JP6894716B2 - Active energy ray-curable fingerprint resistance imparting agent - Google Patents

Description

The present invention relates to an active energy ray-curable fingerprint resistance imparting agent. More specifically, the present invention relates to an active energy ray-curable fingerprint resistance imparting agent having excellent antifouling property against stains such as fingerprints and sebum.

Conventionally, various plastic films having a hard coat layer for preventing scratches have been used on the surface of a liquid crystal display such as a liquid crystal television or a mobile phone.
However, in recent years, with the spread of touch panel displays that can be operated by pressing the display on the screen, deterioration of visibility due to adhesion of fingerprints and sebum has become a problem, and not only scratch resistance but also fingerprints and fingerprints have become a problem. There is a strong demand for performance that makes it difficult to see dirt caused by sebum and makes it easier to wipe off dirt (hereinafter abbreviated as fingerprint resistance).
In order to impart fingerprint resistance, for example, the use of a fluorine-based acrylate (for example, Patent Document 1) and the use of a polyalkylene glycol diacrylate (for example, Patent Document 2) have been proposed.

Japanese Unexamined Patent Publication No. 2004-305845 Japanese Patent No. 5757065

However, although the fingerprint resistance imparting agent described in Patent Document 1 improves the wiping property of fingerprints and sebum, the fingerprints and sebum stains adhering to the surface of the coating film become oil droplets, so that light is scattered and the fingerprints are fingerprinted. There is a problem that the stains on the skin and sebum are more noticeable.
Further, the fingerprint resistance imparting agent described in Patent Document 2 exerts an excellent effect on fingerprint resistance, but requires a large amount of polyalkylene glycol diacrylate used as the fingerprint resistance imparting agent, resulting in scratch resistance. There is a problem that the sex is reduced.
An object of the present invention is to provide an active energy ray-curable fingerprint resistance imparting agent capable of exhibiting excellent fingerprint resistance with a small amount and imparting fingerprint resistance without deteriorating the scratch resistance of the cured coating film. is there.

The present inventors have arrived at the present invention as a result of diligent studies to solve the above problems. That is, the present invention is an active energy ray-curable fingerprint resistance imparting agent containing a monofunctional (meth) acrylate compound (A) represented by the following general formula (1), in the (X). The (A) is an active energy ray-curable fingerprint resistance imparting agent (X) of 70% by weight or more ; the (X) and a polyfunctional (meth) acrylate having 2 to 12 (meth) acryloyl groups. B) is an active energy ray-curable resin composition (Y) containing and.
General formula (1):
CH ₂ = C (R ¹ ) -C (= O) O- (a0) -O- (b0)
[In the formula, R ¹ is an H or methyl group; (a0) is a residue obtained by removing a hydroxyl group from a (poly) alkylene (alkylene having 2 to 4 carbon atoms) glycol (a); (b0) is a carbon number. It represents the residue obtained by removing the hydroxyl group from the monohydric alcohol (b) of 1-36. The above (b) is a branched monohydric alcohol having 8 to 36 carbon atoms. ]

The active energy ray-curable fingerprint resistance imparting agent (X) of the present invention has the following effects.
(1) Gives a cured product excellent fingerprint resistance with a small amount.
(2) The cured product has excellent scratch resistance.
(3) The cured product has excellent transparency.

<Monofunctional (meth) acrylate compound (A)>
The monofunctional (meth) acrylate compound (A) in the present invention is represented by the following general formula (1).

General formula (1):
CH ₂ = C (R ¹ ) -C (= O) O- (a0) -O- (b0)

In the general formula (1), R ¹ is an H or a methyl group; (a0) is a residue obtained by removing a hydroxyl group from a (poly) alkylene (alkylene having 2 to 4 carbon atoms) glycol (a); (b0) is , Represents a residue obtained by removing a hydroxyl group from a monohydric alcohol (b) having 1 to 36 carbon atoms.

In the general formula (1), (a0) represents a residue obtained by removing a hydroxyl group from a (poly) alkylene (alkylene group having 2 to 4 carbon atoms) glycol (a).
Examples of the (poly) alkylene glycol (a) include (poly) ethylene glycol, (poly) propylene glycol, and (poly) tetramethylene glycol.
Of the above (a), (poly) propylene glycol is preferable from the viewpoint of fingerprint resistance.

The number average molecular weight (hereinafter abbreviated as Mn) of the (poly) alkylene glycol (a) is, for example, 200 or more, preferably 400 to 10,000, more preferably 400 to 10,000 from the viewpoint of fingerprint resistance and transparency of the cured product. Is 800 to 8,000, particularly preferably 1,000 to 6,000, and most preferably 1,500 to 4,000. The amount of oxypropylene in the (a) is preferably 70% by weight or more, more preferably 90% by weight or more, from the viewpoint of fingerprint resistance.
Mn in the present invention is measured by a gel permeation chromatography (GPC) method using N, N-dimethylformamide or tetrahydrofuran as a solvent with reference to standard polystyrene.

In the general formula (1), (b0) represents a residue obtained by removing a hydroxyl group from a monohydric alcohol (b) having 1 to 36 carbon atoms [hereinafter, may be abbreviated as C].
Examples of the monohydric alcohol (b) having 1 to 36 carbon atoms [hereinafter, may be abbreviated as C] include a linear alkyl alcohol (b1) and a branched alkyl alcohol (b2).
The carbon number of the (b) is 1 to 36, and is preferably 8 to 32, more preferably 12 to 28, from the viewpoint of fingerprint resistance and scratch resistance of the cured product.

(B1) Linear alkyl alcohol:
C1-36, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-nonyl alcohol, n- Decyl alcohol, n-undecyl alcohol, n-dodecyl alcohol, n-tridecyl alcohol, n-tetradecyl alcohol, n-pentadecyl alcohol, n-hexadecyl alcohol, n-heptadecyl alcohol, n-octadecyl alcohol, n -Nonadecyl alcohol, n-eicosyl alcohol, n-docosyl alcohol, n-tetracosyl alcohol, n-hexaicosyl alcohol, n-octaicosyl alcohol, n-triacontyl alcohol, n-dotriacon Tyl alcohol, n-tetratriacontyl alcohol, n-hexatriacontyl alcohol;

(B2) Branched alkyl alcohol:
C8-36, such as 2-ethylhexyl alcohol, 2-butyl octyl alcohol, 2-butyl decyl alcohol, 2-hexyl octyl alcohol, 2-hexyl decyl alcohol, 2-octyl decyl alcohol, 2-hexyl decyl alcohol, 2- Octyldodecyl alcohol, 2-decyltetradecyl alcohol, 2-dodecyl hexadecyl alcohol, 2-tetradecyl octadecyl alcohol, 2-hexadecyl icosyl alcohol.

Of the above (b), from the viewpoint of imparting fingerprint resistance, (b2) is preferable, and 2-butyl octyl alcohol, 2-butyl decyl alcohol, 2-hexyl octyl alcohol, and 2-hexyl decyl alcohol are more preferable. 2-octyldecyl alcohol, 2-hexyldodecyl alcohol, 2-octyldodecyl alcohol, 2-decyltetradecyl alcohol, 2-dodecylhexadecyl alcohol, 2-tetradecyloctadecyl alcohol, particularly preferably 2-butyldecyl alcohol, 2 -Hexyl octyl alcohol, 2-hexyl decyl alcohol, 2-octyl decyl alcohol, 2-hexyl decyl alcohol, 2-octyldo decyl alcohol, 2-decyl tetradecyl alcohol.

The weight average molecular weight (hereinafter abbreviated as Mw) of the monofunctional (meth) acrylate compound (A) in the present invention is preferably 1,500 to 15,000 from the viewpoint of fingerprint resistance and transparency of the cured product. It is preferably 2,000 to 10,000, particularly preferably 2,500 to 5,000.
Mw in the present invention is measured by GPC in the same manner as Mn described above, using N, N-dimethylformamide or tetrahydrofuran as a solvent and using standard polystyrene as a reference.

As a method for producing the monofunctional (meth) acrylate compound (A) in the present invention, for example, an alkylene oxide (2-4 carbon atoms) adduct of the monohydric alcohol (b) and (meth) acrylic acid are required. There is a method of adding an esterification catalyst to carry out an esterification reaction.

<Active energy ray-curable fingerprint resistance imparting agent (X)>
The active energy ray-curable fingerprint resistance imparting agent (X) of the present invention contains the monofunctional (meth) acrylate compound (A). The (A) in the (X) is preferably 70% by weight or more, more preferably 90% by weight or more, from the viewpoint of fingerprint resistance.
In addition to the above (A), an alkyl-modified (poly) alkylene oxide may be contained within a range that does not impair the scratch resistance and transparency of the cured product.
The (X) is suitably used as a fingerprint resistance imparting agent for the active energy ray-curable resin composition (Y) described later.

<Active energy ray-curable resin composition (Y)>
The active energy ray-curable resin composition (Y) of the present invention is a polyfunctional (meth) having the active energy ray-curable fingerprint resistance imparting agent (X) and 2 to 12 (meth) acryloyl groups described later. Contains acrylate (B).

<Polyfunctional (meth) acrylate (B)>
The polyfunctional (meth) acrylate (B) in the present invention has 2 to 12 (meth) acryloyl groups.
If the number of the (meth) acryloyl groups is less than 2, the scratch resistance of the cured product may be deteriorated, and if the number is more than 12, the transparency of the cured product may be deteriorated.
Examples of the polyfunctional (meth) acrylate (B) include C7 to C52 polyfunctional (meth) acrylate (B1), polyfunctional urethane (meth) acrylate (B2), polyfunctional polyester (meth) acrylate (B3), and these. A mixture of.

(B1) Polyfunctional (meth) acrylates of C7 to C52:
Examples of (B1) include bifunctional (meth) acrylate (B11) and 3 to 12 functional (meth) acrylate (B12).

Examples of (B11) include 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 2,4-dimethyl-1,5. -Pentanediol di (meth) acrylate, butyl ethyl propanediol di (meth) acrylate, ethoxylated cyclohexane methanol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene glycol di ( Meta) acrylate, ethylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate of hydroxypivalate, ethylene oxide (hereinafter abbreviated as EO). ) Modified bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, polypropylene glycol di (meth) acrylate, oligopropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate , 2-Ethyl-2-butyl-propanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate;

Examples of (B12) include trimethylolpropane tri (meth) acrylate, trimethylol ethanetri (meth) acrylate, alkylene oxide-modified tri (meth) acrylate of trimethylolpropane, pentaerythritol tri (meth) acrylate, and dipentaeryth. Tri (meth) acrylate with 1 to 30 molar additions of C2 to C4 alkylene oxides of rutor tri (meth) acrylate, trimethylol propantri ((meth) acryloyloxypropyl) ether, sorbitol tri (meth) acrylate, and pentaerythritol. , Ethylated glycerin tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate, pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, dipentaerythritol tetra ( Meta) acrylate, dipentaerythritol tetra (meth) acrylate of propionate, tetra (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate with 1 to 30 mol of alkylene oxide 1 to 30 mol of C2 to C4 of pentaerythritol. ) Acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate;

(B2) Polyfunctional urethane (meth) acrylate:
The polyfunctional urethane (meth) acrylate (B2) is not particularly limited as long as it is a compound obtained by reacting a (meth) acrylic acid derivative having a bifunctional or higher (meth) acryloyl group having a hydroxyl group with isocyanate. For example, it can be obtained by reacting 1 equivalent of a compound having two isocyanate groups with 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group in the presence of a metal compound (for example, tin compound).

The isocyanate used as a raw material for the polyfunctional urethane (meth) acrylate (B2) is not particularly limited, and the same raw material as in (A) can be used. The (meth) acrylic acid derivative having a bifunctional or higher functional (meth) acryloyl group having a hydroxyl group is also not particularly limited, and for example, a di (meth) acrylate of a trihydric alcohol such as trimethylolethane, trimethylolpropane, or glycerin, Examples thereof include tri (meth) acrylates of tetrahydric alcohols such as pentaerythritol and sorbitol, and penta (meth) acrylates of hexahydric alcohols such as dipentaerythritol and sorbitol.

The isocyanate may be obtained by reacting a polyol such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, or polycaprolactone diol with an excess of isocyanate. The resulting chain-extended isocyanate compound can also be used.

(B3) Polyfunctional polyester (meth) acrylate:
The polyfunctional polyester (meth) acrylate is obtained by esterifying the hydroxyl group of a polyester oligomer having a hydroxyl group at the terminal obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or by using a polyvalent carboxylic acid. It can be obtained by esterifying the hydroxyl group at the end of the oligomer obtained by adding an alkylene oxide to (meth) acrylic acid.
Examples of the polyhydric alcohol which is a constituent unit of the polyfunctional polyester (meth) acrylate (B3) include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanjiol, and neopentyl. Alkylene glycols such as glycols, 1,4-butenediols, 1,5-pentanediols and 1,6-hexanediols; alkylenes such as diethylene glycols, triethylene glycols, dipropylene glycols, polyethylene glycols, polypropylene glycols and polytetramethylene glycols. Ether glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; bisphenols such as bisphenol A, bisphenol F and bisphenol S; alkylene oxides of bisphenol [EO, propylene oxide (PO), butylene oxide ( BO)] Additives (average number of moles added 2 to 8), glycerin, trimethylolpropane, pentaerythritol and the like.

Examples of the polyvalent carboxylic acid which is a constituent unit of the polyfunctional polyester (meth) acrylate (B3) include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and succinic acid. , Adipic acid, sevantic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, isooctenyl succinic acid, n-octyl succinic acid , Isooctylsuccinic acid, aconitic acid, trimellitic acid, pyromellitic acid and the like, or anhydrides or lower alkyl esters of these acids.

Of the above polyfunctional (meth) acrylates (B), (B1) and (B2) are preferable from the viewpoint of scratch resistance of the cured product, (B1) is more preferable, and pentaerythritol tetra (meth) is particularly preferable. ) Acrylate, dipentaerythritol hexa (meth) acrylate, most preferably dipentaerythritol hexa (meth) acrylate.

The content of the monofunctional (meth) acrylate compound (A) based on the weight of the polyfunctional (meth) acrylate (B) is preferably 0.1% from the viewpoint of imparting fingerprint resistance and transparency of the cured product. It is ~ 5.0%, more preferably 0.5% to 4.0%, and particularly preferably 1.0% to 3.0%.

<Other unsaturated monomers (C)>
The active energy ray-curable resin composition (Y) includes the active energy ray-curable fingerprint resistance imparting agent (A) and the polyfunctional (meth) acrylate (B) as long as the effects of the present invention are not impaired. If necessary, other unsaturated monomer (C) can be used in combination.
Other unsaturated monomers (C) include the following (C1) to (C3) and mixtures thereof.

(C1) Monofunctional (meth) acrylates of C3 to C35:
(Meta) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl ( Meta) acrylate, 2,3-dimethylhexyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, icosyl (meth) Acrylate, n-docosyl (meth) acrylate, n-tetracosyl (meth) acrylate, n-hexaicosyl (meth) acrylate, n-octaicosyl (meth) acrylate, n-triacontyl (meth) acrylate, n-dotriacyl (meth) acrylate, n-Tetratriacontyl (meth) acrylate, n-hexatriacontyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, Bornyl (meth) acrylate, Isobornyl (meth) Acrylate, benzyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate, cyanoethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meth) acrylate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4-butylphenyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, 4-chlorophenyl (meth) acrylate, phenoxymethyl ( Meta) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, glycidyloxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) Acrylate, hydroxyalkyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( Meta) Acrylate, Dimethylaminoethyl (Meta) Acrylate, Diethylaminoethyl (Meta) Acrylate G, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, acryloylmorpholine, dimethylacrylamide, polyethylene glycol Mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, 2-Hydroxy-3-phenoxypropyl (meth) acrylate, etc .;

(C2) Compound having a vinyl group:
Examples of the compound having a vinyl group (C2) include a compound having one vinyl group (C21) and a compound having two or more (preferably 2 to 6) vinyl groups (C22).

(C21) Compound of C2-C35 having one vinyl group For example, vinylamine, N-methylvinylamine, N-ethylvinylamine, N-propylvinylamine, Nn-butylvinylamine, Nt-butyl Vinylamine, N-butoxymethylvinylamine, N-isopropylvinylamine, N-methylolvinylamine, N, N-dimethylvinylamine and N, N-diethylvinylamine, N-vinylmorpholine, methylvinyl ether, ethylvinyl ether, butyl Vinyl ether, tert-butyl vinyl ether, hexyl vinyl ether, 2-ethylhexyl vinyl ether, tert-octyl vinyl ether, 2,3-dimethylhexyl vinyl ether, isoamyl vinyl ether, decyl vinyl ether, isodecyl vinyl ether, stearyl vinyl ether, isostearyl vinyl ether, cyclohexyl vinyl ether, 4- n-Butylcyclohexyl vinyl ether, Bornyl vinyl ether, Isobornyl vinyl ether, benzyl vinyl ether, 2-Ethylhexyl diglycol vinyl ether, Butoxy ethyl vinyl ether, 2-Chloroethyl vinyl ether, 4-Bromobutyl vinyl ether, Cyanoethyl vinyl ether, Butoxymethyl vinyl ether, methoxy Propropylene monovinyl ether, 3-methoxybutyl vinyl ether, alkoxymethyl vinyl ether, 2-ethylhexylcarbitol vinyl ether, alkoxyethyl vinyl ether, 2- (2-methoxyethoxy) ethyl vinyl ether, 2- (2-butoxyethoxy) ethyl vinyl ether, 2 , 2,2-Tetrafluoroethyl vinyl ether, 1H, 1H, 2H, 2H-perfluorodecylvinyl ether, 4-butylphenyl vinyl ether, phenylvinyl ether, 2,4,5-tetramethylphenylvinyl ether, 4-chlorophenylvinyl ether, phenoxymethyl Vinyl ether, phenoxyethyl vinyl ether, glycidyl vinyl ether, glycidyloxybutyl vinyl ether, glycidyloxyethyl vinyl ether, glycidyloxypropyl vinyl ether, tetrahydrofurfuryl vinyl ether, hydroxyalkyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2- Hydroxypropyl vinyl ether, 2-Hydroxybutyl vinyl ether, 4-hydroxybutyl vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, dimethylaminopropyl vinyl ether, diethylaminopropyl vinyl ether, trimethoxysilylpropyl vinyl ether, trimethoxysilylpropyl vinyl ether, trimethylsilylpropyl vinyl ether, polyethylene oxide monomethyl ether Vinyl ether, oligoethylene oxide monomethyl ether vinyl ether, polyethylene oxide vinyl ether, oligoethylene oxide vinyl ether, oligoethylene oxide monoalkyl ether vinyl ether, polyethylene oxide monoalkyl ether vinyl ether, dipropylene glycol vinyl ether, polypropylene oxide monoalkyl ether vinyl ether, oligopropylene oxide monoalkyl Ether vinyl ether, 2-methacrylooxyethyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid, butoxydiethylene glycol vinyl ether, trifluoroethyl vinyl ether, perfluorooctyl ethyl vinyl ether, 2-hydroxy-3-phenoxypropyl vinyl ether, EO-modified phenol Vinyl ether, EO-modified cresol vinyl ether, EO-modified nonylphenol vinyl ether, PO-modified nonylphenol vinyl ether, EO-modified -2-ethylhexyl vinyl ether, etc .;

(C22) Compounds C8 to C50 having 2 to 6 vinyl groups:
For example, 1,6-hexanediol divinyl ether, 1,10-decanediol divinyl ether, neopentyl glycol divinyl ether, 2,4-dimethyl-1,5-pentanediol divinyl ether, butylethylpropanediol divinyl ether, ethoxylated. Cyclohexanemethanol divinyl ether, polypropylene glycol divinyl ether, polyethylene glycol divinyl ether, oligoethylene glycol divinyl ether, ethylene glycol divinyl ether, 2-ethyl-2-butyl-butanediol divinyl ether, neopentyl glycol divinyl ether hydroxypivalate, EO modification Bisphenol A divinyl ether, EO modified bisphenol F divinyl ether, polypropylene glycol divinyl ether, oligopropylene glycol divinyl ether, 1,4-butanediol divinyl ether, 2-ethyl-2-butyl-propanediol divinyl ether, 1,9-nonane Didiol divinyl ether, propoxylated ethoxylated bisphenol A divinyl ether, trimetylolpropane trivinyl ether, trimethylol ethanetrivinyl ether, alkylene oxide-modified trivinyl ether of trimethylolpropane, pentaerythritol trivinyl ether, dipentaerythritol trivinyl ether, trimethylol Propanetri (vinyloxypropyl) ether, sorbitol trivinyl ether, trivinyl ether with 1 to 30 molar additions of C2 to C4 alkylene oxide of pentaerythritol, glycerin trivinyl ether ethoxylated, dipentaerythritol trivinyl ether propionate, pentaerythritol tetravinyl ether , Sorbitol tetravinyl ether, ditrimethylolpropane tetravinyl ether, dipentaerythritol tetravinyl ether, dipentaerythritol tetravinyl ether propionate, tetravinyl ether with 1 to 30 molar additions of alkylene oxides of C2 to C4 of pentaerythritol, sorbitol pentavinyl ether, dipenta. Ellisritol pentavinyl ether, dipentaerythritol hexavinyl ether, sorbitol hexavinyl ether, caprolactone-modified dipentaerythritol hexavinyl ether, etc.

(C3) Compound having an allyl group:
Examples of the compound having an allyl group (C3) include a compound having one allyl group (C31), a compound having 2 to 6 allyl groups (C32), a bifunctional or higher functional urethane allyl ether (C33), and a bifunctional compound. Examples thereof include the above polyester allyl ether (C34).

(C31) Compounds C3 to C35 having one allyl group:
For example, allylamine, N-methylallylamine, N-ethylallylamine, N-propylallylamine, Nn-butylallylamine, Nt-butylallylamine, N-butoxymethylallylamine, N-isopropylallylamine, N-methylolallylamine, N. , N-dimethylallylamine and N, N-diethylallylamine, N-allylmorpholine, methylallyl ether, ethylallyl ether, butylallyl ether, tert-butylallyl ether, hexylallyl ether, 2-ethylhexylallyl ether, tert-octylallyl Ether, 2,3-dimethylhexyl allyl ether, isoamyl allyl ether, decyl allyl ether, isodecyl allyl ether, stearyl allyl ether, isostearyl allyl ether, cyclohexyl allyl ether, 4-n-butylcyclohexyl allyl ether, bornyl allyl Ether, isobornyl allyl ether, benzyl allyl ether, 2-ethylhexyl diglycol allyl ether, butoxyethyl allyl ether, 2-chloroethyl allyl ether, 4-bromobutyl allyl ether, cyanoethyl allyl ether, butoxymethyl allyl ether, methoxypropylene Monoallyl ether, 3-methoxybutyl allyl ether, alkoxymethylallyl ether, 2-ethylhexylcarbitol allyl ether, alkoxyethylallyl ether, 2- (2-methoxyethoxy) ethylallyl ether, 2- (2-butoxyethoxy) ) Ethylallyl ether, 2,2,2-tetrafluoroethylallyl ether, 1H, 1H, 2H, 2H-perfluorodecylallyl ether, 4-butylphenylallyl ether, phenylallyl ether, 2,4,5-tetramethyl Phenylallyl ether, 4-chlorophenylallyl ether, phenoxymethylallyl ether, phenoxyethyl allyl ether, glycidyl allyl ether, glycidyloxybutyl allyl ether, glycidyloxyethyl allyl ether, glycidyloxypropyl allyl ether, tetrahydrofurfuryl allyl ether , Hydroxyalkylallyl ether, 2-hydroxyethylallyl ether, 3-hydroxypropylallyl ether, 2-hydroxypropylallyl ether, 2-hydroxybutylallyl ether, 4-hydroxybuty Luaryl ether, dimethylaminoethyl allyl ether, diethylaminoethyl allyl ether, dimethylaminopropyl allyl ether, diethylaminopropyl allyl ether, trimethoxysilylpropyl allyl ether, trimethoxysilylpropyl allyl ether, trimethylsilylpropyl allyl ether, polyethylene oxide monomethyl ether allyl. Ether, oligoethylene oxide monomethyl ether allyl ether, polyethylene oxide allyl ether, oligoethylene oxide allyl ether, oligoethylene oxide monoalkyl ether allyl ether, polyethylene oxide monoalkyl ether allyl ether, dipropylene glycol allyl ether, polypropylene oxide monoalkyl ether allyl Ether, oligopropylene oxide monoalkyl ether allyl ether, 2-methacrylooxyethyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid, butoxydiethylene glycol allyl ether, trifluoroethyl allyl ether, perfluorooctylethyl allyl ether, 2- Hydroxy-3-phenoxypropylallyl ether, EO-modified phenolallyl ether, EO-modified cresolallyl ether, EO-modified nonylphenolallyl ether, PO-modified nonylphenolallyl ether and EO-modified -2-ethylhexylallyl ether;

(C32) Compounds of C3 to C35 having 2 to 6 allyl groups:
For example, 1,6-hexanediol diallyl ether, 1,10-decanediol diallyl ether, neopentyl glycol diallyl ether, 2,4-dimethyl-1,5-pentanediol diallyl ether, butyl ethyl propanediol diallyl ether, ethoxylation. Cyclohexanemethanol diallyl ether, polypropylene glycol diallyl ether, polyethylene glycol diallyl ether, oligoethylene glycol diallyl ether, ethylene glycol diallyl ether, 2-ethyl-2-butyl-butanediol diallyl ether, neopentyl glycol diallyl ether hydroxypivalate, EO modification Bisphenol A diallyl ether, EO modified bisphenol F diallyl ether, polypropylene glycol diallyl ether, oligopropylene glycol diallyl ether, 1,4-butanediol diallyl ether, 2-ethyl-2-butyl-propanediol diallyl ether, 1,9-nonane Didiol diallyl ether, propoxylated ethoxylated bisphenol A diallyl ether, trimethylolpropane triallyl ether, trimethylol ethanetriallyl ether, alkylene oxide-modified triallyl ether of trimethylolpropane, pentaerythritol triallyl ether, dipentaerythritol tri Allyl ether, trimethylolpropantri (allyloxypropyl) ether, sorbitol triallyl ether, triallyl ether with 1 to 30 molar additions of C2 to C4 alkylene oxide of pentaerythritol, glycerin triallyl ether ethoxylated, dipenta propionate Elythritol triallyl ether, pentaerythritol tetraallyl ether, sorbitol tetraallyl ether, ditrimethylol propanetetraallyl ether, dipentaerythritol tetraallyl ether, dipentaerythritol tetraallyl ether propionate, C2-C4 alkylene oxides 1 to pentaerythritol Tetraallyl ether, sorbitol pentaallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, sorbitol hexaallyl ether, caprolactone-modified dipentaerythritol hexaallyl ether;

The bifunctional or higher (preferably 2 to 8 functional, more preferably bifunctional) urethane allyl ether (C33) is not particularly limited as long as it is a compound obtained by reacting isocyanate with an allyl alcohol derivative having a hydroxyl group. For example, it can be obtained by reacting 1 equivalent of a compound having two isocyanate groups with 2 equivalents of an allyl alcohol derivative having a hydroxyl group in the presence of a metal compound (for example, tin compound) as a catalyst.

The isocyanate used as the raw material of the bifunctional or higher functional urethane allyl ether (C33) is not particularly limited, and the isocyanate used as the raw material of the above-mentioned (A) can be used.
The allyl alcohol derivative having a hydroxyl group as a raw material for bifunctional or higher functional urethane allyl ether (C33) is also not particularly limited, and for example, 2-hydroxyethyl allyl ether, 2-hydroxypropyl allyl ether, 4-hydroxybutyl allyl ether, etc. Divalent alcohol monoallyl ethers such as 2-hydroxybutylallyl ether, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol, trimethylolethane. , Monoallyl ethers or diallyl ethers of trivalent alcohols such as trimethylolpropane and glycerin, and epoxyallyl ethers such as bisphenol A-modified epoxyallyl ethers.

The bifunctional or higher (preferably 2 to 8 functional, more preferably bifunctional) polyester allyl ether (C34) contains allyl of the hydroxyl group of the polyester oligomer having a hydroxyl group at the terminal obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol. It can be obtained by etherifying with bromide, or by etherifying the hydroxyl group at the end of the oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with allyl bromide.

The polyhydric alcohol which is a constituent unit of the bifunctional or higher functional polyester allyl ether (C34) and the polyvalent carboxylic acid are not particularly limited, and the polyhydric alcohol used in the above-mentioned polyfunctional polyester (meth) acrylate (B3). Polyvalent carboxylic acid can be used.

The content of the other unsaturated monomer (C) is usually 20% based on the total weight of the active energy ray-curable fingerprint resistance imparting agent (X) and the polyfunctional (meth) acrylate (B). Hereinafter, from the viewpoint of imparting fingerprint resistance, scratch resistance and transparency, it is preferably 0.1% to 10%, and more preferably 0.5% to 5%.

The active energy ray-curable resin composition (Y) of the present invention may be diluted with an organic solvent (D). Examples of the organic solvent (D) include an aromatic hydrocarbon solvent (D1), an aliphatic hydrocarbon solvent (D2), a halogenated hydrocarbon solvent (D3), an ester solvent (D4), an ether solvent (D5), and a ketone solvent. (D6), alcohol solvent (D7) and mixtures thereof.

(D1) Aromatic hydrocarbon solvent:
For example, toluene, xylene, ethylbenzene;
(D2) Aliphatic hydrocarbon solvent:
For example, cyclohexane, cyclopentane;
(D3) Halogenated Hydrocarbon Solvent For example, methyl chloride, methyl iodide, carbon tetrachloride, trichlorethylene, perchloroethylene;
(D4) Ester solvent:
For example, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, methyl propionate. , Ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl 2-hydroxyisobutyrate, methyl lactate, ethyl lactate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, methyl pyruvate and Ethyl pyruvate;
(D5) Ether Solvent For example, tetrahydrofuran, dioxane, dioxolane, ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether;
(D6) Ketone solvent For example, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone;
(D7) Alcohol solvent For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, benzyl alcohol, 2,2,3,3-tetrafluoropropanol and trifluoro. ethanol.

As the organic solvent (D), the solubility parameter (hereinafter abbreviated as SP value) is preferably 8.0 to 9.5. When the solubility parameter is smaller than 8.0, the polyfunctional (meth) acrylate (B) is cured. When the solubility parameter is larger than 9.5, the monofunctional (meth) acrylate compound (A) becomes cloudy without being dissolved. Later transparency may decrease.

Of the organic solvents (D), (D4), (D5), (D6), and more preferably (D4), are preferable from the viewpoint of transparency after curing, fingerprint resistance, and energy saving at the time of coating. (D6), particularly preferably (D6), most preferably methyl ethyl ketone.

The content of the organic solvent (D) is preferably 1 to 50%, more preferably 5 to 5 based on the total weight of the cured products (A) and (B) from the viewpoint of transparency and industrial aspects of the cured product. It is 40%, particularly preferably 10 to 30%.

The active energy ray-curable resin composition (Y) of the present invention contains, if necessary, a photopolymerization initiator (e1), a leveling agent (e2), an antioxidant (e3), as long as the effects of the present invention are not impaired. It may contain at least one additive (e) selected from the group consisting of UV absorbers (e4) and fillers (e5).

Examples of the photopolymerization initiator (e1) include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and 2-methyl-1- (4-methylthio). Phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 1,2- (dimethylamino) -2-[(4-methylphenyl) ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2- Hydroxy-2-methyl-1-phenyl-propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hirodoxy -1- {4- [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 1, 2-octanedione-1- (4- [phenylthio) -2- (O-benzoyloxime)], etanone-1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (0-acetyloxime), bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, etc. Can be mentioned.

As the leveling agent (e2), polydimethylsiloxane, a copolymer thereof, an acrylic polymer having a polydimethylsiloxane skeleton, a urethane polymer having a polydimethylsiloxane skeleton, and an acryloyl group or a methacryloyl group are introduced into these, and an active energy ray is used. Examples thereof include compounds having imparted reactivity.

Examples of the antioxidant (e3) include di-t-butylhydroxytoluene (BHT) and 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)-. 1,3,5-triazine, pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5) -Di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexa Methylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4) -Hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, diphenylamine octylated, 2,4-bis [(octylthio) methyl] -O-cresol, isooctyl Examples thereof include -3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and dibutylhydroxytoluene.

Examples of the ultraviolet absorber (e4) include 2- (2-hydroxy-5-methyl) benzotriazole and 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole. , 2- (2'-Hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole, 2- (2'- Hydroxy-3', 5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-t-butylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazole- 2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2'-hydroxy-3', 5'-t-pentylbenzotriazole, 2- [2'-hydroxy- 5'-(1,1,3,3, -tetramethylbutyl)] benzotriazole, 2- (2'-hydroxy-3'-s-butyl-5'-t-butylbenzotriazole, 2- (2') -Hydroxy-3-dodecyl-5'-methylbenzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy- 5'-Methylphenyl) benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl)] -6- (2H-benzotriazole-2-yl) phenol], 3-[ Examples thereof include 3- (2H-benzotriazole-2-yl) -5-t-butyl-4-hydroxyphenyl] propionate and polyethylene glycol.
Examples of the filler (e5) include silica, alumina, and compounds obtained by introducing an acryloyl group or a methacryloyl group into these to impart active energy ray reactivity.

These additives (e) can be used alone or in combination of two or more. The amount of the additive (e) added is preferably 10% by weight or less, more preferably 0.1 to 5% by weight, based on the weight of the active energy ray-curable resin composition (Y).

<Cured product (P)>
The cured product (P) of the present invention is a cured product (Y) of the active energy ray-curable resin composition (Y). That is, the active energy ray-curable resin composition (Y) is cured by the active energy rays to become a cured product. Examples of the active energy ray include ultraviolet rays and electron beams.
When irradiating the ultraviolet rays, a known ultraviolet irradiation device equipped with a high-pressure mercury lamp, a metal halide lamp, or the like can be used. The irradiation amount of ultraviolet rays is preferably 30 to 2,000 mJ / cm ² . If the irradiation amount is ^{less than 30 mJ / cm 2} , the curable composition is insufficiently cured, and if it ^{exceeds 2,000 mJ / cm 2} , the cured product may be yellowed and deteriorated.
When irradiating the electron beam, a known electron beam irradiating device can be used. The irradiation amount of the electron beam is preferably 1 to 10 Mrad. If the irradiation amount is less than 1 Mrad, the curable composition is insufficiently cured, and if it exceeds 10 Mrad, the cured product may be deteriorated.

The active energy ray-curable resin composition (Y) of the present invention can impart fingerprint resistance, scratch resistance, and transparency to the cured product.
Therefore, the composition and the cured product can be used as an optical lens (prism sheet, collimator lens, Fresnel lens, lenticular lens, back-reflection lens, hologram, etc.), a coating agent for a decorative film, a hard coat film, and an antireflection film. , Decorative sheets (interior materials for building floors, walls, ceilings, etc.) are useful.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the following examples, parts represent parts by weight and% represents% by weight.

<Example 1>
A SUS autoclave equipped with a thermometer and a stirrer was charged with 675 parts of 2-butyloctanol [trade name "ISOFOL 12", manufactured by SASOL] and 1.6 parts of sodium hydroxide, and after sufficient nitrogen substitution in the container, the inside of the container was sufficiently replaced with nitrogen. It was sealed and heated to 100 ° C. After a reaction of blowing 7250 parts of propylene oxide at 100 ° C. for 1 hour, the temperature was raised to 180 ° C., aged at 180 ° C. for 2 hours, and then cooled to 25 ° C.
The contents were transferred to a glass reactor equipped with a thermometer, a stirrer, a generated water separator, and a reflux condenser, and 0.048 parts of hydroquinone, 0.36 parts of sulfuric acid, 652 parts of acrylic acid and 1510 parts of toluene were charged. The temperature was raised to 115 ° C. At this temperature, the reaction was continued until the produced water was no longer separated into the produced water separator, and then toluene was distilled off at 0.1 kPa and 115 ° C.
Then, the mixture was cooled to 25 ° C. to obtain an active energy ray-curable fingerprint resistance imparting agent (X-1) containing the compound (A-1) [Mw = 2.2 × 10 ³ ].

<Example 2>
A SUS autoclave equipped with a thermometer and a stirrer was charged with 121 parts of 2-decyltetradecanol [trade name "ISOFOL 24", manufactured by SASOL] and 0.15 parts of sodium hydroxide, and the inside of the container was sufficiently replaced with nitrogen. After that, it was sealed and the temperature was raised to 100 ° C. 682 parts of propylene oxide was blown at 100 ° C. for 1 hour, then heated to 180 ° C. and aged at 180 ° C. for 2 hours, and then cooled to 25 ° C.
Transfer the contents to a glass reactor equipped with a thermometer, stirrer, generated water separator, and reflux condenser, and add 0.0045 parts of hydroquinone, 0.033 parts of sulfuric acid, 61.4 parts of acrylic acid, and 153 parts of toluene. It was charged and the temperature was raised to 115 ° C. At this temperature, the reaction was continued until the produced water was no longer separated into the produced water separator, and then toluene was distilled off at 0.1 kPa and 115 ° C.
Then, the mixture was cooled to 25 ° C. to obtain an active energy ray-curable fingerprint resistance imparting agent (X-2) containing the compound (A-2) [Mw = 2.4 × 10 ³ ].

<Example 3>
A SUS autoclave equipped with a thermometer and a stirrer was charged with 169 parts of 2-hexadecylicosanol [trade name "ISOFOL 36", manufactured by SASOL] and 0.15 parts of sodium hydroxide, and the inside of the container was sufficiently replaced with nitrogen. After that, it was sealed and the temperature was raised to 100 ° C. 647 parts of propylene oxide was blown at 100 ° C. for 1 hour, then heated to 180 ° C. and aged at 180 ° C. for 2 hours, and then cooled to 25 ° C.
Transfer the contents to a glass reactor equipped with a thermometer, stirrer, generated water separator, and reflux condenser, and add 0.0043 parts of hydroquinone, 0.032 parts of sulfuric acid, 58.2 parts of acrylic acid, and 154 parts of toluene. It was charged and the temperature was raised to 115 ° C. At this temperature, the reaction was continued until the produced water was no longer separated into the produced water separator, and then toluene was distilled off at 0.1 kPa and 115 ° C.
Then, the mixture was cooled to 25 ° C. to obtain an active energy ray-curable fingerprint resistance imparting agent (X-3) containing the compound (A-3) [Mw = 2.6 × 10 ³ ].

< Reference example 4>
Stearyl alcohol [trade name "Calcol 8098", manufactured by Kao Corporation] 95.2 parts and 0.16 parts of sodium hydroxide were charged into a SUS autoclave equipped with a thermometer and a stirrer, and the inside of the container was sufficiently replaced with nitrogen. After that, it was sealed and the temperature was raised to 100 ° C. After a reaction of blowing 706 parts of propylene oxide at 100 ° C. for 1 hour, the temperature was raised to 180 ° C., aged at 180 ° C. for 2 hours, and then cooled to 25 ° C.
Transfer the contents to a glass reactor equipped with a thermometer, stirrer, generated water separator, and reflux condenser, and add 0.0047 parts of hydroquinone, 0.035 parts of sulfuric acid, 63.5 parts of acrylic acid, and 153 parts of toluene. It was charged and the temperature was raised to 115 ° C. At this temperature, the reaction was continued until the produced water was no longer separated into the produced water separator, and then toluene was distilled off at 0.1 kPa and 115 ° C.
Then, the mixture was cooled to 25 ° C. to obtain an active energy ray-curable fingerprint resistance imparting agent (X-4) containing the compound (A-4) [Mw = 2.3 × 10 ³ ].

<Example 5>
In an autoclave made of SUS equipped with a thermometer and a stirrer, 29.4 parts of 2-decyltetradecanol (JIS reagent special grade manufactured by the company) and 0.037 parts of sodium hydroxide were charged, and the inside of the container was sufficiently replaced with nitrogen, and then the inside of the container was sufficiently replaced with nitrogen. It was sealed and heated to 100 ° C. After a reaction of blowing 166 parts of propylene oxide at 100 ° C. for 1 hour, the temperature was raised to 180 ° C., aged at 180 ° C. for 2 hours, and then cooled to 25 ° C.
Transfer the contents to a glass reactor equipped with a thermometer, stirrer, generated water separator, and reflux condenser, and transfer the contents to 0.0011 parts of hydroquinone, 0.0081 parts of sulfuric acid, 14.9 parts of acrylic acid, and 37.1 parts of toluene. The temperature was raised to 115 ° C. At this temperature, the reaction was continued until the produced water was no longer separated into the produced water separator, and then toluene was distilled off at 0.1 kPa and 115 ° C.
Then, the mixture was cooled to 25 ° C. to obtain an active energy ray-curable fingerprint resistance imparting agent (X-5) containing the compound (A-5) [Mw = 2.4 × 10 ³ ].

<Example 6>
A SUS autoclave equipped with a thermometer and a stirrer was charged with 100 parts of 2-butyloctanol [trade name "ISOFOL 12", manufactured by SASOL] and 0.24 parts of sodium hydroxide, and the inside of the container was sufficiently replaced with nitrogen. It was sealed and heated to 100 ° C. After blowing 803 parts of ethylene oxide at 100 ° C. for 1 hour and reacting, it was aged at the same temperature for 1 hour. Next, 809 parts of propylene oxide was blown at 100 ° C. for 1 hour, then heated to 180 ° C. and aged at 180 ° C. for 2 hours, and then cooled to 25 ° C.
Transfer the contents to a glass reactor equipped with a thermometer, stirrer, generated water separator, and reflux condenser, and add 0.0071 parts of hydroquinone, 0.053 parts of sulfuric acid, 96.6 parts of acrylic acid, and 319 parts of toluene. It was charged and the temperature was raised to 115 ° C. At this temperature, the reaction was continued until the produced water was no longer separated into the produced water separator, and then toluene was distilled off at 0.1 kPa and 115 ° C.
Then, the mixture was cooled to 25 ° C. to obtain an active energy ray-curable fingerprint resistance imparting agent (X-6) containing the compound (A-6) [Mw = 3.2 × 10 ³ ].

<Example 7>
In a SUS autoclave equipped with a thermometer and a stirrer, 131 parts of 2-butyloctanol [trade name "ISOFOL 12", manufactured by SASOL] and 0.32 parts of sodium hydroxide were charged, and after sufficient nitrogen substitution in the container, the inside of the container was sufficiently replaced with nitrogen. It was sealed and heated to 100 ° C. After a reaction of blowing 1060 parts of propylene oxide at 100 ° C. for 1 hour, it was aged at the same temperature for 1 hour. Next, 1050 parts of ethylene oxide was blown at 100 ° C. for 1 hour, then heated to 180 ° C. and aged at 180 ° C. for 2 hours, and then cooled to 25 ° C.
The contents were transferred to a glass reactor equipped with a thermometer, a stirrer, a generated water separator, and a reflux condenser, and 0.0093 parts of hydroquinone, 0.069 parts of sulfuric acid, 127 parts of acrylic acid and 418 parts of toluene were charged. The temperature was raised to 115 ° C. At this temperature, the reaction was continued until the produced water was no longer separated into the produced water separator, and then toluene was distilled off at 0.1 kPa and 115 ° C.
Then, the mixture was cooled to 25 ° C. to obtain an active energy ray-curable fingerprint resistance imparting agent (X-7) containing the compound (A-7) [Mw = 3.2 × 10 ³ ].

<Example 8>
A SUS autoclave equipped with a thermometer and a stirrer was charged with 173 parts of 2-butyloctanol [trade name "ISOFOL 12", manufactured by SASOL] and 0.32 parts of sodium hydroxide, and the inside of the container was sufficiently replaced with nitrogen. It was sealed and heated to 100 ° C. A mixture of 1060 parts of propylene oxide and 1050 parts of ethylene oxide was blown at 100 ° C. for 2 hours, then heated to 180 ° C. and aged at 180 ° C. for 2 hours, and then cooled to 25 ° C.
The contents were transferred to a glass reactor equipped with a thermometer, a stirrer, a generated water separator, and a reflux condenser, and 0.0093 parts of hydroquinone, 0.069 parts of sulfuric acid, 127 parts of acrylic acid and 426 parts of toluene were charged. The temperature was raised to 115 ° C. At this temperature, the reaction was continued until the produced water was no longer separated into the produced water separator, and then toluene was distilled off at 0.1 kPa and 115 ° C.
Then, the mixture was cooled to 25 ° C. to obtain an active energy ray-curable fingerprint resistance imparting agent (X-8) containing the compound (A-8) [Mw = 2.5 × 10 ³ ].

<Example 9>
In a SUS autoclave equipped with a thermometer and a stirrer, 87 parts of 2-decyltetradecanol (JIS reagent special grade manufactured by the company) and 0.11 part of sodium hydroxide were charged, and the inside of the container was sufficiently replaced with nitrogen and then sealed. , The temperature was raised to 100 ° C. After a reaction of blowing 975 parts of propylene oxide at 100 ° C. for 1 hour, the temperature was raised to 180 ° C., aged at 180 ° C. for 2 hours, and then cooled to 25 ° C.
Transfer the contents to a glass reactor equipped with a thermometer, stirrer, generated water separator, and reflux condenser, and add 0.0032 parts of hydroquinone, 0.024 parts of sulfuric acid, 44.2 parts of acrylic acid, and 195 parts of toluene. It was charged and the temperature was raised to 115 ° C. At this temperature, the reaction was continued until the produced water was no longer separated into the produced water separator, and then toluene was distilled off at 0.1 kPa and 115 ° C.
Then, the mixture was cooled to 25 ° C. to obtain an active energy ray-curable fingerprint resistance imparting agent (X-9) containing the compound (A-9) [Mw = 4.4 × 10 ³ ].

<Example 10>
A SUS autoclave equipped with a thermometer and a stirrer was charged with 101 parts of 2-hexadecylicosanol [trade name "ISOFOL 36", manufactured by SASOL] and 0.087 parts of sodium hydroxide, and the inside of the container was sufficiently replaced with nitrogen. After that, it was sealed and the temperature was raised to 100 ° C. 387 parts of propylene oxide was blown at 100 ° C. for 1 hour, then heated to 180 ° C. and aged at 180 ° C. for 2 hours, and then cooled to 25 ° C.
Transfer the contents to a glass reactor equipped with a thermometer, stirrer, generated water separator, and reflux condenser, and transfer the contents to 0.0026 parts of hydroquinone, 0.019 parts of sulfuric acid, 41.6 parts of methacrylic acid, and 93.5 parts of toluene. The temperature was raised to 115 ° C. At this temperature, the reaction was continued until the produced water was no longer separated into the produced water separator, and then toluene was distilled off at 0.1 kPa and 115 ° C.
Then, the mixture was cooled to 25 ° C. to obtain an active energy ray-curable fingerprint resistance imparting agent (X-10) containing the compound (A-10) [Mw = 2.6 × 10 ³ ].

<Comparative example 1>
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, and a water diversion tube, 790 parts of 2-hexyldecanol [trade name "ISOFOL 16" manufactured by SASOL] and 330 parts of methacrylic acid were charged (molar ratio 1: 2). 8 parts of p-toluenesulfonic acid was added as a catalyst, and 0.8 parts of hydroquinone was added as a polymerization inhibitor. At a reaction temperature of 125 to 135 ° C., the produced water was continuously removed from the system by a water pipe, and the esterification reaction was carried out at normal pressure for 2 hours.
After further reacting under reduced pressure of 30 to 40 kPa for 1 hour, excess methacrylic acid was distilled off at 0.1 kPa.
Then, it was cooled to 25 ° C. to obtain an active energy ray-curable fingerprint resistance imparting agent (ratio X-1) containing a compound (ratio A-1) [Mw = 3.1 × 10 ² ].

<Examples 10 to 12, 14 to 31, Reference Example 13 , Comparative Examples 2 to 4>
According to the compounding composition (part) shown in Table 1, the components were collectively compounded and stirred with a disperser until uniform to obtain each active energy ray-curable resin composition.
Next, each active energy ray-curable resin composition is a surface-treated 100 μm-thick PET (polyethylene terephthalate) film [trade name “Cosmo Shine A4300”, manufactured by Toyobo Co., Ltd., hereinafter abbreviated as A4300. ], Apply to a film thickness of 10 μm using an applicator, dry the solvent with warm air, and then use an EB tester (EC250: manufactured by iElectron Beam Co., Ltd.) in a nitrogen atmosphere. Curing was performed at an irradiation amount of 4 Mrad to obtain a cured product.
Regarding the active energy ray-curable resin composition of Example 31, the obtained active energy ray-curable resin composition was applied in the same manner as above, the solvent was dried with warm air, and then the atmosphere was nitrogen. , Belt conveyor type UV irradiation device [“ECS-151U” manufactured by Eye Graphics Co., Ltd., the same device was used for the following evaluation. ], The cured product was obtained by curing at an exposure amount of 500 mJ / cm ^2.
The above cured product was evaluated according to the following evaluation method. The results are shown in Table 1.

The abbreviations in Table 1 are as follows.
DPHA (B-1):
Dipentaerythritol hexaacrylate [Product name "NK ester A-DPH", manufactured by Shin-Nakamura Chemical Co., Ltd.]
PETA (B-2):
Pentaerythritol tetraacrylate [Product name "NK ester A-TMMT", manufactured by Shin-Nakamura Chemical Co., Ltd.]
U-10PA (B-3):
Urethane acrylate [Product name "NK Oligo U-10PA", manufactured by Shin-Nakamura Chemical Co., Ltd.]
ACMO (C-1):
Acryloyl morpholine [Product name "ACMO", manufactured by KJ Chemicals Co., Ltd.]
DMAA (C-2):
Dimethyl acrylamide [trade name "DMAA", manufactured by KJ Chemicals Co., Ltd.]
STMA (C-3):
Stearyl methacrylate [trade name "Light Ester S", manufactured by Kyoeisha Chemical Co., Ltd.]
PPGMM (C-4):
Polypropylene glycol monomethacrylate [Product name "Blemmer PP-500", manufactured by NOF CORPORATION]
MAPO (e1-1):
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [trade name "LUCIRIN TPO", manufactured by BASF Limited]

[Evaluation method]
(1) Pencil hardness test [evaluation of scratch resistance]
The cured film surface of the coating was scratched with a pencil having different hardness according to JIS K5600, and the degree of scratches was evaluated according to the following criteria.
<Evaluation criteria>
×: Those that are scratched by pencils of F or less △: Those that are not scratched by H pencils, but those that are scratched by 2H pencils ○: Those that are not scratched by 2H pencils, but are scratched by 3H pencils Things ◎: Things that are not scratched with a 3H pencil, but are scratched with a 4H pencil

(2) Steel wool test [evaluation of scratch resistance]
After rubbing the cured film surface 10 times back and forth with a load of 300 g / cm ² using steel wool # 0000, the appearance was visually evaluated according to the following criteria.
<Evaluation criteria>
⊚: No scratches at all.
◯: There are few scratches.
Δ: There are scratches.
×: There are many scratches.

(3) Fingerprint adhesion test [Evaluation of fingerprint resistance]
A fingerprint was attached to the surface of the cured product by pressing the right thumb for 10 seconds, and a visual sensory test was evaluated for its visibility according to the following criteria by comparison with the fingerprint attached to the A4300 in the same manner.
<Evaluation criteria>
⊚: Fingerprints were clearly less noticeable than “A4300”.
◯: The fingerprint was less noticeable than “A4300”.
Δ: Fingerprint is about the same as “A4300”.
X: Fingerprints were more prominent than "A4300".

(4) Fingerprint wiping test [Evaluation of fingerprint resistance]
After the above test (3), the coating film to which the fingerprints are attached is wiped back and forth in one direction with Kim Towel [Nippon Paper Crecia Co., Ltd.] until the fingerprints cannot be seen. Evaluated in.
<Evaluation criteria>
⊚: Within 2 round trips until the fingerprint attached to the coating film surface cannot be confirmed.
◯: 3 to 5 round trips until the fingerprint attached to the coating film surface cannot be confirmed.
Δ: 6 to 10 round trips until the fingerprint attached to the coating film surface cannot be confirmed.
X: Fingerprints can be visually recognized even after 11 round trips.

(5) Haze (%) [Evaluation of transparency]
The haze was measured using a total light transmittance measuring device [trade name "haze-garddual" manufactured by BYK gardener Co., Ltd.] in accordance with JIS-K7136.

From the results in Table 1, the active energy ray-curable fingerprint resistance imparting agent of the present invention has excellent scratch resistance and fingerprint resistance to the cured product of the active energy ray curable resin composition, as compared with the comparative ones. It can be seen that transparency is imparted.

The active energy ray-curable fingerprint resistance imparting agent of the present invention can impart excellent scratch resistance, fingerprint resistance, and transparency to a cured product of an active energy ray curable resin composition. For this reason, optical lenses (prism sheets, collimator lenses, Fresnel lenses, lenticular lenses, back-reflection lenses, holograms, etc.), decorative film coating agents, hard coat films, antireflection films, decorative sheets (floor surfaces of buildings). It can be widely used for applications such as wall surfaces, interior materials for ceilings, etc.) and is extremely useful.

Claims (5)

An active energy ray-curable fingerprint resistance imparting agent containing a monofunctional (meth) acrylate compound (A) represented by the following general formula (1), wherein the (A) in the (X) is An active energy ray-curable fingerprint resistance imparting agent (X) of 70% by weight or more .
General formula (1):
CH ₂ = C (R ¹ ) -C (= O) O- (a0) -O- (b0)
[In the formula, R ¹ is an H or methyl group; (a0) is a residue obtained by removing a hydroxyl group from a (poly) alkylene (alkylene having 2 to 4 carbon atoms) glycol (a); (b0) is a carbon number. It represents the residue obtained by removing the hydroxyl group from the monohydric alcohol (b) of 1-36. The above (b) is a branched monohydric alcohol having 8 to 36 carbon atoms. ] The active energy ray-curable fingerprint resistance imparting agent according to claim 1, wherein the weight average molecular weight of 1,000 to 15,000 of said (A). An active energy comprising the active energy ray-curable fingerprint resistance imparting agent (X) according to claim 1 or 2 and a polyfunctional (meth) acrylate (B) having 2 to 12 (meth) acryloyl groups. The active energy ray-curable resin composition (Y) which is a ray-curable resin composition and has a content of (A) of 0.1% by weight to 5.0% by weight based on the weight of (B). .. A cured product (P) obtained by curing the active energy ray-curable resin composition (Y) according to claim 3. The cured product according to claim 4, which is an optical lens, a decorative film, a decorative sheet, a hard coat film or an antireflection film.