an α, β-monoethylenically unsaturated group, and other copolymerizable monomers; It can also be produced by a method in which a polymer composed of is reacted by generating radicals.

  Similarly, a part of the thermoplastic elastomer (A) modified with a functional group is added to a monomer comprising an α, β-monoethylenically unsaturated group and another copolymerizable monomer. After polymerization while feeding the polymerizable monomer (B) and the polymerization initiator, or a part of the thermoplastic elastomer (A) modified with a functional group and an α, β-monoethylenically unsaturated group Manufacture by a method of polymerizing the monomer and other copolymerizable monomer (B) while feeding a polymerization initiator, or a method of further generating a radical and reacting thereafter. Can do. Also, a copolymerization property comprising a part of the thermoplastic elastomer (A) modified with a functional group, a monomer having an α, β-monoethylenically unsaturated group, and other copolymerizable monomers. It can also be produced by a method in which a polymer composed of the monomer (B) is reacted with a radical.

In producing the resin, at least one selected from the group consisting of fats and oils, derivatives of fats and oils, epoxy resins, polyester resins, petroleum hydrocarbon resins, rosin resins, and terpene resins is used as the third component. be able to.
Examples of the fats and oils used as the third component include linseed oil, soybean oil, castor oil, and purified products thereof.
Oils and fats used as the third component are short oil alkyds obtained by modifying polybasic acids such as phthalic anhydride and polyhydric alcohols such as glycerin, pentaerythritol and ethylene glycol with oils (fatty acids). Resin, medium oil alkyd resin, long oil alkyd resin, etc., or rosin modified alkyd resin modified with natural resin, synthetic resin and polymerizable monomer, phenol modified alkyd resin, epoxy modified alkyd resin, acrylated alkyd resin, urethane modified Examples include alkyd resins.

  Examples of the epoxy resin used as the third component include an epoxy resin obtained by glycidyl etherification of bisphenol A, bisphenol F, novolac, etc., an epoxy resin obtained by adding propylene oxide or ethylene oxide to bisphenol A, and the like. be able to. Moreover, you may use the amine modified epoxy resin etc. which added the polyfunctional amine to the epoxy group. Furthermore, an aliphatic epoxy resin, an alicyclic epoxy resin, a polyether type epoxy resin, etc. are mentioned.

  The polyester resin used as the third component is obtained by condensation polymerization of a carboxylic acid component and an alcohol component. Examples of the carboxylic acid component include terephthalic acid, isophthalic acid, phthalic anhydride, naphthalenedicarboxylic acid, succinic acid, and glutar Acid, adipic acid, azelaic acid, 1,10-decanedicarboxylic acid, cyclohexanedicarboxylic acid, polycarboxylic acid such as trimellitic acid, maleic acid, fumaric acid and its lower alcohol ester, hydroxycarboxylic acid such as paraoxybenzoic acid, Monovalent carboxylic acids such as benzoic acid can be used, and two or more kinds can be used in combination.

  Examples of the alcohol component include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10 -Decanediol, 3-methyl-pentanediol, 2,2'-diethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, glycerin, Pentaerythritol, bisphenol A ethylenoxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct, etc. It is also possible to use.

Moreover, the resin which contained the polymerizable unsaturated bond in the molecule | numerator obtained by adding the carboxylic anhydride which has a polymerizable unsaturated bond in a molecule | numerator to the said polyester resin which has a hydroxyl group can also be used.
The petroleum hydrocarbon resin used as the third component includes, for example, an aliphatic petroleum resin whose main raw material is a C5 fraction of tar naphtha, an aromatic petroleum resin whose main raw material is a C9 fraction, and their Copolymeric alicyclic. C5 petroleum resin (resin obtained by polymerizing C5 fraction of naphtha cracked oil), C9 petroleum resin (resin obtained by polymerizing C9 fraction of naphtha cracked oil), C5C9 copolymerized petroleum resin (C5 fraction of naphtha cracked oil) C9 fraction copolymerized resin), styrene, indene, coumarone, coumarone indene resin containing dicyclopentadiene, etc., and condensation of ρ-tertiarybutylphenol and acetylene. Examples thereof include alkylphenol resins typified by products, xylene resins obtained by reacting o-xylene, ρ-xylene, and m-xylene with formalin. These can be used alone or in combination of two or more. Among these, petroleum hydrocarbon resins having a weight average molecular weight of 1,000 to 50,000 as measured by GPC are preferable, and 1,500 to 30,000 are particularly preferable. Moreover, what has a polar group in these resin is still more preferable.

  Examples of the rosin resin (E) used as the third component include modified rosin modified with natural rosin, polymerized rosin, maleic acid, fumaric acid, (meth) acrylic acid, and the like. Examples of the rosin derivative include esterified products, phenol-modified products and esterified products of the above rosins, and these hydrogenated products are preferable.

  Examples of the terpene resin used as the third component include resins made of α-pinene, β-pinene, limonene, dipentene, terpene phenol, terpene alcohol, terpene aldehyde, and the like. Α-pinene, β-pinene, Examples thereof include aromatic-modified terpene resins obtained by polymerizing aromatic monomers such as styrene on limonene, dipentene, and the like, and hydrogenated products thereof can also be mentioned. Among these, terpene phenol resins and aromatic modified terpene resins are preferable because of these hydrogenated products.

  The third component can be used alone or in combination of two or more. Further, it can be added while being fed into the reactor, or it can be first charged into the reactor and used. The amount of the third component added is usually 0.5 to 60% by weight, preferably 2 to 40% by weight, based on the resin component.

  Among the optical coating materials of the present invention, those having active hydrogen and / or hydroxyl groups containing hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, acrylic acid, methacrylic acid and the like as structural units are active hydrogen. In addition, a curing agent capable of reacting with a hydroxyl group can be used. For example, it can be used as an optical coating material having a urethane bond by mixing with a curing agent having an isocyanate group in the molecule, which is one of the curing agents capable of reacting with active hydrogen and / or hydroxyl groups.

  Examples of the curing agent having an isocyanate group in the molecule capable of reacting with active hydrogen and / or a hydroxyl group include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate. , Aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, alicyclic diisocyanates such as isophorone diisocyanate, dicyclohexylmethane diisocyanate, and other isocyanates One or more compounds and a dihydric alcohol such as ethylene glycol, propylene glycol, xylylene glycol, and butylene glycol, and a trivalent amine such as glycerin, trimethylolpropane, and trimethylolethane. Adducts of polyhydric alcohols such as coal, adducts of low molecular weight polyester resins having functional groups capable of reacting with isocyanate groups or water, or bullets, polymers of diisocyanates, lower monohydric alcohols, What blocked the isocyanate group with well-known blocking agents, such as methyl ethyl ketoxime, can be used. Also in the case of using an isocyanate prepolymer, for example, an external catalyst such as dibutyltin dilaurate or triethylamine can be added.

  Further, it is a resin synthesized from at least one of melamine, urea, benzoguanamine, glycoluril, and formaldehyde and formaldehyde, for example, a part of a methylol group or a lower alcohol such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol or the like. Amino resins which are all alkyl etherified can also be used as curing agents.

The optical coating material of the present invention and the curing agent capable of reacting with active hydrogen and / or hydroxyl group can be used in any ratio.
When the curing agent capable of reacting with active hydrogen and / or hydroxyl group is a curing agent having an isocyanate group, the mixing ratio of active hydrogen and isocyanate group is 0.5: 1.0 to 1.0: The range of 0.5 is preferable, and the range of 0.8: 1.0 to 1.0: 0.8 is more preferable.
When the curing agent capable of reacting with active hydrogen and / or a hydroxyl group is an amino resin, the weight ratio of the optical coating material / amino resin solid of the present invention is 95/5 to 20/80. Is preferable, and the range of 90/10 to 60/40 is more preferable.
The mixture of the curing agents described above can be applied and cured as it is, but a reactive catalyst can be used in combination as required.
The optical coating material of the present invention obtained above can be used as it is, but further, various stabilizers such as antioxidants, weathering stabilizers, heat resistance inhibitors, etc., inorganic materials that do not impair transparency, if necessary. These components can be contained.

The method for applying the optical coating material of the present invention is not particularly limited, but it is preferably applied by spraying, roll coater, or spin coating. For example, spray coating is performed on the surface to be coated with a spray gun. Coating can be performed with a relief printing plate, a lithographic printing plate, a gravure, a screen printing machine, or with a spin coater. The coating can usually be carried out easily at room temperature, and the drying method after coating is not particularly limited, and it can be dried by an appropriate method such as natural drying or heat forced drying.
And the optical coating material of this invention can be used as a coating material to the base material used for an optical use. For example, an alicyclic structure-containing polymer composed of triacetyl cellulose and polynorbornene, ethylene-tricyclodecane, ethylene-tetracyclododecene, ethylene-propylene-hexadiene, ethylene-propylene-ethylidene norbornene, ethylene-propylene-cyclopentadiene, etc. It can be suitably used as an optical coating material for a film, a sheet of a coalescence, polycarbonate, polyester or the like, or a molded product. In particular, it is an optical coating material that adheres widely from a highly polar substrate to a less polar substrate.
In addition to the above, the optical coating material of the present invention can be applied to solvent-type thermoplastic acrylic resins, solvent-type thermosetting acrylic resins, acrylic-modified alkyd resins, epoxy resins, urethane resins, and melamine resins. It can be used by adding.

Hereinafter, although the manufacturing method and various test examples of the resin dispersion of this invention are given and demonstrated further, this invention is not limited to these Examples.
Production Example 1 of Thermoplastic Elastomer (A)
Into a 2 liter autoclave thoroughly purged with nitrogen, 950 cm 3 of hexane and 60 g of 1-butene were added, 1 mmol of triisobutylaluminum was added, the temperature was raised to 70 ° C., and propylene and ethylene were supplied to bring the total pressure to 0. 69 MPaG, 0.30 mmol of methylaluminoxane, and 0.001 mmol of rac-dimethylsilylene-bis {1- (2-n-propyl-4- (9-phenanthryl) indenyl)} zirconium dichloride in terms of Zr atom are added. Then, propylene and ethylene were continuously supplied at a molar ratio of 95: 5, and polymerization was carried out for 30 minutes while maintaining the total pressure at 0.69 MPaG. After the polymerization, the polymer was degassed and the polymer was recovered in a large amount of methanol and dried under reduced pressure at 110 ° C. for 12 hours to obtain 24.1 g of a thermoplastic elastomer (A). The polymerization activity was 48 kg · polymer / mmol Zr · hr.

[Example 1]
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube, 160 parts of Dynalon 1320P (manufactured by JSR), which is a thermoplastic elastomer (A), and methylcyclohexane as an organic solvent 740 parts were charged and heated to 95 ° C. while replacing with nitrogen. Next, in this, 2 parts of styrene as a polymerizable monomer, 8 parts of methyl methacrylate, 21.3 parts of butyl acrylate, 6.7 parts of hydroxyethyl methacrylate, 2 parts of methacrylic acid, and tert-butyl persulfate as a polymerization initiator. A mixed solution of 0.4 part of oxy-2-ethylhexanoate (hereinafter abbreviated as PBO) was fed over 4 hours. 0.4 parts of PBO was added 1 hour and 2 hours after the end of the feed. Furthermore, 1 part of PBO was added and reacted after 1 hour. After adding PBO, the mixture was allowed to react for 2 hours to obtain an optical coating material.

[Example 2]
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube is charged with 100 parts of Dynalon 1320P, which is a thermoplastic elastomer (A), and 600 parts of methylcyclohexane as an organic solvent, and the atmosphere is replaced with nitrogen. The temperature was raised to 95 ° C. Next, a mixture of 45 parts of methyl methacrylate, 34 parts of butyl acrylate, 20 parts of hydroxyethyl acrylate, 1 part of methacrylic acid and 3 parts of PBO as a polymerizable monomer was fed over 4 hours. One part of PBO was added 1 hour and 2 hours after the end of the feed. After an additional hour, 2 parts of PBO was added and reacted. After adding PBO, the mixture was allowed to react for 2 hours to obtain an optical coating material.

[Example 3]
In a four-necked flask equipped with a stirrer, a thermometer, a reflux cooling device, and a nitrogen introduction tube, 60 parts of Dynalon 1320P, which is a thermoplastic elastomer (A), and 400 of Isopar E (manufactured by Exxon Chemical) as an organic solvent are used. The temperature was raised to 110 ° C. while charging part and replacing with nitrogen. Next, a mixture of 63 parts of methyl methacrylate, 47.6 parts of butyl acrylate, 28 parts of hydroxyethyl acrylate, 1.4 parts of methacrylic acid and 4.2 parts of PBO as a polymerizable monomer was added for 4 hours. I fed it. 1.4 parts of PBO were added 1 hour and 2 hours after the end of the feed. After 1 hour, 2.8 parts of PBO was added and reacted. After adding PBO, the mixture was allowed to react for 2 hours to obtain an optical coating material.
[Example 4]
An optical coating material was obtained in the same manner as in Example 2, except that the thermoplastic elastomer (A) was changed to Septon 2002 (manufactured by Kuraray Co., Ltd.) and the organic solvent was changed to 250 parts of methylcyclohexane.

[Example 5]
In a four-necked flask equipped with a stirrer, a thermometer, a reflux cooling device, and a nitrogen introduction tube, 100 parts of the resin obtained in Production Example 1 of the thermoplastic elastomer (A) and 340 parts of Isopar E as an organic solvent were charged. The temperature was raised to 110 ° C. while replacing with nitrogen. Next, as a polymerizable monomer, a mixed solution of 45 parts of methyl methacrylate, 34 parts of butyl acrylate, 20 parts of hydroxyethyl acrylate, 1 part of methacrylic acid and 3 parts of PBO was fed over 4 hours. One part of PBO was added 1 hour and 2 hours after the end of the feed. After an additional hour, 2 parts of PBO was added and reacted. After the PBO was added and allowed to react for 2 hours, 320 parts of methylcyclohexane was added and mixed to obtain an optical coating material.

[Example 6]
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube is charged with 200 parts of APEL 8008T (Mitsui Chemicals), which is a thermoplastic elastomer (A), and 800 parts of methylcyclohexane. Then, the temperature was raised to 95 ° C. while replacing with nitrogen. Next, as a polymerizable monomer, 4 parts of a mixed solution of 10 parts of methyl methacrylate, 19.5 parts of butyl acrylate, 20 parts of hydroxyethyl acrylate, 0.5 part of methacrylic acid and 0.5 part of PBO were used. Feeded over time. After 1 hour and 2 hours from the end of the feed, 0.25 parts of PBO was added. Furthermore, 0.5 part of PBO was added and reacted after 1 hour. After adding PBO, the mixture was allowed to react for 2 hours to obtain an optical coating material.

[Example 7]
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was charged with 100 parts of APEL 8008T, which is a thermoplastic elastomer (A), and 567 parts of methylcyclohexane, and 95 ° C. while substituting nitrogen. The temperature was raised to Then, as a polymerizable monomer, 26 parts of methyl methacrylate, 56 parts of butyl acrylate, 17 parts of hydroxyethyl acrylate, 1 part of methacrylic acid and 1 part of PBO were fed over 4 hours. 0.5 parts of PBO was added 1 hour and 2 hours after the end of the feed. Furthermore, 1 part of PBO was added and reacted after 1 hour. After adding PBO, the mixture was allowed to react for 2 hours to obtain an optical coating material.
[Example 8]
An optical coating material was obtained in the same manner as in Example 7, except that the thermoplastic elastomer (A) was changed to ZEONOR 750R (manufactured by Nippon Zeon Co., Ltd.).

[Example 9]
A four-necked flask equipped with a stirrer, a thermometer, a reflux cooling device, and a nitrogen introduction tube was charged with 100 parts of Dynalon 1320P, which is a thermoplastic elastomer (A), and 600 parts of methylcyclohexane, and 95 ° C. while substituting nitrogen. The temperature was raised to Next, as a copolymerizable monomer containing a functional group, 5 parts of maleic anhydride and PBO were added and polymerized for 2 hours, followed by 45 parts of methyl methacrylate, 34 parts of butyl acrylate, 20 parts of hydroxyethyl acrylate, methacrylic acid. A mixture of 1 part of acid and 3 parts of PBO was fed over 4 hours. One part of PBO was added 1 hour and 2 hours after the end of the feed. After an additional hour, 2 parts of PBO was added and reacted. After adding PBO, the mixture was allowed to react for 2 hours to obtain an optical coating material.

[Examples 10 to 13]
To the coating materials obtained in Examples 1, 2, 3, and 7, the photopolymerizable monomer Aronix M400 (manufactured by Toagosei Co., Ltd.) was mixed so that the weight ratio of the resin was 100/30. Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.), which is a photopolymerization initiator, was added at 3% to these resin components to obtain an optical coating material.

[Examples 14 to 15]
The coating materials obtained in Examples 2 and 7 were mixed with D-177N (manufactured by Mitsui Takeda Chemical Co., Ltd.) as a curing agent so that OH / NCO = 0.95, respectively, to obtain an optical coating material. .

[Comparative Example 1]
100 parts of Dynalon 1320P and 500 parts of methylcyclohexane as an organic solvent were charged and heated to 95 ° C. to obtain a coating material.
[Comparative Example 2]
100 parts of APEL 8008T and 500 parts of methylcyclohexane as an organic solvent were charged and heated to 95 ° C. to obtain a coating material.
[Comparative Example 3]
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was charged with 300 parts of toluene and 100 parts of butyl acetate as organic solvents, and heated to 100 ° C. while purging with nitrogen. Next, in this, a mixture of 26 parts of methyl methacrylate as a polymerizable monomer, 56 parts of ethyl acrylate, 17 parts of hydroxyethyl acrylate, 1 part of methacrylic acid and 1 part of PBO as a polymerization initiator is taken over 4 hours. Feeded. 0.3 parts of PBO was added 1 hour and 2 hours after the end of the feed. A coating material was obtained by allowing to react for 2 hours after the addition of PBO.

<< Evaluation >>
<Storage stability of resin solution>
The coating materials obtained in Examples 1 to 9 and Comparative Examples 1 to 3 were allowed to stand for 1 month at 40 ° C., and the state of the solution was evaluated. After 1 month, the coating material in which neither separation nor precipitation was confirmed was marked with ○, separation and / or precipitation observed and Δ that could be easily dispersed by stirring, separation and / or Those that could not be easily dispersed by stirring where precipitation was observed were evaluated as x, and the results are shown in Table 1. In addition, about Examples 10-15, evaluation was performed only at room temperature.
<Sprayability of resin solution>
Using a paint gun, spray the resin dispersion obtained in Examples 1-15 and Comparative Examples 1-3 at a temperature of 30 ° C. in the paint booth, and observe whether stringing occurs, Those that did not occur were marked with ◯, and those that occurred even with one were marked with ×, and the results are shown in Table-1.

<Evaluation of coating film>
1. Evaluation with TAC film The coating materials obtained in Examples 1 to 15 and Comparative Examples 1 to 3 were diluted 100% with methyl isobutyl ketone, and applied to the TAC film as a substrate so that the dry film thickness was 2 μm. , Dried at 70 ° C. for 5 minutes, and mixed with Olestar Q186 (Mitsui Chemicals) and MT Olester NM89-50G (Mitsui Chemicals Polyurethane) at OH / NCO = 0.95 Then, TINUVIN 327 (manufactured by Ciba Specialty Chemicals Co., Ltd.), which is an ultraviolet absorber, is added to the resin content at a rate of 3 μm, and the dry film thickness is 3 μm. The following evaluation was performed on the dried product.
(1) Test / Peel Test after 24 Hours After Drying: A peel test was performed with an adhesive tape.
-Transparency: About the thing which did not peel in the said evaluation, the transmittance | permeability of the monochromatic light of wavelength 550nm was measured before and behind coating, and the difference of the transmittance | permeability was evaluated.
(2) Test after Durability Test For those that did not peel in the above evaluation, a durability test at 50 ° C., 90% RH, 240 hours was performed, and the same peel test and transparency test were performed as described above.

2. Evaluation with TAC film The coating materials obtained in Examples 1 to 15 and Comparative Examples 1 to 3 were diluted 100% with methyl isobutyl ketone, and applied to the TAC film as a substrate so that the dry film thickness was 2 μm. , Dried at 70 ° C. for 5 minutes, and further diluted with Olestar RA1573 (manufactured by Mitsui Chemicals Co., Ltd.) to 3% of the resin component Irgacure 184 with a resin content diluted to 80% with ethyl acetate Then, the coating was applied so that the dry film thickness was 3 μm, and allowed to stand at room temperature for 10 minutes, and then an ultraviolet irradiation device (manufactured by Nippon Battery Co., Ltd., EPSH) installed with one 80 W / cm high-pressure mercury lamp perpendicular to the passing direction. -600-3S type) was placed at a position of 15 cm under the light source, the conveyor speed was moved at a speed of 10 m / min, and irradiation with ultraviolet rays was performed by the same method as the method of coating film evaluation 1.

3. Evaluation with the saponification-treated TAC film The evaluation was performed in the same manner as the method of the coating film evaluation 1 except that the base material was changed to the saponification-treated TAC film.
4). Evaluation with the saponification-treated TAC film The evaluation was performed in the same manner as the method of the coating film evaluation 2 except that the base material was changed to the saponification-treated TAC film.
5. Evaluation with an appel film Evaluation was performed in the same manner as the method of the coating film evaluation 1 except that the solvent for dilution was changed to methylcyclohexane and the base material was changed to an appel 8008T film.
6). Evaluation with an appel film The evaluation was performed in the same manner as the method for coating film evaluation 2 except that the solvent for dilution was changed to methylcyclohexane and the base material was changed to an appel 8008T film.
7). Evaluation with an Apel Molded Product The evaluation was performed in the same manner as the method of the coating film evaluation 5 except that the base material was changed to a molded product of Apel 6015.
8). Evaluation with an Apel Molded Product The evaluation was performed in the same manner as the method of the coating film evaluation 6 except that the base material was changed to a molded product of Apel 6015.
9. Evaluation was performed in the same manner as the method of coating film evaluation 5 except that the evaluation base material in the ZEONOR molded product was changed to a molded product of ZEONOR 1020R.
10. The evaluation was performed in the same manner as the method of coating film evaluation 6 except that the evaluation base material in the ZEONOR molding was changed to the ZEONOR 1020R molding.

<Initial physical properties>
The following tests were performed 24 hours after film formation.
Peel test: Adhesive tape was affixed to the coating film and peeled vigorously in the 90 ° C. direction.
Transparency: The transmittance of monochromatic light having a wavelength of 550 nm was measured before and after coating using a spectrophotometer. The results are shown in Table 1 where the difference in transmittance before and after coating is 2% or less, and the case where it is greater than 2% and 5% or less is Δ, and the case where it is greater than 5% is x.
<Durability>
A humidity resistance test was conducted after 50 hours at 50 ° C. and 90% RH, and the following tests were conducted.
Peel test: Evaluation was performed in the same manner as in 24 hours.
Transparency: Transmittance of monochromatic light having a wavelength of 550 nm was measured before and after the test using a spectrophotometer. The results are shown in Table 1 where the difference in transmittance before and after coating is 2% or less, and the case where it is greater than 2% and 5% or less is Δ, and the case where it is greater than 5% is x.

Claims (6)

From a thermoplastic elastomer (A), a copolymerizable monomer (B) comprising a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers, and an organic solvent (C) And the copolymerizable monomer (B) contains at least one monomer having no functional group. The optical coating material according to claim 1, comprising a thermoplastic elastomer (A) that is at least partially modified with a functional group. The optical coating material according to claim 1 or 2, further comprising a copolymerizable monomer (D) having a photopolymerizable unsaturated bond and a photopolymerization initiator (E). The optical coating material containing the main agent containing the coating material in any one of Claims 1-3 which has active hydrogen and / or a hydroxyl group, and the hardening | curing agent which can react with active hydrogen and / or a hydroxyl group. A triacetyl cellulose molded article coated with the coating material according to claim 1. A molded product of an alicyclic structure-containing polymer coated with the coating material according to any one of claims 1 to 4.