JP7643100B2 - Acrylic urethane resin having polymerizable unsaturated group, active energy ray curable resin composition, cured product and article - Google Patents

Description

The present invention relates to an acrylic urethane resin having a polymerizable unsaturated group, an active energy ray-curable resin composition, a cured product, and an article.

Automobile exterior parts such as headlamps, safety sensors, and roofs have the problem that their functionality is temporarily impaired by snowfall and rainfall. In recent years, methods have been investigated that allow snow and rain to slide off the surface of components naturally while the vehicle is in motion, as well as methods of applying coating agents to prevent dirt from adhering and improve dirt removal.

As a method for applying a coating agent on top, a method for introducing a fluorine structure or a silicone structure for the purpose of imparting water repellency to the coating layer is known. For example, an active energy ray curable resin composition is known which is obtained by blending a urethane (meth)acrylate compound containing a polysiloxane structure with a reactive fluorine-containing compound of a specific structure (see, for example, Patent Document 1). However, the water repellency of the obtained cured product does not satisfy the increasingly high required characteristics in the future, and is not sufficient for today's market demands.

Therefore, there was a demand for materials with even better water repellency.

JP 2014-080585 A

The problem that the present invention aims to solve is to provide an acrylic urethane resin having a polymerizable unsaturated group that has excellent water repellency, and an active energy ray-curable resin composition, cured product, and article that contain the same.

As a result of intensive research into solving the above problems, the present inventors discovered that the above problems could be solved by using an acrylic urethane resin having a polymerizable unsaturated group, the essential raw materials of which are a polyol compound made from two specific types of polysiloxane compounds and a compound having a hydroxyl group and a polymerizable unsaturated group, and an isocyanate compound having a polymerizable unsaturated group, and thus completed the present invention.

That is, the present invention provides an acrylic urethane resin having a polymerizable unsaturated group, the essential raw materials of which are an acrylic polyol compound (A) and an isocyanate compound (B) having a polymerizable unsaturated group,
The present invention relates to an acrylic urethane resin having a polymerizable unsaturated group, characterized in that the acrylic polyol compound (A) is an acrylic copolymer containing, as essential raw materials, a polysiloxane compound (a1) having one (meth)acryloyl group in one molecule, a polysiloxane compound (a2) having at least two (meth)acryloyl groups in one molecule, and a compound (a3) having a hydroxyl group and a polymerizable unsaturated group, and an active energy ray-curable resin composition, cured product, and article containing the same.

The acrylic urethane resin having a polymerizable unsaturated group of the present invention has excellent water repellency and can be suitably used in paints, etc.

The acrylic urethane resin having a polymerizable unsaturated group of the present invention is characterized in that it contains, as essential raw materials, an acrylic polyol compound (A) and an isocyanate compound having a polymerizable unsaturated group (B).

As the acrylic polyol compound (A), an acrylic copolymer is used whose essential raw materials are a polysiloxane compound (a1) having one (meth)acryloyl group in one molecule, a polysiloxane compound (a2) having at least two (meth)acryloyl groups in one molecule, and a compound (a3) having a hydroxyl group and a polymerizable unsaturated group.

In the present invention, "(meth)acryloyl" means acryloyl and/or methacryloyl. "(meth)acrylate" means acrylate and/or methacrylate. "(meth)acrylic" means acrylic and/or methacrylic.

The polysiloxane compound (a1) having one (meth)acryloyl group per molecule (hereinafter abbreviated as "polysiloxane compound (a1)") may, for example, be a polysiloxane compound represented by the following general formula (1):

[In formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrocarbon group having 2 to 10 carbon atoms, R ³ each independently represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 4 to 100.]

In addition, examples of commercially available products of the polysiloxane compound (a1) include "Silaplane FM-0711" (number average molecular weight Mn: 1,000), "Silaplane FM-0721" (number average molecular weight Mn: 5,000), "Silaplane FM-0725" (number average molecular weight Mn: 10,000), and "Silaplane FM-0731" (number average molecular weight Mn: 10,000), all manufactured by JNC Corporation. Examples of such compounds include "X-22-174ASX" (number average molecular weight Mn: 900), "X-22-174BX" (number average molecular weight Mn: 2,300), "KF-2012" (number average molecular weight Mn: 4,600), "X-22-2426" (number average molecular weight Mn: 12,000), and "X-22-2404" (number average molecular weight Mn: 420) manufactured by Shin-Etsu Chemical Co., Ltd. Among these, "Silaplane FM-0711", "Silaplane TM-0701T", "X-22-174ASX", and "X-22-174BX" are preferred because they produce urethane (meth)acrylate resins capable of forming cured products with excellent water repellency. These polysiloxane compounds can be used alone or in combination of two or more kinds.

The number average molecular weight of the polysiloxane compound (a1) is preferably less than 10,000, and more preferably in the range of 300 to 3,000, since an acrylic urethane resin capable of forming a cured product having excellent water repellency can be obtained. In the present invention, the number average molecular weight indicates a value measured by gel permeation chromatography (GPC).

The polysiloxane compound (a2) having at least two (meth)acryloyl groups in one molecule (hereinafter abbreviated as "polysiloxane compound (a2)") includes, for example, a polysiloxane compound represented by the following general formula (2):

[In formula (2), R ¹ 's each independently represent a hydrogen atom or a methyl group, R ² 's each independently represent a hydrocarbon group having 2 to 10 carbon atoms, R ³ 's each independently represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 4 to 100.]

In addition, examples of commercially available products of the polysiloxane compound (a1) include "Silaplane FM-7711" (number average molecular weight Mn: 1,000), "Silaplane FM-7721" (number average molecular weight Mn: 5,000), and "Silaplane FM-7731" (number average molecular weight Mn: 5,000), all manufactured by JNC Corporation. FM-7725" (number average molecular weight Mn: 10,000), Shin-Etsu Chemical Co., Ltd.'s "X-22-164" (number average molecular weight Mn: 380), "X-22-164AS" (number average molecular weight Mn: 900), "X-22-164A" (number average molecular weight Mn: 1,740), "X-22-164B" (number average molecular weight Mn: 3,200), "X-22-164C" (number average molecular weight Mn: 4,800), "X-22-164E" (number average molecular weight Mn: 7,800), and "X-22-2445" (number average molecular weight Mn: 3,200). Among these, "Silaplane FM-7721", "Silaplane FM-7725", "X-22-164B", "X-22-164C", "X-22-164E", and "X-22-2445" are preferred because they produce urethane (meth)acrylate resins capable of forming cured products with excellent water repellency. These polysiloxane compounds can be used alone or in combination of two or more types.

The number average molecular weight of the polysiloxane compound (a2) is preferably 2,000 or more and less than 15,000, more preferably in the range of 2,000 to 12,000, since this produces an acrylic urethane resin capable of forming a cured product with excellent water repellency.

Examples of the compound (a3) having a hydroxyl group and a polymerizable unsaturated group include aliphatic (meth)acrylate compounds such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol tri(meth)acrylate; 4-hydroxyphenyl acrylate, β-hydroxyphenethyl acrylate, 4-hydroxyphenethyl acrylate, 1-phenyl-2-hydroxyethyl acrylate, 3-hydroxy-4-acetylphenyl acrylate, 2-hydroxyethyl ... -hydroxy-3-phenoxypropyl acrylate and other aromatic ring-containing (meth)acrylate compounds; polyether-modified (meth)acrylate compounds obtained by ring-opening polymerization of the above-mentioned (meth)acrylate compounds with various cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether; lactone-modified (meth)acrylate compounds obtained by polycondensation of the above-mentioned (meth)acrylate compounds with lactone compounds such as ε-caprolactone, and the like. These compounds having a hydroxyl group and a polymerizable unsaturated group can be used alone or in combination of two or more kinds. Among these, 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate are preferred because they can produce acrylic urethane resins capable of forming cured products with excellent water repellency.

The method for producing the acrylic polyol compound (A) is not particularly limited, and the compound can be produced by a known method. For example, the compound (a1), the compound (a2), and the compound (a3) can be copolymerized in the presence of a polymerization initiator.

The various conditions for producing the acrylic polyol compound (A) can be appropriately set according to the raw materials used and their amounts. For example, some of the raw materials are first added to a reaction vessel, heated to 80°C to 160°C, and then the remaining raw materials are added dropwise over 2 to 8 hours to carry out a polymerization reaction; an organic solvent is added to a reaction vessel, heated to 80°C to 160°C, and then the mixture of raw materials used in the reaction is added dropwise over 2 to 8 hours to carry out a polymerization reaction; an organic solvent is added to a reaction vessel, heated to above the boiling point of the organic solvent under sealed and pressurized conditions, and then the mixture of raw materials used in the reaction is added dropwise over 2 to 8 hours to carry out a polymerization reaction.

Examples of the isocyanate compound (B) having a polymerizable unsaturated group include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate. In addition, commercially available products can be used as the isocyanate compound (B) having a polymerizable unsaturated group, and examples of the commercially available products include Karenz AOI, Karenz MOI, and Karenz BEI manufactured by Showa Denko K.K. These isocyanate compounds having a polymerizable unsaturated group can be used alone or in combination of two or more types.

The isocyanate compound (B) having a polymerizable unsaturated group may be one obtained by adding a (meth)acrylate compound having a hydroxyl group to one of the isocyanate groups of a diisocyanate compound.

Examples of the diisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; and aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate.

Examples of the (meth)acrylate compound having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, etc.

The method for producing the acrylic urethane resin having a polymerizable unsaturated group of the present invention is not particularly limited, and it can be produced by a known method. For example, a method of subjecting a polymerizable compound containing the acrylic polyol compound (A) and the isocyanate compound (B) having a polymerizable unsaturated group to a urethane reaction in a reaction vessel can be mentioned.

The various conditions for producing the acrylic urethane resin having a polymerizable unsaturated group of the present invention can be appropriately set depending on the raw materials used and their amounts. For example, the acrylic polyol compound (A) and the organotin catalyst are first added to a reaction vessel, and the reaction vessel is heated to 60°C to 100°C while air is being blown into the reaction vessel, and then the isocyanate compound (B) having a polymerizable unsaturated group is added dropwise to carry out a urethane reaction to produce the resin.

The active energy ray-curable resin composition of the present invention contains the urethane (meth)acrylate resin of the present invention, a compound having a polymerizable unsaturated group other than the urethane (meth)acrylate resin, and a photopolymerization initiator.

Examples of compounds having a polymerizable unsaturated group other than the urethane (meth)acrylate resin (hereinafter, sometimes referred to as "other compounds having a polymerizable unsaturated group") include aliphatic mono(meth)acrylate compounds such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and octyl(meth)acrylate; alicyclic mono(meth)acrylate compounds such as cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and adamantyl mono(meth)acrylate; (meth)acrylate compounds; heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; mono(meth)acrylates such as benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, and aromatic mono(meth)acrylate compounds such as phenylphenoxyethyl (meth)acrylate;

1,6-Hexanediol di(meth)acrylate, 1,4-Butanediol di(meth)acrylate, 1,3-Butylene glycol di(meth)acrylate, 1,9-Nonanediol di(meth)acrylate, 1,10-Decanediol di(meth)acrylate, Neopentyl glycol di(meth)acrylate, Ethylene oxide modified 1,6-Hexanediol di(meth)acrylate, Hydroxypivalic acid neopentyl glycol di(meth)acrylate, Propylene oxide modified neopentyl glycol di(meth)acrylate, Tripropylene glycol di(meth)acrylate, Dipropylene glycol di (meth)acrylate, triethylene glycol di(meth)acrylate, ethylene oxide modified di(meth)acrylate of bisphenol A, propylene oxide modified di(meth)acrylate of bisphenol A, ethylene oxide modified di(meth)acrylate of bisphenol F, tricyclodecane dimethanol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, propylene oxide modified tri(meth)acrylate of glycerin, 2-hydroxy-3-acryloyloxypropyl(meth)acrylate, p) acrylate, ethylene oxide modified di(meth)acrylate of bisphenoxyethanol fluorene, polytetramethylene glycol di(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, phenoxyethylene glycol (meth)acrylate, stearyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, trifluoroethyl (meth)acrylate 3-methyl-1,5 pentanediol di(meth)acrylate, 2,3-[(meth)acryloyloxymethyl]norbornane, 2,5-[(meth)acryloyloxymethyl]norbornane, 2,6-[(meth )acryloyloxymethyl]norbornane, 1,3-adamantyl di(meth)acrylate, 1,3-bis[(meth)acryloyloxymethyl]adamantane, tris(hydroxyethyl)isocyanuric acid di(meth)acrylate, 3,9-bis[1,1-dimethyl-2-(meth)acryloyloxyethyl]-2,4,8,10-tetraoxospiro[5.5]undecane, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, ditrimethylolpropane di(meth)acrylate and other bifunctional (meth)acrylates;

Trifunctional (meth)acrylates such as EO-modified glycerol (meth)acrylate, PO-modified glycerol tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, EO-modified phosphoric acid tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, HPA-modified trimethylolpropane tri(meth)acrylate, (EO) or (PO)-modified trimethylolpropane tri(meth)acrylate, alkyl-modified dipentaerythritol tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, and tris(methacryloxyethyl)isocyanurate;

Tetrafunctional (meth)acrylates such as ditrimethylolpropane tetra(meth)acrylate, pentaerythritol ethoxy tetra(meth)acrylate, and pentaerythritol tetra(meth)acrylate;

Pentafunctional (meth)acrylates such as dipentaerythritol hydroxypenta(meth)acrylate and alkyl-modified dipentaerythritol penta(meth)acrylate;

Examples include hexafunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate.

Further examples include (poly)oxyalkylene-modified (meth)acrylates in which a polyoxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various (meth)acrylates mentioned above, and lactone-modified (meth)acrylates in which a (poly)lactone structure has been introduced into the molecular structure of the various (meth)acrylates mentioned above.

These compounds having polymerizable unsaturated groups can be used alone or in combination of two or more. In addition, compounds having an average of 2 to 6 polymerizable unsaturated groups per molecule are preferred, as they can produce urethane (meth)acrylate resins capable of forming cured products with excellent water repellency.

Examples of the photopolymerization initiator include photoradical polymerization initiators such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone.

Commercially available photopolymerization initiators include, for example, "Omnirad 1173", "Omnirad 184", "Omnirad 127", "Omnirad 2959", "Omnirad 369", "Omnirad 379", "Omnirad 907", "Omnirad 4265", "Omnirad 1000", "Omnirad 651", "Omnirad TPO", "Omnirad 819", "Omnirad 2022", "Omnirad 2100", "Omnirad 754", "Omnirad 784", "Omnirad 500", "Omnirad 81" (IGM) Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", "KAYACURE OA" (Nippon Kayaku Co., Ltd.); "Vicure 10", "Vicure 55" (Stoffa Chemical Co.); "Trigonal P1" (Akzo Nobel Co., Ltd.), "SANDORAY 1000" (SANDOZ Co., Ltd.); "DEAP" (Upjohn Chemical Co., Ltd.), "Quantacure PDO", "Quantacure ITX", "Quantacure EPD" (Ward Blenkinsop Co., Ltd.); "Runtecure 1104" (manufactured by Runtec). These photopolymerization initiators can be used alone or in combination of two or more.

The amount of the photopolymerization initiator added is preferably in the range of 0.5 to 20% by mass in the active energy ray-curable resin composition.

In addition, since the active energy ray-curable resin composition can improve the curability of the cured coating film of the active energy ray-curable resin composition, a photosensitizer can be further added to improve the curability, if necessary.

The photosensitizers include 2,4,6-trimethylbenzophenone, 2,3,4-trimethylbenzophenone, 4-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4-(1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl)benzophenone, methyl-o-benzoylbenzoate, [4-(methylphenylthio)phenyl]phenylmethanone, (4-benzoylbenzyl)trimethylammonium chloride, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)2-hydroxy-2-methyl-1-phenyl Examples of photosensitizers include 1-nylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one polymers, diethoxyacetophenone, dibutoxyacetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin normal butyl ether, amine compounds such as aliphatic amines and aromatic amines, urea compounds such as o-tolylthiourea, and sulfur compounds such as sodium diethyldithiophosphate and s-benzylisothiuronium-p-toluenesulfonate. These photosensitizers can be used alone or in combination of two or more types.

The active energy ray-curable resin composition of the present invention may also contain various additives, such as ultraviolet absorbers, polymerization inhibitors, antioxidants, organic solvents, inorganic fillers, polymer particles, pigments, defoamers, viscosity adjusters, leveling agents, flame retardants, and storage stabilizers, as necessary.

Examples of the ultraviolet absorber include triazine derivatives such as 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These ultraviolet absorbers can be used alone or in combination of two or more.

Examples of the polymerization inhibitor include phenolic compounds such as p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline; quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, and diphenoquinone; melamine, p-phenylenediamine, 4-aminodiphenylamine, and N. N'-diphenyl-p-phenylenediamine, N-i-propyl-N'-phenyl-p-phenylenediamine, N-(1.3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, reaction products of styrenated diphenylamine and 2,4,4-trimethylpentene, reaction products of diphenylamine and 2,4,4-trimethylpentene, and other amine compounds, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl=bis[3-(dodecylthio)propionate], ditridecane-1-yl= Thioether compounds such as 3,3'-sulfanediyldipropanoate, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl-p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-N-n-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, N- Nitroso compounds such as nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N-n-propylurethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-sodium sulfonate, 2-nitroso-1-naphthol-4-sodium sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, and 2-nitroso-5-methylaminophenol hydrochloride; esters of phosphoric acid and octadecane-1-ol; triphenyl phosphite; 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane; trisnonylphenyl phosphite; and (1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl phosphite. Examples of the polymerization inhibitor include phosphate compounds such as esters, 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, and tris(2,4-di-tert-butylphenyl)phosphite, zinc compounds such as bis(dimethyldithiocarbamato-κ(2)S,S')zinc, zinc diethyldithiocarbamate, and zinc dibutyl dithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel, and sulfur compounds such as 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilauryl thiodipropionate, and 3,3'-thiodipropionate distearyl. These polymerization inhibitors can be used alone or in combination of two or more.

The antioxidant may be the same as the compounds exemplified as the polymerization inhibitor, and the antioxidant may be used alone or in combination of two or more kinds.

In addition, examples of commercially available products of the polymerization inhibitor and the antioxidant include "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumilizer BBM-S" and "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd.

The organic solvent may be the same as those exemplified above, and the organic solvent may be used alone or in combination of two or more kinds.

Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, etc. These inorganic fillers can be used alone or in combination of two or more kinds.

As the pigment, known inorganic pigments or organic pigments can be used.

Examples of the inorganic pigments include white pigments, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, carbon black, graphite, etc. These inorganic pigments can be used alone or in combination of two or more kinds.

Examples of the white pigment include titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, zinc sulfide, etc. These white pigments can be used alone or in combination of two or more kinds.

Examples of the organic pigments include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, azo pigments, etc. These organic pigments can be used alone or in combination of two or more.

Examples of the defoaming agent include silicone-based defoaming agents, polyether-based defoaming agents, and fatty acid ester-based defoaming agents. These defoaming agents can be used alone or in combination of two or more types.

Examples of the viscosity modifier include acrylic polymers and synthetic rubber latexes that can be thickened by adjusting the alkalinity, urethane resins that can be thickened by molecular association, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol, water-added castor oil, amide wax, polyethylene oxide, metal soaps, dibenzylidene sorbitol, etc. These viscosity modifiers can be used alone or in combination of two or more kinds.

Examples of the leveling agent include silicone-based compounds, acetylene diol-based compounds, and fluorine-based compounds. These leveling agents can be used alone or in combination of two or more types.

Examples of the flame retardant include inorganic phosphorus compounds such as red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and phosphoric acid amides; phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxy, Examples of such flame retardants include organic phosphorus compounds such as cyclic organic phosphorus compounds such as 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof reacted with compounds such as epoxy resins and phenolic resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine; silicone-based flame retardants such as silicone oil, silicone rubber, and silicone resin; and inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. These flame retardants can be used alone or in combination of two or more.

The cured product of the present invention can be obtained by irradiating the active energy ray-curable resin composition with active energy rays. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, irradiation may be performed in an inert gas atmosphere such as nitrogen gas, or in an air atmosphere in order to efficiently carry out the curing reaction by ultraviolet rays.

As a source of ultraviolet light, ultraviolet lamps are commonly used from the standpoint of practicality and economy. Specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs, etc.

The cumulative light amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ/m ² , and more preferably 0.5 to 10 kJ/m ^2. When the cumulative light amount is within the above range, it is preferable because the occurrence of uncured portions can be prevented or suppressed.

The irradiation of the active energy rays may be carried out in one step or in two or more steps.

The article of the present invention has a coating film of the cured product. Examples of the article include plastic molded products such as mobile phones, home appliances, automobile interior and exterior materials, and office automation equipment, as well as semiconductor devices, display devices, and imaging devices.

The present invention will be specifically described below with reference to examples and comparative examples. Note that the present invention is not limited to the examples listed below.

In the present examples, the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using a gel permeation chromatograph (GPC) under the following conditions:

Measuring device: Tosoh Corporation HLC-8220
Column: Tosoh Corporation guard column _HXL -H
+ Tosoh Corporation TSKgel G5000HXL
+ Tosoh Corporation TSKgel G4000HXL
+ Tosoh Corporation TSKgel G3000HXL
+ Tosoh Corporation TSKgel G2000HXL
Detector: RI (differential refractometer)
Data processing: Tosoh Corporation SC-8010
Measurement conditions: Column temperature 40°C
Solvent Tetrahydrofuran
Flow rate: 1.0 ml/min. Standard: polystyrene Sample: 100 μl of a tetrahydrofuran solution containing 0.4% by mass of resin solids filtered through a microfilter

(Example 1: Preparation of acrylic urethane resin (1) having a polymerizable unsaturated group)
A flask equipped with a stirring rod, a temperature sensor, and a water-cooled condenser was charged with 65 parts by mass of butyl acetate, and the mixture was heated to 110 ° C. while stirring and flowing dry nitrogen. A mixture of 37 parts by mass of methyl methacrylate, 33 parts by mass of isobornyl acrylate, 17 parts by mass of normal butyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate, 2 parts by mass of polysiloxane compound (a1) (manufactured by JNC Corporation, "Silaplane FM-0701T", number average molecular weight 423), 1 part by mass of polysiloxane compound (a2) (manufactured by JNC Corporation, "Silaplane FM-7721", number average molecular weight 5,000), 5 parts by mass of (2-ethylhexanoyl) (tert-butyl) peroxide (manufactured by NOF Corporation, "Perbutyl O"), and 17 parts by mass of butyl acetate was added dropwise from a dropping funnel over a period of 4 hours to carry out acrylic polymerization. After confirming that the viscosity and non-volatile content were constant, the mixture was cooled to 70°C to obtain polyol compound (1). Next, 0.1 parts by mass of dibutyltin dilaurate and 3.2 parts by mass of 2-acryloyloxyethyl isocyanate ("Kallens AOI" manufactured by Showa Denko K.K.) were charged into the same flask containing polyol compound (1). The temperature was raised to 80°C, and the reaction was continued as it was. The reaction was terminated when the isocyanate group disappeared, and the non-volatile content was adjusted to 55% by mass with butyl acetate to obtain acrylic urethane resin (1) having a polymerizable unsaturated group. The number average molecular weight (Mn) of this acrylic urethane resin (1) having a polymerizable unsaturated group was 4,400, and the weight average molecular weight (Mw) was 14,700.

(Comparative Example 1: Preparation of urethane acrylate resin (R1))
A flask equipped with a stirring rod, a temperature sensor, and a water-cooled condenser was charged with 165 parts by mass of butyl acetate, 111.0 parts by mass of isophorone diisocyanate (isocyanate group content 37.8% by mass), 0.01 parts by mass of methylhydroquinone, and 0.1 parts by mass of dibutyltin dilaurate, and the temperature was raised to 60° C. Next, 296.2 parts by mass of a hydroxyl group-containing polysiloxane compound ("Silaplane FM-DA11" manufactured by JNC Corporation, number average molecular weight 1,000, hydroxyl value 94.7) was charged and reacted at 80° C. When the residual isocyanate groups reached 3.1% by mass, 120 parts by mass of pentaerythritol (tri/tetra)acrylate ("Aronix M-305" manufactured by Toagosei Co., Ltd., hydroxyl value 126 mgKOH/g) was further added, and the reaction was continued as is. When the isocyanate groups disappeared, the reaction was terminated to obtain a urethane acrylate resin (R1). The non-volatile content of this urethane acrylate resin (R1) was 80% by mass.

(Example 2: Preparation of active energy ray-curable resin composition (1))
A photopolymerization initiator, an ultraviolet absorber, and a light stabilizer were blended with the acrylic urethane resin (1) having a polymerizable unsaturated group obtained in Example 1 so as to obtain the ratio shown in Table 1 in terms of solid content, and the ratio was adjusted with butyl acetate to obtain an active energy ray-curable resin composition (1) having a non-volatile content of 50 mass %.

(Comparative Example 2: Preparation of active energy ray curable resin composition (R1))
An ethylenically unsaturated compound (dipentaerythritol hexaacrylate, "DPA-600T" manufactured by Toagosei Co., Ltd.), a photopolymerization initiator, an ultraviolet absorber, and a light stabilizer were blended into the urethane acrylate resin (R1) obtained in Comparative Example 1 so as to obtain the ratio shown in Table 1 in terms of solid content, and the ratio was adjusted with butyl acetate to obtain an active energy ray-curable resin composition (R1) having a non-volatile content of 50 mass %.

The following evaluations were carried out using the active energy ray-curable resin compositions (1) and (R1) obtained in the above examples and comparative examples.

[Method for evaluating coating appearance]
The active energy ray curable resin compositions obtained in the Examples and Comparative Examples were applied to a polycarbonate substrate using a bar coater so that the film thickness after drying would be 10 μm, and after drying at 70° C. for 5 minutes, a cured coating film was formed by irradiating the film with ultraviolet light using a high pressure mercury lamp (lamp output 160 W/cm) so that the cumulative irradiation amount was 30 kJ/m ^2. The appearance of the obtained cured coating film was visually observed and evaluated according to the following criteria.

○: The coating film was transparent and had no abnormalities.
×: The coating film was clouded or craters were found on the surface of the coating film.

[Method for evaluating adhesion]
Using the above cured coating film, 100 1 mm square grids were made on the surface of the coating film by cutting with a cutter knife in a 10 x ¹⁰ grid pattern at 1 mm intervals. Next, cellophane tape was applied to the grids and then quickly peeled off to conduct a grid test, and the number of remaining grids out of the 100 grids was evaluated according to the following criteria.

A: The number of remaining pieces was 100.
Δ: The number of remaining particles was 90 or more and less than 100.
×: The number of remaining particles was less than 90.

[Water repellency evaluation method]
The water repellency was evaluated by measuring the water contact angle and the water sliding angle.

[Method for measuring water contact angle]
The contact angle of purified water of the cured coating film formed on the polycarbonate substrate was measured using "DMo-501" manufactured by Kyowa Interface Science Co., Ltd. The higher the value, the better the water repellency.

[Method of measuring water sliding angle]
The sliding angle of purified water was measured for the cured coating film formed on the polycarbonate substrate using "DMo-501" manufactured by Kyowa Interface Science Co., Ltd. The sliding angle was measured by placing a 20 μL water droplet on the coating surface, tilting the measuring table by 1° each time, and measuring the angle at which the water droplet moved 2 cm. The lower the value, the better the sliding property and water repellency. If the water droplet did not slide even when tilted by 90° or more, it was indicated as "X".

The compositions and evaluation results of the active energy ray-curable resin composition (1) prepared in Example 2 and the active energy ray-curable resin composition (R1) prepared in Comparative Example 2 are shown in Table 1.

In addition, the parts by mass of the acrylic resin (1) having a polymerizable unsaturated group and the urethane acrylate resin (R1) in Table 1 are solid content values.

In Table 1, "Photopolymerization initiator (A)" refers to "Omnirad 184" manufactured by IGM Resins.

"Photopolymerization initiator (B)" in Table 1 refers to "Omnirad TPO" manufactured by IGM Resins.

"UV absorber" in Table 1 refers to "Tinuvin 400" manufactured by BASF Japan Ltd.

"Light stabilizer" in Table 1 refers to "Tinuvin 123" manufactured by BASF Japan Ltd.

Example 2 shown in Table 1 is an example of an active energy ray-curable resin composition of the present invention. It was confirmed that this active energy ray-curable resin composition has excellent water repellency.

On the other hand, Comparative Example 2 is an example of an active energy ray-curable resin composition that does not use an acrylic urethane resin having a polymerizable unsaturated group. It was confirmed that this active energy ray-curable resin composition has a water sliding angle of 90 degrees or more and has insufficient water repellency.

Claims (8)

The present invention relates to an acrylic urethane resin having a polymerizable unsaturated group, the resin containing an acrylic polyol compound (A) and an isocyanate compound (B) having a polymerizable unsaturated group as essential raw materials,
The acrylic urethane resin having a polymerizable unsaturated group is characterized in that the acrylic polyol compound (A) is an acrylic copolymer containing, as essential raw materials, a polysiloxane compound (a1) having one (meth)acryloyl group in one molecule, a polysiloxane compound (a2) having at least two (meth)acryloyl groups in one molecule, and a compound (a3) having a hydroxyl group and a polymerizable unsaturated group. The acrylic urethane resin having a polymerizable unsaturated group according to claim 1, wherein the number average molecular weight of the polysiloxane compound (a1) is less than 10,000. The acrylic urethane resin having a polymerizable unsaturated group according to claim 1, wherein the number average molecular weight of the polysiloxane compound (a2) is 2,000 or more and less than 1,5000. An active energy ray-curable resin composition comprising the acrylic urethane resin having a polymerizable unsaturated group according to any one of claims 1 to 3 and a photopolymerization initiator. The active energy ray-curable resin composition according to claim 4, further comprising a compound having a polymerizable unsaturated group other than the acrylic urethane resin. 6. The active energy ray-curable resin composition according to claim 5 , wherein the compound having a polymerizable unsaturated group has an average of 2 to 6 polymerizable unsaturated groups in one molecule. A cured product of the active energy ray-curable resin composition according to any one of claims 4 to 6. An article having a coating film of the cured product according to claim 7.