JP7293579B2 - Active energy ray-curable antifogging composition and cured product - Google Patents

Description

TECHNICAL FIELD The present invention relates to an active energy ray-curable antifogging composition having excellent antifogging properties and a cured product.

In recent years, automotive headlamps, virtual reality (VR) displays, and the like are required to have high antifogging properties to prevent fogging. Here, fogging is a phenomenon that occurs when water droplets adhering to the surface cause irregular reflection of light. Antifogging methods for preventing such fogging generally include a method of reducing the contact angle of water, a method of absorbing moisture adhering to the surface, a method of imparting water repellency to the surface to repel water, and the like. Are known. Among these methods, the method of reducing the contact angle of water is often used because it is simple and has good anti-fogging performance.

As a method for reducing the contact angle of water, an attempt has been made to form an antifogging film by applying an antifogging resin composition to the surface of a glass or plastic substrate. Conventionally known antifogging resin compositions include a monomer (A) which is a hydroxyalkyl (meth)acrylamide having a predetermined structure, a hydroxyl group-containing diacrylate (B) having a predetermined structure, A di(meth)acrylate monomer (C) having a predetermined structure and a photopolymerization initiator (D) are contained, and the monomers (A) to (D) are contained in a predetermined content. Examples include clouding agent compositions (see, for example, Patent Document 1). Although the anti-fogging agent composition is excellent in primary anti-fogging properties immediately after the coating film is formed, The secondary anti-fogging property was insufficient, and it did not satisfy the required properties that will increase more and more in the future.

Therefore, there has been a demand for a material capable of forming a coating film having even better primary antifogging properties and secondary antifogging properties.

JP 2015-218227 A

The problem to be solved by the present invention is to provide an active energy ray-curable antifogging composition capable of forming a cured coating film having excellent antifogging properties, and a cured product.

The present inventors have conducted intensive studies to solve the above problems, and found that a hydroxyl group-containing (meth)acrylate compound, a nonionic antifogging agent, an aqueous unsaturated group-containing miscibility accelerator, and a polyisocyanate compound The inventors have found that the above problems can be solved by using an active energy ray-curable antifogging composition containing, and completed the present invention.

That is, the present invention comprises a hydroxyl group-containing (meth)acrylate compound (A), a nonionic antifogging agent (B), an aqueous unsaturated group-containing miscibility accelerator (C), and a polyisocyanate compound (D). The present invention relates to an active energy ray-curable antifogging composition and a cured product characterized by containing

Since the active energy ray-curable antifogging composition of the present invention can form a cured coating film having excellent antifogging properties, it can be used for automobile headlamps, virtual reality (VR) displays, etc., with high antifogging properties. can be suitably used as an anti-fogging coating agent to be applied to the surface in applications where is required. The term "excellent anti-fogging property" as used in the present invention means anti-fogging property immediately after coating film formation (hereinafter referred to as "primary anti-fogging property"), and anti-fogging property after water resistance test, i.e., 25 °C water for 10 days (hereinafter referred to as "secondary anti-fogging property").

The active energy ray-curable antifogging composition of the present invention comprises a hydroxyl group-containing (meth)acrylate compound (A), a nonionic antifogging agent (B), and an aqueous unsaturated group-containing miscibility accelerator (C). , and a polyisocyanate compound (D).

The hydroxyl group-containing (meth)acrylate compound (A) has a function of imparting antifogging properties to the resulting cured product. Further, if the hydroxyl group-containing (meth)acrylate compound (A) has two or more (meth)acryloyl groups in one molecule, a cured product having even better antifogging properties and excellent hardness can be obtained. It is preferable because

In addition, in this invention, "(meth)acrylate" means an acrylate and/or a methacrylate. Moreover, "(meth)acryloyl" means acryloyl and/or methacryloyl. Furthermore, "(meth)acryl" means acryl and/or methacryl.

Examples of the hydroxyl group-containing (meth)acrylate compound (A) include (meth)acrylic acid adducts of epoxy compounds (hereinafter sometimes referred to as "epoxy (meth)acrylate"), hydroxyl group-containing urethane (meth) Examples include acrylate compounds.

The (meth)acrylic acid adduct of the epoxy compound is obtained by reacting the epoxy group of the epoxy compound with acrylic acid and/or methacrylic acid.

Examples of the epoxy compound include compounds having one or more epoxy groups in the molecule.

Examples of compounds having one epoxy group in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethylpropylene oxide, styrene oxide, hexafluoropropylene oxide, cyclohexene oxide, 3-glycidyl ether, Cydoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-glycidylphthalimide, (nonafluoro-N-butyl)epoxide, perfluoroethylglycidyl ether, epichlorohydrin, epibromohydride phosphorus, N,N-diglycidylaniline, 3-[2-(perfluorohexyl)ethoxy]-1,2-epoxypropane and the like. These compounds can be used alone or in combination of two or more.

Examples of the compound having two or more epoxy groups in the molecule include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycidyl polyglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 3,4-epoxycyclohexenylmethyl-3 Examples include ',4'-epoxycyclohexene carboxylate, 3-(N,N-diglycidyl)aminopropyltrimethoxysilane, polyglycidyl ether of cresol novolac resin, and polyglycidyl ether of phenol novolac resin. Among these, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexane can be obtained, since an active energy ray-curable antifogging composition capable of forming a cured product having excellent antifogging properties can be obtained. Diol diglycidyl ether, glycerol polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and hydrogenated bisphenol F diglycidyl ether are preferred. In addition, these compounds can be used alone or in combination of two or more.

The epoxy equivalent of the epoxy compound is preferably 300 g/equivalent or less, and 200 g/equivalent, since an active energy ray-curable anti-fogging composition capable of forming a cured product having excellent anti-fogging properties can be obtained. More preferred are:

As the hydroxyl group-containing urethane (meth)acrylate compound, for example, a hydroxyl group-containing (meth)acrylate monomer and a polyisocyanate compound are used, and the isocyanate group of the polyisocyanate compound is higher than the hydroxyl group of the hydroxyl group-containing (meth)acrylate monomer. Examples include those obtained by reacting a polyol compound with a urethane prepolymer having an isocyanate group, which is obtained by reacting such that the amount is excessive.

The urethane prepolymer has an isocyanate group and a (meth)acryloyl group derived from the hydroxyl group-containing (meth)acrylate monomer.

Examples of the hydroxyl group-containing (meth)acrylate monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and the like. Various hydroxyalkyl (meth)acrylate compounds; polyacrylate compounds of various polyvalent hydroxyl group-containing compounds such as di(meth)acrylate of trimethylolpropane, tri(meth)acrylate of pentaerythritol, hexa(meth)acrylate of dipentaerythritol, etc. is mentioned. These (meth)acrylate monomers can be used alone or in combination of two or more.

Examples of the polyisocyanate compounds include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate and trimethylhexamethylene diisocyanate; polyisocyanates having an alicyclic structure such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate; - aromatic polyisocyanates such as tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, diphenylmethane-4,4-diisocyanate, 1,5-naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate; mentioned. In addition, nurate modified products, adduct modified products, biuret modified products, allophanate modified products, etc. of these polyisocyanates can also be used. These polyisocyanate compounds can be used alone or in combination of two or more.

In the reaction between the hydroxyl group-containing (meth)acrylate monomer and the polyisocyanate compound, the molar ratio [NCO/OH] between the hydroxyl group of the hydroxyl group-containing (meth)acrylate monomer and the isocyanate group of the polyisocyanate compound is , preferably in the range of 1.5 to 3.

Examples of the polyol compound include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,3-propylene glycol and 1,2-propylene glycol. dipropylene glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,6-hexanediol 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentanediol, 3-methyl-1,5- Pentanediol, dichloroneopentyl glycol, dibromoneopentyl glycol, hydroxypivalic acid neopentyl glycol ester, cyclohexanedimethylol, 1,4-cyclohexanediol, ethylene oxide adduct of hydroquinone, hydroquinone propylene oxide adduct of, spiroglycol, tricyclodecanedimethylol, hydrogenated bisphenol A, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, 1,6-hexane Polyol compounds such as diol-based polycarbonate diols; the above polyol compounds, various α,β-unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, chlorinated maleic acid, or their anhydrides and phthalates acid, tetrahydrophthalic acid, hexahydrophthalic acid, monochlorophthalic acid, dichlorophthalic acid, trichlorophthalic acid, hetic acid, chlorendic acid, dimer acid, adipic acid, pimelic acid, succinic acid, alkenylsuccinic acid, sebacic acid , azelaic acid, 2,2,4-trimethyladipic acid, terephthalic acid, dimethyl terephthalic acid, 2-sodium sulfoterephthalic acid, 2-potassium sulfoterephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid Saturated polycarboxylic acids such as acid, orthophthalic acid, 4-sulfophthalic acid, 1,10-decamethylenedicarboxylic acid, muconic acid, oxalic acid, malonic acid, glutaric acid, hexahydrophthalic acid, tetrabromophthalic acid, or acids thereof Ring-opening polymerization of polyester polyols obtained by condensation with anhydrides, β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, etc. polyester polyols obtained by These polyol compounds can be used alone or in combination of two or more.

In the production of the urethane (meth)acrylate compound, various catalysts such as dibutyltin laurate and dibutyltin acetate can be used as necessary. In this case, if necessary, solvents such as ethyl acetate, butyl acetate, methyl isobutyl ketone, toluene, and xylene can be used.

The hydroxyl value of the hydroxyl group-containing (meth)acrylate compound (A) is 250 mgKOH/g or more because an active energy ray-curable antifogging composition capable of forming a cured product having excellent antifogging properties can be obtained. preferably 350 mgKOH/g or more. In addition, the hydroxyl value in the present invention is a value measured based on the neutralization titration method of JIS K 0070 (1992).

The content of the hydroxyl group-containing (meth)acrylate compound (A) is preferably in the range of 10 to 60% by mass, more preferably 20 to 40% by mass, based on the solid content of the active energy ray-curable antifogging composition. preferable.

The nonionic antifogging agent (B) has a function of imparting antifogging performance to the cured product. In the present invention, "nonionic" means those that do not form ions in water.

Examples of the nonionic antifog agent (B) include sucrose long-chain fatty acid esters, glycerin long-chain fatty acid esters, polyglycerin long-chain fatty acid esters, sorbitan long-chain fatty acid esters, polyoxyethylene long-chain alkyl ethers, and the like. mentioned. In the present invention, the term "long chain" means having 6 or more carbon atoms, preferably 7 to 40 carbon atoms, more preferably 7 to 40 carbon atoms, from the viewpoint of obtaining excellent antifogging properties. It has 8 to 30 carbon atoms, more preferably 10 to 20 carbon atoms.

The sucrose long-chain fatty acid ester is an ester of sucrose and a substituted or unsubstituted saturated long-chain fatty acid or unsaturated long-chain fatty acid (hereinafter collectively referred to simply as "long-chain fatty acid"). is.

Sucrose, also called sucrose, is a disaccharide composed of glucose and fructose and has eight hydroxyl groups. The sucrose long-chain fatty acid ester according to this embodiment has a structure in which one or more of the hydroxyl groups form an ester bond with the long-chain fatty acid. When two or more hydroxyl groups form an ester bond with a long-chain fatty acid, the long-chain fatty acids bonded to the respective hydroxyl groups may be the same or different.

The long-chain fatty acid is a substituted or unsubstituted saturated long-chain fatty acid or unsaturated long-chain fatty acid. Specific long-chain fatty acids include, for example, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, Saturated long-chain fatty acids such as behenic acid; unsaturated long-chain fatty acids such as eicosapentaenoic acid, docosahexaenoic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, arachidonic acid, palmitoleic acid, oleic acid, erucic acid, and nervonic acid etc.

The long-chain fatty acid may have a substituent, and examples of such substituents include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert- Alkyl groups having 1 to 10 carbon atoms such as butyl group, pentyl group, hexyl group, octyl group and decyl; Number of carbon atoms such as cyclopropyl group, cyclobutyl group, methylcyclobutyl group, cyclopentyl group, cyclohexyl group and cyclodecyl group Cycloalkyl groups of 3 to 10; alkenyl groups of 2 to 10 carbon atoms such as vinyl group, allyl group, butenyl group and octenyl group; alkynyl groups of 2 to 10 carbon atoms such as propargyl group and butynyl group; methoxy group , ethoxy group, alkyloxy group having 1 to 10 carbon atoms such as propyloxy group; alkylcarbonyl group having 2 to 10 carbon atoms such as acetyl group and ethylcarbonyl group; phenyl group, tolyl group, xylyl group, chlorophenyl group aryl group having 6 to 10 carbon atoms such as; aralkyl group having 7 to 10 carbon atoms such as benzyl group; fluorine atom, chlorine atom, bromine atom, halogen atom such as iodine atom; hydroxyl group; . These substituents may be present alone or in combination of two or more.

Among the above, the long-chain fatty acid is preferably a saturated long-chain fatty acid, more preferably a saturated long-chain fatty acid having 8 to 40 carbon atoms, from the viewpoint of obtaining a good coating film appearance. Capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, and palmitic acid are more preferable from the viewpoint of property stability of the product.

The sucrose long-chain fatty acid ester may be a synthesized product or a commercially available product. When synthesizing the sucrose long-chain fatty acid ester, a known method can be appropriately employed. For example, a sucrose long-chain fatty acid ester can be synthesized by subjecting sucrose and a long-chain fatty acid to a dehydration condensation reaction in the presence of an acid catalyst. In addition, commercial products of sucrose long-chain fatty acid esters include, for example, Rikemar (registered trademark) A, XO-100, L-250A, L-71-D, O-71-DE, OL-100E, Poem (registered Trademark) J-0021, DO-100V, O-80V, DS-100A (manufactured by Riken Vitamin Co., Ltd.), Ryoto (registered trademark) sugar ester S-070, S-170, S-270, S-370, S470, S-570, S-970, S-1170, S-1570, S-1670, P-1570, P-1670, M-1695, O-170, O-1570, L-195, L-595, L- 1695, LWA-1570, B-370, ER-190, ER-290, POS-135 (Mitsubishi Kagaku Foods Co., Ltd.), DK Ester SS, F-160, F-140, F-110, F-90, F-70, F-50, F-20W, F-10, F-A10E (Daiichi Kogyo Seiyaku Co., Ltd.), Cosmelike SA-10, S-190, S-160, S-110, S-70 , S-50, S-10, R-20, R-10, B-30, O-150, O-10, P-160P-10, M-160, L-160, L-160, L-160A , L-150A, L-50, L-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like.

The glycerin long-chain fatty acid ester is an ester of glycerin and a long-chain fatty acid.

The glycerin is a triol represented by _the chemical formula _{of C3H8O3} . The glycerin long-chain fatty acid ester according to this embodiment has a structure in which one or more of the three hydroxyl groups of glycerin form an ester bond with the long-chain fatty acid. When two or more hydroxyl groups form an ester bond with a long-chain fatty acid, the long-chain fatty acids bonded to the respective hydroxyl groups may be the same or different.

The long-chain fatty acid is the same as described above.

As the glycerin long-chain fatty acid ester, a synthesized product or a commercially available product may be used. When synthesizing the glycerin long-chain fatty acid ester, a known method can be appropriately employed. In addition, commercial products of glycerin long-chain fatty acid esters include, for example, Rikemar (registered trademark) S-100, S-100P, S-100A, H-100, B-100, HC-100, XO-100, S- 200 (manufactured by Riken Vitamin Co., Ltd.) and the like.

The polyglycerin long-chain fatty acid ester is an ester of polyglycerin and a long-chain fatty acid.

The polyglycerin is a polymer of two or more glycerins. The polyglycerin has different numbers of hydroxyl groups depending on the degree of polymerization of glycerin. For example, diglycerin has four hydroxyl groups, triglycerin has five hydroxyl groups, and hexaglycerin has eight. The degree of polymerization of polyglycerin is preferably 2 to 6, more preferably 2 to 3 from the viewpoint of obtaining excellent water resistance.

The polyglycerin long-chain fatty acid ester according to the present embodiment has a structure in which one or more hydroxyl groups of polyglycerin form an ester bond with the long-chain fatty acid. When two or more hydroxyl groups form an ester bond with a long-chain fatty acid, the long-chain fatty acids bonded to the respective hydroxyl groups may be the same or different.

The long-chain fatty acid is the same as described above.

As the polyglycerin long-chain fatty acid ester, a synthesized product or a commercially available product may be used. When synthesizing the polyglycerin long-chain fatty acid ester, a known method can be appropriately adopted. Commercially available polyglycerin long-chain fatty acid esters include, for example, Rikemar (registered trademark) L-71-D, S-71-D, O-71-D (manufactured by Riken Vitamin Co., Ltd.), and Poem J-4081V. , J-0021, J-0081HV, J-0381V, PR-100, PR-300 (manufactured by Riken Vitamin Co., Ltd.), Ryoto (registered trademark) polyglyester CE-19D, CA-F4, L-10D, L- 7D, M-10D, M-7D, S-28D, S-24D, SWA-20D, SWA-15D, SWA-10D, SWA-10DB, O-50D, O-500P, O-15D, B-100D, B-100DF, B-70D (manufactured by Mitsubishi Kagaku Foods Co., Ltd.) and the like.

The sorbitan long-chain fatty acid ester is an ester of sorbitan and a long-chain fatty acid.

The sorbitan is a compound obtained by a dehydration reaction of sorbitol (glucitol). Specific structures include, for example, 1,4-anhydrosorbitol, 1,5-anhydrosorbitol, 2,5-anhydrosorbitol, 1,4:3,6-dianhydrosorbitol and the like. Sorbitan differs in the number of hydroxyl groups it has depending on its structure. For example, 1,4-anhydrosorbitol has four hydroxyl groups and 1,4:3,6-dianhydrosorbitol has two hydroxyl groups. The sorbitan long-chain fatty acid ester according to the present embodiment has a structure in which one or more hydroxyl groups of sorbitan form an ester bond with the long-chain fatty acid. When two or more hydroxyl groups form an ester bond with a long-chain fatty acid, the long-chain fatty acids bonded to the respective hydroxyl groups may be the same or different.

The long-chain fatty acid is the same as described above.

As the sorbitan long-chain fatty acid ester, a synthesized product or a commercially available product may be used. When synthesizing the sorbitan long-chain fatty acid ester, a known method can be appropriately employed. In addition, commercial products of sorbitan long-chain fatty acid esters include, for example, Rikemar (registered trademark) L-250A, P-300, S-300W, OV-250 (manufactured by Riken Vitamin Co., Ltd.), Rhodol (registered trademark) SP- L10, SP-P10 (manufactured by Kao Corporation) and the like.

The polyoxyethylene long-chain alkyl ether is usually an ether obtained by reacting a long-chain alcohol with ethylene oxide to extend the polyoxyethylene chain.

Examples of long-chain alcohols include saturated long-chain alcohols such as caprylic alcohol, 2-ethylhexanol, pelargon alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetanol, stearyl alcohol, isostearyl alcohol, and arachidyl alcohol; alcohol, unsaturated long-chain alcohols such as oleyl alcohol, linoleyl alcohol, linolenyl alcohol and ricinoleyl alcohol;

The polyoxyethylene chain is preferably 2 to 30 mol, more preferably 4 to 20 mol, more preferably 8 to 16 mol of ethylene oxide per 1 mol of the long-chain alcohol. preferable.

As the polyoxyethylene long-chain alkyl ether, a synthesized product or a commercially available product may be used. When synthesizing the polyoxyethylene long-chain alkyl ether, known methods can be employed as appropriate. Commercially available polyoxyethylene long-chain alkyl ethers include, for example, Rikemal (registered trademark) B-205 and O-852 (manufactured by Riken Vitamin Co., Ltd.).

Among the above-described nonionic antifogging agents (B), it is preferable to use sucrose long-chain fatty acid esters from the viewpoint of obtaining excellent antifogging properties. Acid ester, sucrose tridecylate, and sucrose myristate are more preferably used, and sucrose undecylate, sucrose laurate, sucrose tridecylate, and sucrose myristate are more preferably used. .

In addition, the above-mentioned nonionic antifog agent (B) can be used alone or in combination of two or more.

The HLB (Hydrophile-Lipophile Balance) of the nonionic antifogging agent (B) is preferably 10-20, more preferably 15-20. When the HLB of the nonionic antifogging agent (B) is 10 or more, it is preferable because sufficient antifogging properties can be exhibited. On the other hand, when the HLB of the nonionic antifogging agent (B) is 20 or less, it is preferable because sufficient water resistance can be maintained. In addition, in this specification, the value of "HLB" shall employ the value measured by the Griffin method.

The content of the nonionic antifogging agent (B) is preferably 3% by mass or more, more preferably 7.5% by mass or more, in the solid content of the active energy ray-curable antifogging composition. is more preferable, and 10 to 50% by mass is even more preferable. A content of the nonionic antifogging agent of 3% by mass or more is preferable because high antifogging properties can be obtained.

The aqueous unsaturated group-containing miscibility accelerator (C) has a function of promoting miscibility between the hydroxyl group-containing (meth)acrylate (A) and the nonionic antifogging agent (B). As a result, a cured product having high hardness and high transparency can be obtained. In this specification, the term "aqueous" means that the solubility in water (100 mL) (25°C, 25% RH) is 5% by mass or more.

The aqueous unsaturated group-containing miscibility accelerator (C) contains a nonionic monopolymerizable unsaturated group-containing monomer. In addition, if necessary, a nonionic di-polymerizable unsaturated group-containing monomer and the like may be further included.

Since the nonionic monopolymerizable unsaturated group-containing monomer is aqueous and nonionic, the nonionic antifogging agent (B) having a surface active action is combined with the hydroxyl group-containing (meth)acrylate compound (A). They can be suitably mixed, and the obtained cured product can maintain suitable miscibility. In the present invention, the "monopolymerizable unsaturated group-containing monomer" means having one polymerizable unsaturated group in the molecule. At this time, the "polymerizable unsaturated group" means an unsaturated group that can be polymerized by an active energy ray, and a vinyl group (a vinyl group in which at least one of the hydrogen atoms constituting the vinyl group is substituted with a substituent (including), (meth)acryloyl group, (meth)acrylamide group, and the like.

Examples of the nonionic monopolymerizable unsaturated group-containing monomer include vinyl monomers such as vinyl acetate, acrylonitrile, N-vinyl-2-pyrrolidone, N-vinylformamide, N-vinylacetamide; (Meth)acrylic monomers such as ethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, acryloylmorpholine; N,N-dimethyl (meth)acrylamide, N,N-diethyl ( Examples thereof include (meth)acrylamide monomers such as meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and hydroxyethyl(meth)acrylamide. Among these, vinyl monomers are preferred, acrylonitrile, N-vinyl-2-pyrrolidone, N-vinylformamide, N-vinylacetamide and hydroxyethyl (meth)acrylamide are more preferred, and hydroxyethyl (meth)acrylamide is particularly preferred. .

The above-mentioned nonionic monopolymerizable unsaturated group-containing monomers can be used alone or in combination of two or more.

The content of the nonionic monopolymerizable unsaturated group-containing monomer is preferably 3% by mass or more, more preferably 5% by mass or more, in the solid content of the active energy ray-curable antifogging composition. is more preferable, 10 to 60% by mass is more preferable, and 15 to 45% by mass is particularly preferable.

Since the nonionic di-polymerizable unsaturated group-containing monomer is aqueous and nonionic, the nonionic antifogging agent (B) having surface activity is suitable for the hydroxyl group-containing (meth)acrylate compound (A). can be miscible with In one embodiment, since the molecule has two polymerizable unsaturated groups, the degree of cross-linking is increased, and the hardness and water resistance of the obtained cured product can be improved. In addition, in the present invention, the “dipolymerizable unsaturated group-containing monomer” means having two polymerizable unsaturated groups in the molecule.

Examples of the nonionic di-polymerizable unsaturated group-containing monomer include ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, (Meth)acrylates, (poly)ethylene glycol di(meth)acrylates such as polyethylene glycol di(meth)acrylates, and the like. Among these, from the viewpoint of obtaining excellent water resistance, (poly)ethylene glycol di(meth)acrylate is preferable, and polyethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol diacrylate. is more preferred, and polyethylene glycol diacrylate, polyethylene glycol diacrylate, and polyethylene glycol diacrylate are even more preferred.

The nonionic di-polymerizable unsaturated group-containing monomers described above can be used alone or in combination of two or more.

The content of the nonionic di-polymerizable unsaturated group-containing monomer is preferably 3% by mass or more, more preferably 5% by mass or more, in the solid content of the active energy ray-curable antifogging composition. is more preferable, 7.5 to 50% by mass is more preferable, and 10 to 40% by mass is particularly preferable.

The content of the aqueous unsaturated group-containing miscibility accelerator (C) is preferably 10% by mass or more, preferably 15 to 80% by mass, in the solid content of the active energy ray-curable antifogging composition. more preferably 20 to 75% by mass.

Further, the mass ratio of the aqueous unsaturated group-containing miscibility accelerator (C) to the nonionic antifogging agent (B) (aqueous unsaturated group-containing miscibility accelerator (C)/nonionic antifogging agent (B)) is , is preferably 0.75 or more, more preferably 1.5 or more, even more preferably 1.75 or more, and particularly preferably 1.75 to 3. The mass ratio of the aqueous unsaturated group-containing miscibility accelerator (C) to the nonionic antifogging agent (B) (aqueous unsaturated group-containing miscibility accelerator (C)/nonionic antifogging agent (B)) is 0. When it is 75 or more, the miscibility promoting function of the nonionic antifogging agent (B) to the hydroxyl group-containing (meth)acrylate compound (A) by the aqueous unsaturated group-containing miscibility accelerator (C) acts favorably. It is preferable because the transparency of the cured product obtained can be increased.

In one embodiment, the aqueous unsaturated group-containing compatibilizer (C) preferably comprises at least a highly aqueous unsaturated group-containing compatibilizer. By including the highly aqueous unsaturated group-containing miscibility accelerator, it may be possible to effectively mix the hydroxyl group-containing (meth)acrylate compound (A) and the nonionic antifogging agent (B).

In another embodiment, it is preferable to use a low aqueous unsaturated group-containing miscibility accelerator and a high aqueous unsaturated group-containing miscibility accelerator in combination. The combination of a low-aqueous unsaturated group-containing miscibility accelerator and a high-aqueous unsaturated group-containing miscibility accelerator promotes miscibility between the hydroxyl group-containing (meth)acrylate compound (A) and the nonionic antifogging agent (B). In addition, it may be possible to further increase the hardness, water resistance, and the like.

In the present invention, the term "highly water-soluble" means, among the unsaturated group-containing miscibility accelerators corresponding to water-based, those having relatively high solubility in water, i.e., solubility in water (100 mL) (25 ° C., 25 % RH) is more than 50% by mass. On the other hand, the term “low water” means, among the unsaturated group-containing miscibility accelerators corresponding to water, those with relatively low solubility in water, i.e., solubility in water (100 mL) (25 ° C., 25% RH) is 5 to 50% by mass.

Examples of the highly aqueous unsaturated group-containing miscibility accelerator include vinyl acetate, N-vinyl-2-pyrrolidone, 2-hydroxyethyl (meth)acrylate, among the above-mentioned aqueous unsaturated group-containing miscibility accelerators (C). acryloylmorpholine, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, dimethylaminopropyl(meth)acrylamide, diacetone(meth)acrylamide, N-vinylformamide, and N-vinylacetamide.

Further, as the low aqueous unsaturated group-containing miscibility accelerator, among the above-mentioned aqueous unsaturated group-containing miscibility accelerators (C), for example, acrylonitrile, methyl acrylate, divinylbenzene, ethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol diacrylate and the like.

The mass ratio of the high-aqueous unsaturated group-containing compatibilizer to the low-aqueous unsaturated group-containing compatibilizer (high-aqueous unsaturated group-containing compatibilizer/low-aqueous unsaturated group-containing compatibilizer) provides excellent antifogging properties. From the viewpoint of obtaining, it is preferably 0.25 or more, more preferably 0.25 to 2.0.

Examples of the polyisocyanate compound (D) include, for example, hexamethylene diisocyanate, lysine diisocyanate, aliphatic polyisocyanates such as trimethylhexamethylene diisocyanate; cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, polyisocyanates having an alicyclic structure such as isophorone diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, diphenylmethane-4,4-diisocyanate, 1,5-naphthalene diisocyanate, aromatic polyisocyanate such as polymethylene polyphenyl polyisocyanate and isocyanate. In addition, nurate modified products, adduct modified products, biuret modified products, allophanate modified products, etc. of these polyisocyanates can also be used. These polyisocyanate compounds can be used alone or in combination of two or more.

The content of the polyisocyanate compound (D) is the sum of the hydroxyl group-containing (meth)acrylate compound (A), the nonionic antifogging agent (B), and the aqueous unsaturated group-containing miscibility accelerator (C). It is preferably in the range of 5 to 40 parts by mass with respect to 100 parts by mass.

The active energy ray-curable antifogging composition of the present invention may further contain a hydrophilic resin (E).

The hydrophilic resin (E) has functions such as imparting leveling properties and adherence to substrates to the resulting cured product.

Examples of the hydrophilic resin (E) include polyethylene glycol, hydroxyethyl cellulose, polycarboxylic acid, polyvinylpyrrolidone, and the like. Among these, polyvinylpyrrolidone is preferable from the viewpoint of obtaining excellent water resistance.

The content of the hydrophilic resin (E) is preferably in the range of 0.5 to 10% by mass in the solid content of the active energy ray-curable antifogging composition.

The active-energy-ray-curable antifogging composition of the present invention contains other than the hydroxyl group-containing (meth)acrylate compound (A) and the aqueous unsaturated group-containing miscibility accelerator (C) as long as the effects of the present invention are not impaired. may contain other unsaturated group-containing compounds.

Examples of the other unsaturated group-containing compounds include phenoxyethyl (meth)acrylate, phenoxybenzyl (meth)acrylate, cyclohexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, cyclohexylethyl ( meth)acrylate, 2-ethylhexyl (meth)acrylate, dipropylene glycol mono(meth)acrylate, isobornyl (meth)acrylate, isononyl (meth)acrylate, benzyl (meth)acrylate, phenylbenzyl (meth)acrylate, lauryl (meth)acrylate acrylates, tetrahydrofurfuryl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, methyl methacrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl ( meth)acrylate, n-hexyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylmethoxy (meth)acrylate, 2 - Ethylethoxy (meth) acrylate, 2-ethylbutoxy (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, butoxydiethylene glycol (meth) acrylate, butoxytriethylene glycol (meth) ) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-(meth) acryloyloxyethyl succinic acid, 2-(meth) acryloyloxyethyl hexahydrophthalate, glycidyl (meth) acrylate, 2 - hydroxy-3-phenoxypropyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, pentamethylpiperidinyl (meth)acrylate, tetramethylpiperidinyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (3-ethyloxetane- 3-yl) Non-aqueous non-ionic mono-polymerizable unsaturated group-containing monomers such as methyl acrylate and cyclic trimethylolpropane formal (meth) acrylate; (meth) acrylic acid, itaconic acid, crotonic acid, sodium styrenesulfonate, vinyl Aqueous ionic monopolymerizable unsaturated group-containing monomers such as sulfonic acid, dimethylaminopropyl (meth)acrylamide methyl chloride quaternary salt; 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, neopentyl glycol hydroxypivalate 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, tricyclode candimethanol 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, ethylene oxide-modified di(meth)acrylate of bisphenoxyethanolfluorene, polytetramethylene glycol di(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, phenoxyethylene glycol (meth)acrylate, stearyl Non-aqueous nonionic polypolymerizable unsaturated groups such as (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, trifluoroethyl (meth)acrylate 3-methyl-1,5 pentanediol di(meth)acrylate Containing monomers; unsaturated group-containing oligomers such as unsaturated polyesters, and the like. These other unsaturated group-containing compounds can be used alone or in combination of two or more.

The content of the other unsaturated group-containing compound is preferably 50% by mass or less, and 0.1 to 30% by mass, in the solid content of the active energy ray-curable antifogging composition. is more preferred.

In addition, the active energy ray-curable antifogging composition of the present invention may contain an ionic surfactant within a range that does not impair the effects of the present invention. In addition, in the present invention, the term “ionic” means that which ionizes in water to form ions.

Examples of the ionic surfactant include anionic surfactants, cationic surfactants, and amphoteric surfactants.

Examples of the anionic surfactant include sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, magnesium stearate, calcium stearate, calcium oleate, and calcium stearoyl lactylate. carboxylic acids such as sodium 1-hexanesulfonate, sodium 1-octane sulfonate, sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazobisamino-8 -Sulfonic acids such as sodium naphthol-6-sulfonate, orthocarboxybenzeneazodimethylaniline, sodium 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazobis-β-naphthol-6-sulfonate Sulfuric acid esters such as sodium lauryl sulfate (sodium dodecyl sulfate: SDS), sodium tetradecyl sulfate, sodium pentadecyl sulfate, and sodium octyl sulfate; Polyoxyethylenes such as sodium polyoxyethylene alkyl ether sulfate (sodium polyoxyethylene lauryl ether sulfate) Alkyl ether sulfates; Phosphoric acids such as lauryl phosphate, and the like.

Examples of the cationic surfactant include tetramethylammonium chloride, tetramethylammonium hydroxide, tetrabutylammonium chloride, dodecyldimethylbenzylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, and benzalkonium chloride. , quaternary ammonium salts such as benzethonium chloride; alkylamine salts such as monomethylamine hydrochloride and dimethylamine hydrochloride; pyridinium salts such as butylpyridinium chloride.

Examples of the amphoteric surfactant include alkylbetaines such as betaine lauryldimethylaminoacetate and betaine stearyldimethylaminoacetate; fatty acid amidopropylbetaines such as cocamidopropyl betaine; 2-alkyl-N-carboxymethyl-N- Alkylimidazoles such as hydroxyethylimidazolinium betaine; amino acids such as sodium lauroyl glutamate; and amine oxides such as lauryldimethylamine N-oxide and oleyldimethylamine N-oxide.

The above-mentioned ionic surfactants can be used alone or in combination of two or more.

More preferably, the content of the ionic surfactant is 5% by mass or less in the solid content of the active energy ray-curable antifogging composition.

Moreover, the active energy ray-curable antifogging composition of the present invention may contain a solvent. By containing a solvent, the viscosity of the composition can be adjusted.

Examples of the solvent include alcohol solvents such as methanol, ethanol, 1-propanol, t-butanol, and diacetone alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol. alcohol ether solvents such as monoethyl ether, carbitol and cellosolve; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; Aromatic solvents and the like are included.

The above solvents can be used alone or in combination of two or more.

The content of the solvent is preferably 0 to 300 parts by mass, more preferably 10 to 100 parts by mass, based on 100 parts by mass of the active energy ray-curable antifogging composition. . When the content of the solvent is 300 parts by mass or less, it is preferable because the film thickness can be easily controlled. A solvent content of 10 parts by mass or more is preferable because various coating methods such as spray coating and flow coating can be employed.

Moreover, the active energy ray-curable antifogging composition of the present invention may contain a photopolymerization initiator.

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl 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-morpholinopropane-1- one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like.

Commercial products of the photopolymerization initiator 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” (manufactured by IGM), “Kayacure-DETX”, “Kayacure-MBP”, “Kayacure-DMBI”, “Kayacure-EPA”, "Kayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "Vicure-10", "Vicure-55" (manufactured by Stouffer Chemical), "Trigonal P1" (manufactured by Akzo), "Sunray 1000" (Sandos) ), “Deep” (manufactured by Upjohn), “Quantacure-PDO”, “Quantacure-ITX”, “Quantacure-EPD” (manufactured by Ward Blenkinsop), “Runtecure-1104” (manufactured by Runtec ) and the like.

The above photopolymerization initiators can be used alone or in combination of two or more.

The content of the photopolymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, with respect to 100 parts by mass of the solid content of the active energy ray-curable antifogging composition. is more preferable. When the content of the photopolymerization initiator is 0.1 parts by mass or more, the curing reaction proceeds favorably, and a cured product having high hardness can be obtained, which is preferable. On the other hand, when the content of the photopolymerization initiator is 10 parts by mass or less, yellowing or the like is less likely to occur, and a cured product having high transparency can be obtained, which is preferable.

Furthermore, the active energy ray-curable antifogging composition of the present invention may contain other additives as necessary.

Examples of other additives include antifoaming agents, plasticizers, film-forming aids, thickeners, pigments, pigment dispersants, weather resistance improvers, and heat stabilizers. These other additives can be used alone or in combination of two or more.

The method for producing the active energy ray-curable antifogging composition of the present invention is not particularly limited, and known methods can be applied.

For example, the active energy ray-curable antifogging composition is prepared by mixing a hydroxyl group-containing (meth)acrylate compound (A) and an aqueous unsaturated group-containing miscibility accelerator (C), followed by a nonionic antifogging agent (B). Alternatively, after mixing the nonionic antifogging agent (B) and the aqueous unsaturated group-containing miscibility accelerator (C), the hydroxyl group-containing (meth) acrylate compound (A) is mixed. may be manufactured by In addition, the active energy ray-curable antifogging composition contains, as an aqueous unsaturated group-containing miscibility accelerator (C), a nonionic mono-polymerizable unsaturated group-containing monomer together with a nonionic di-polymerizable unsaturated group-containing monomer. If it contains a nonionic mono-polymerizable unsaturated group-containing monomer and a non-ionic di-polymerizable unsaturated group-containing monomer are mixed in advance, and this is mixed with a hydroxyl group-containing (meth) acrylate compound (A), Then, it may be further mixed with a nonionic antifogging agent (B), or a nonionic monopolymerizable unsaturated group-containing monomer and a hydroxyl group-containing (meth)acrylate compound (A), and a nonionic dipolymerizable The unsaturated group-containing monomer and the nonionic antifogging agent (B) may be mixed, respectively, and the resulting two mixtures may be mixed. Furthermore, when the active energy ray-curable antifogging composition contains other unsaturated group-containing compounds, ionic surfactants, solvents, polymerization initiators, other additives, etc., these are appropriately mixed. be able to.

The mixing conditions are also not particularly limited, and may be dry or wet. Also, the mixing temperature, mixing pressure, etc. are not particularly limited and can be determined as appropriate.

The cured product of the present invention can be obtained by applying the active energy ray-curable antifogging composition and irradiating the resulting coating film with an active energy ray.

The method of applying the active energy ray-curable antifogging composition is not particularly limited, and may be bar coater coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, or flexographic printing. , a known method such as a screen printing method can be employed.

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, the irradiation may be performed in an atmosphere of an inert gas such as nitrogen gas or in an air atmosphere in order to efficiently perform the curing reaction using the ultraviolet rays.

As the source of the ultraviolet rays, an ultraviolet lamp is generally used from the viewpoint 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, and LEDs.

The integrated amount of active energy rays is not particularly limited, but is preferably 50 to 5000 mJ/cm ² , more preferably 300 to 1000 mJ/cm ² . It is preferable that the integrated amount of light is within the above range because the generation of uncured portions can be prevented or suppressed.

In addition, the irradiation with the active energy ray may be performed in one step, or may be performed in two or more steps.

The film thickness of the cured product is preferably 5 to 100 μm, more preferably 10 to 50 μm, although it varies depending on the application.

Since the cured product has excellent anti-fog properties, it can be suitably used for applications such as automobile headlamps and virtual reality (VR) displays. Moreover, it can be suitably used for applications such as spectacles, goggles, various mirrors, and various windows.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples.

(Synthesis Example 1: Production of hydroxyl group-containing (meth)acrylate compound (A1))
Into a four-necked flask equipped with a stirrer, a thermometer and a cooling tube, 578.3 parts by mass of liquid bisphenol A type epoxy resin ("Epiclon 850" manufactured by DIC Corporation, epoxy equivalent: 188 g/equivalent), and 217.4 parts by mass of acrylic acid. Parts by mass and 0.2 parts by mass of methoquinone (polymerization inhibitor) were added, and after the temperature was raised to 100° C., 4.0 parts by mass of triphenylphosphine (catalyst) was added. A reaction was carried out at 100° C. for 12 hours to obtain a hydroxyl group-containing (meth)acrylate compound (A1). This hydroxyl-containing (meth)acrylate compound (A1) had an epoxy equivalent of 18,000 g/equivalent, an acid value of 0.4 mgKOH/g, and a hydroxyl value of 431 mgKOH/g. The acid value and hydroxyl value are values measured based on the neutralization titration method of JIS K 0070 (1992).

(Synthesis Example 2: Production of hydroxyl group-containing (meth)acrylate compound (A2))
596.8 parts by mass of liquid hydrogenated bisphenol A type epoxy resin (“Denacol EX-252” manufactured by Nagase ChemteX Corporation, epoxy equivalent 212 g/equivalent) was placed in a four-necked flask equipped with a stirrer, thermometer and cooling tube. , 199.0 parts by mass of acrylic acid, and 0.2 parts by mass of methoquinone were charged, heated to 100° C., and then 4.0 parts by mass of triphenylphosphine were added. A reaction was carried out at 100° C. for 12 hours to obtain a hydroxyl group-containing (meth)acrylate compound (A2). This hydroxyl-containing (meth)acrylate compound (A2) had an epoxy equivalent of 15,000 g/equivalent, an acid value of 0.8 mgKOH/g, and a hydroxyl value of 395 mgKOH/g.

(Synthesis Example 3: Production of hydroxyl group-containing (meth)acrylate compound (A3))
In a four-necked flask equipped with a stirrer, thermometer and cooling tube, neopentyl glycol diglycidyl ether (“Denacol EX-211” manufactured by Nagase ChemteX Corporation, epoxy equivalent 138 g / equivalent) 526.2 parts by mass, acrylic After charging 269.5 parts by mass of acid and 0.2 parts by mass of methoquinone and raising the temperature to 100° C., 4.0 parts by mass of triphenylphosphine was added. A reaction was carried out at 100° C. for 12 hours to obtain a hydroxyl group-containing (meth)acrylate compound (A3). This hydroxyl-containing (meth)acrylate compound (A3) had an epoxy equivalent of 15,000 g/equivalent, an acid value of 1.0 mgKOH/g, and a hydroxyl value of 534 mgKOH/g.

(Synthesis Example 4: Production of hydroxyl group-containing (meth)acrylate compound (A4))
Into a four-necked flask equipped with a stirrer, a thermometer and a cooling tube, 692.7 parts by mass of a solid bisphenol A type epoxy resin ("Epiclon 1055" manufactured by DIC Corporation, epoxy equivalent 475 g/equivalent), and 103.1 parts acrylic acid. Parts by mass and 0.2 parts by mass of methoquinone were added, and after the temperature was raised to 120° C., 4.0 parts by mass of triphenylphosphine was added. A reaction was carried out at 120° C. for 12 hours to obtain a hydroxyl group-containing (meth)acrylate compound (A4). This hydroxyl-containing (meth)acrylate compound (A4) had an epoxy equivalent of 25,000 g/equivalent, an acid value of 1.5 mgKOH/g, and a hydroxyl value of 205 mgKOH/g.

(Comparative Synthesis Example 4: Production of (meth)acrylate compound (A'1))
310.2 parts by weight of isophorone diisocyanate, 1.6 parts by weight of tert-butylhydroxytoluene, 0.2 parts by weight of methoxyhydroquinone, and 0.2 parts by weight of dibutyltin diacetate were placed in a four-necked flask equipped with a stirrer, thermometer and condenser. 2 parts by mass was added, the temperature was raised to 70° C., and 162 parts by mass of 2-hydroxyethyl acrylate was added dropwise over 1 hour. After the dropwise addition, the mixture was allowed to react at 70° C. for 3 hours, and then 326 parts by mass of polypropylene glycol having a number average molecular weight of 700 ("Actocol T-700" manufactured by Mitsui Chemicals) was charged in portions over 2 hours. After the dropwise addition, the mixture was allowed to react at 70° C. for 3 hours, and then reacted until the infrared absorption spectrum at 2250 cm ⁻¹ indicating the isocyanate group disappeared to obtain a (meth)acrylate compound (A′1).

(Example 1: Preparation of active energy ray-curable antifogging composition (1))
30 parts by mass of the hydroxyl group-containing (meth)acrylate compound (A1) obtained in Synthesis Example 1, 45 parts by mass of diglycerin monolaurate, 24 parts by mass of hydroxyethylacrylamide, and hexamethylene diisocyanate-based isocyanurate-type polyisocyanate (DIC Co., Ltd. "Barnock DN-980S") 20 parts by weight, ethyl acetate 25 parts by weight, and photopolymerization initiator (IGM Co. "Omnirad 184") 3 parts by weight are mixed to form an active energy ray-curable anti-fogging composition. I got the product (1).

(Examples 2 to 10: Preparation of active energy ray-curable antifogging compositions (2) to (10))
Active energy ray-curable antifogging compositions (2) to (10) were obtained by mixing the compositions and blending amounts shown in Table 1.

(Comparative Examples 1 to 4: Preparation of active energy ray-curable antifogging compositions (C1) to (C4))
Active energy ray-curable antifogging compositions (C1) to (C4) were obtained by mixing the compositions and blending amounts shown in Table 1.

The following evaluations were performed using the active energy ray-curable antifogging compositions obtained in the above Examples and Comparative Examples.

[Preparation of sample]
The active energy ray-curable antifogging composition is applied to a glass plate (thickness: 0.2 cm, area: 7 cm x 15 cm) so that the film thickness is 50 µm, and dried at 70°C for 5 minutes. A membrane was obtained. The obtained coating film was irradiated with ultraviolet rays under the condition of 1000 mJ/cm ² with a high-pressure mercury lamp, and the obtained laminate of the glass plate and the cured product was used as a sample.

[Evaluation of hardness]
The prepared samples were subjected to pencil hardness measurement, and the hardness was evaluated according to the following criteria.

According to JIS K5600-5-4 (1999), the pencil hardness of the cured surface of the sample was measured under a load of 750 g. Each hardness was measured 5 times, and the surface hardness of the laminated film was defined as the hardness at which 4 or more measurements did not cause damage.

5: 3H or more 4: 2H
3:H
2:F
1: HB or less

[Evaluation of Coating Appearance]
For the prepared sample, the cured product was peeled off, and the haze value of the cured product was measured using a haze computer HZ-2 (manufactured by Suga Test Instruments Co., Ltd.). was evaluated.

5: Less than 0.3 4: 0.3 or more and less than 1.0 3: 1.0 or more and less than 2.0 2: 2.0 or more and less than 5.0 1: 5.0 or more

[Evaluation of water resistance]
The prepared sample was immersed in distilled water at 25° C. and allowed to stand for 3 hours. After immersion, the haze value of the cured product was measured in the same manner as in the evaluation of the coating film appearance, and the obtained haze value was evaluated for water resistance according to the following criteria.

5: less than 0.5 4: 0.5 or more and less than 2.0 3: 2.0 or more and less than 4.0 2: 4.0 or more and less than 6.0 1: 6.0 or more

[Evaluation of primary antifogging property]
The prepared sample was held at the top of a container containing hot water at 90° C. (at a position 3 cm from the surface of the hot water in the container) for 3 seconds so that the entire surface of the cured sample was in contact with the steam. After that, the time for the fog to disappear completely was measured at 25° C. and a relative humidity of 50%, and the anti-fogging property was evaluated according to the following criteria.

5: No cloudiness at all 4: Cloudiness disappears within 1 second 3: Cloudiness disappears within 3 seconds 2: Cloudiness disappears within 10 seconds 1: No cloudiness disappears even after 10 seconds

[Evaluation of secondary antifogging property]
After the prepared sample was immersed in water at 25 ° C. for 10 days, the sample was placed at the top of a container containing hot water at 90 ° C. (3 cm from the hot water surface in the container). was held in contact with the steam for 3 seconds. After that, the time for the fog to disappear completely was measured at 25° C. and a relative humidity of 50%, and the anti-fogging property was evaluated according to the following criteria.

5: No cloudiness at all 4: Cloudiness disappears within 1 second 3: Cloudiness disappears within 3 seconds 2: Cloudiness disappears within 10 seconds 1: No cloudiness disappears even after 10 seconds

Active energy ray-curable antifogging compositions (1) to (10) obtained in Examples 1 to 10, and active energy ray curable antifogging compositions (C1) obtained in Comparative Examples 1 to 4 Table 1 shows the compositions and evaluation results of (C4).

"Nonionic antifogging agent (B)" in Table 1 indicates diglycerin monolaurate.

"Aqueous unsaturated group-containing miscibility accelerator (C-1)" in Table 1 indicates hydroxyethyl acrylamide.

"Aqueous unsaturated group-containing miscibility accelerator (C-2)" in Table 1 indicates acryloylmorpholine.

"TMPTA" in Table 1 indicates trimethylolpropane triacrylate.

"Polyisocyanate compound (D)" in Table 1 indicates a hexamethylene diisocyanate-based isocyanurate-type polyisocyanate ("Barnock DN-980S" manufactured by DIC Corporation).

"Hydrophilic resin (E)" in Table 1 indicates polyvinylpyrrolidone.

Examples 1 to 10 shown in Table 1 are examples using the active energy ray-curable antifogging composition of the present invention. The cured product of the active energy ray-curable antifogging composition of the present invention has excellent coating film hardness, coating film appearance, and water resistance, as well as excellent primary and secondary antifogging properties. It was confirmed that the

On the other hand, Comparative Example 1 is an example using an active energy ray-curable antifogging composition that does not contain a hydroxyl group-containing (meth)acrylate compound. The cured product of the active energy ray-curable antifogging composition obtained in Comparative Example 1 was insufficient in coating film hardness and primary antifogging properties, and was significantly insufficient in secondary antifogging properties. I was able to confirm that.

Comparative Example 2 is an example using an active energy ray-curable antifogging composition that does not contain an aqueous unsaturated group-containing miscibility accelerator. The cured product of the active energy ray-curable antifogging composition obtained in Comparative Example 2 was insufficient in coating film appearance and primary antifogging properties, and was significantly insufficient in secondary antifogging properties. I was able to confirm that.

Comparative Example 3 is an example using an active energy ray-curable antifogging composition containing no nonionic antifogging agent. It can be confirmed that the cured product of the active energy ray-curable antifogging composition obtained in Comparative Example 3 has insufficient primary antifogging properties and is significantly insufficient in secondary antifogging properties. rice field.

Comparative Example 4 is an example using an active energy ray-curable antifogging composition that does not contain a polyisocyanate compound. It was confirmed that the cured product of the active energy ray-curable antifogging composition obtained in Comparative Example 4 was remarkably insufficient in both primary antifogging properties and secondary antifogging properties.

Claims (8)

a hydroxyl group-containing (meth)acrylate compound (A) having no amide group;
a nonionic antifogging agent (B);
(meth)acrylamide monomer and/or acryloylmorpholine;
An active energy ray-curable antifogging composition containing a polyisocyanate compound (D),
The nonionic antifogging agent (B) is a compound having no (meth)acryloyl group in the molecule and having an ester bond and/or a polyoxyethylene group,
The content of the hydroxyl group-containing (meth)acrylate compound (A) is in the range of 10% by mass or more and 60% by mass or less in the solid content of the active energy ray-curable antifogging composition,
The content of the nonionic antifogging agent (B) is 3% by mass or more in the solid content of the active energy ray-curable antifogging composition,
The total content of the (meth)acrylamide monomer and/or acryloylmorpholine is in the range of 15% by mass or more and 60% by mass or less in the solid content of the active energy ray-curable antifogging composition,
The content of the polyisocyanate compound (D) is in the range of 1.9% by mass or more and 40% by mass or less in the solid content of the active energy ray-curable antifogging composition,
The total content of the hydroxyl group-containing (meth)acrylate compound (A), the nonionic antifogging agent (B), the (meth)acrylamide monomer and/or acryloylmorpholine, and the polyisocyanate compound (D) is An active energy ray-curable antifogging composition characterized by having a solid content of 95% by mass or more in the active energy ray curable antifogging composition. 2. The active energy ray-curable antifogging composition according to claim 1, wherein the hydroxyl group-containing (meth)acrylate compound (A) having no amide group has a hydroxyl value of 250 mgKOH/g or more. 2. The active energy ray-curable antifogging composition according to claim 1, wherein the hydroxyl group-containing (meth)acrylate compound (A) having no amide group is a (meth)acrylic acid adduct of an epoxy compound. The active energy ray-curable antifogging composition according to claim 1, wherein the nonionic antifogging agent (B) contains a polyglycerin long-chain fatty acid ester. The active energy ray-curable antifogging composition according to claim 1, further comprising a hydrophilic resin (E). 6. The active energy ray-curable antifogging composition according to claim 5, wherein the hydrophilic resin (E) contains polyvinylpyrrolidone. The content of the polyisocyanate compound (D) is such that the hydroxyl group-containing (meth)acrylate compound (A) having no amide group , the nonionic antifogging agent (B), and the (meth)acrylamide monomer and/or The active energy ray-curable antifogging composition according to claim 1, wherein the amount is in the range of 5 to 40 parts by mass with respect to 100 parts by mass of acryloylmorpholine . A cured product, which is a cured reaction product of the active energy ray-curable antifogging composition according to any one of claims 1 to 7.