TWI492975B - Active energy line hardening resin - Google Patents

Description

Active energy ray-curable resin

The present invention relates to an antistatic agent for an active energy ray-curable resin and an active energy ray-curable resin containing the antistatic agent.

The energy ray-curable resin is used for coating, bonding, and the like of various substrates. Such an energy ray-curable resin tends to adhere to dust or dust due to the tendency to carry static electricity, and may have antistatic properties depending on the application.

Therefore, various proposals have been made in order to improve the antistatic performance of the energy ray-curable resin. There is disclosed, for example, a coating composition (Patent Document 1) and an ultraviolet curable resin (Patent Document 2), the coating composition containing a monomer containing a phosphate ester and an acryloxy group in a molecule and / or methacryloxyloxy group, the ultraviolet curable resin contains a monomer having a quaternary ammonium salt group and a (meth) acrylonitrile group. However, although it has been confirmed that these compositions have an effect of lowering a certain surface resistance value, there is still a demand for an antistatic agent for an energy ray-curable resin which has more excellent antistatic properties.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Patent Laid-Open Publication No. SHO 63-006064

Patent Document 2: Japanese Patent Laid-Open Publication No. 2010-285480

The present invention has been made in view of the above circumstances, and an object of the invention is to provide an antistatic agent for an active energy ray-curable resin and an active energy ray-curable resin containing the antistatic agent, which can be antistatic with a known antistatic agent. The active active energy ray-curable resin further reduces the surface resistance value.

The inventors of the present invention have repeatedly made efforts to carry out research, and have found out that when a specific phosphate compound is used, the phosphate compound is locally present on the surface of the resin to exhibit an excellent surface resistance value, and the present invention has been completed. The fact is that, in view of the conventional active energy ray-curable resin having antistatic property, the phosphate resistance group and the quaternary ammonium salt group exhibiting antistatic properties are dispersed in the resin, and the surface resistance value is increased, that is, antistatic. Performance is reduced.

In other words, the first aspect of the present invention is an antistatic agent for an active energy ray-curable resin, which is characterized by the following general formulae (1) and/or (2):

(wherein R represents an alkyl group having 8 to 13 carbon atoms, and 0≦n≦6).

According to a second aspect of the invention, there is provided an active energy ray-curable resin comprising the antistatic agent for an active energy ray-curable resin.

Further, the surface resistance of the active energy ray-curable resin of the present invention is preferably 10 ¹² Ω or less.

[Preferred form of implementing the invention]

Next, an embodiment of the present invention will be described.

The antistatic agent for an active energy ray-curable resin of the present invention (hereinafter referred to as an antistatic agent) is a compound represented by the following general formula (1) and/or (2).

(wherein R represents an alkyl group having 8 to 13 carbon atoms, and 0≦n≦6).

In the formula (1) and/or (2), R is an alkyl group having 8 to 13 carbon atoms. Such substitution The group is not particularly limited and can represent a linear alkyl group such as an octyl group, a decyl group, a decyl group, a dodecyl group, an undecyl group or a tridecyl group; or a trimethylhexyl group or a methylheptyl group; Dimethylheptyl, trimethylheptyl, tetramethylheptyl, ethylheptyl, methyloctyl, methyl decyl, methyl decyl, methyldodecyl, methylundecane a branched alkyl group such as a methyl group or a tridecyl group.

In the general formulae (1) and/or (2), n is 0 or more and 6 or less. When n exceeds 6, the following problem occurs: the antistatic property may be insufficient, that is, the surface resistance may become 10 ¹³ Ω or more.

The compounding ratio of the compounds of the formulae (1) and (2) is not particularly limited, and the molar ratio thereof is preferably 60:40 to 40:60.

The antistatic agent of the present invention may be used singly or in combination of two or more.

A commercially available alkyl (ether) phosphate type surfactant can be used as the antistatic agent of the present invention. For example, "Phosphanol (registered trademark) series" manufactured by Toho Chemical Co., Ltd., "ADEKA COL (registered trademark) PS/CS/TS series manufactured by ADEKA Co., Ltd., and "PLYSURF" (registered trademark) manufactured by Daiichi Kogyo Co., Ltd. ) series" and so on.

The compounding amount of the antistatic agent of the present invention is not particularly limited, and is preferably from 3 to 15 parts by weight, more preferably from 5 to 10 parts by weight, per 100 parts by weight of the active energy ray-curable resin. If it is less than 3 parts by weight, sufficient electrical conductivity cannot be obtained, and if it exceeds 15 parts by weight, the problem of bleeding may occur.

The active energy ray-curable resin of the present invention is not particularly limited, and an active energy ray-curable resin which has hitherto been used for the intended use of the present invention can be used.

A preferred example of the active energy ray-curable resin is an active energy ray-curable resin containing an acrylic polymer having a compound having a carbon number of 1 to 14 as a main component. One or more of acrylate and/or methacrylate.

Further, for example, a one-liquid type or a two-liquid type urethane resin; or an acrylic resin or an epoxy resin which can be polymerized by thermal polymerization or radiation polymerization may be mentioned.

The acrylic polymer of the present invention is not particularly limited, and is obtained by polymerizing a conventional monomer which is conventionally known by thermal polymerization or radiation polymerization. Representative examples of the above monomers include 2-ethylhexyl (meth)acrylate, styrene, methyl methacrylate, acryloylmorpholine, tetrahydrofurfuryl (meth)acrylate, and (methyl). Phenyloxyethyl acrylate, phenoxypropyl (meth)acrylate, polyethoxyphenyl (meth)acrylate, phenylbenzyl (meth)acrylate, o-phenylphenol (methyl) Acrylate, o-phenylphenoxyethoxy(meth)acrylate, polyethoxyethoxyphenoxyethoxy(meth)acrylate, isophorone (meth)acrylate, phthalate Mono(meth) propylene methoxyethyl formate, ethylene glycol di(meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (a) Acrylate, polytetramethylene glycol di(meth)acrylate, 1,4 butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1 , 9-decanediol di(meth)acrylate, EO (ethylene oxide, the same as below) modified bisphenol di(meth)acrylate, PO (propylene oxide, all of the same) modified double Phenol di(meth)acrylate, trimethylolpropane tri Methyl) acrylate, EO modified trimethylolpropane tri(meth) acrylate, PO modified trimethylolpropane tri(methyl) propyl Ethyl ester, pentaerythritol tri(meth)acrylate, ((meth)acryloxyethyl)isocyanurate, pentaerythritol tetra(meth)acrylate, EO modified pentaerythritol tetra(meth)acrylic acid Ester, PO modified pentaerythritol tetra(meth)acrylate, bis(trimethylolpropane)tetra(meth)acrylate, EO modified bis(trimethylolpropane)tetra(meth)acrylate, PO Modified bis(trimethylolpropane)tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, EO modified dipentaerythritol hexa(meth) acrylate, PO modified dipentaerythritol hexa(methyl) ) acrylate, dipentaerythritol penta (meth) acrylate, and the like. These may be used alone or in combination.

Further, an amine ester resin which can be polymerized by thermal polymerization or radiation polymerization is specifically, for example, an amine ester (meth) acrylate.

The amine ester (meth) acrylate is obtained by reacting the following compounds: (A) a polyhydric alcohol, (B) a polyisocyanate, and (C) a (meth) acrylate having a hydroxyl group in the molecule.

The (A) polyol is not particularly limited, and specifically, a polyester polyol, a polycarbonate polyol, a polyether polyol, an aliphatic hydrocarbon polyol, or an alicyclic hydrocarbon polyol can be used.

The (B) polyisocyanate is not particularly limited, and specific examples thereof include an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate, and an aromatic aliphatic polyisocyanate. The aliphatic polyisocyanate may, for example, be tetramethylene diisocyanate, decamethyl diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4 Trimethyl hexamethylene diisocyanate, quaternary acid diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate. Alicyclic The isocyanate may, for example, be isophorone diisocyanate, hydrogenated xylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexyl diisocyanate, 1,3 - bis(isocyanatomethyl)cyclohexane or the like. Examples of the aromatic polyisocyanate include toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate (MDI). 4,4'-Diphenylmethyl diisocyanate, 1,5-naphthalene diisocyanate, xylene diisocyanate, 1,3-benzene diisocyanate, 1,4-phenylene diisocyanate or the like. The aromatic aliphatic polyisocyanate may, for example, be dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate or α,α,α,α-tetramethylxylene diisocyanate or the like. Further, for example, modified bodies such as dimers, trimers, and biuretized isocyanates of such organic polyisocyanates may be mentioned. These can also be used alone or in combination of two or more.

The (meth) acrylate having a hydroxyl group in the above (C) molecule is not particularly limited, and specific examples thereof include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and A. 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, caprolactone modified 2-hydroxyethyl acrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polybutylene glycol monoacrylate, pentaerythritol Triacrylate, dipentaerythritol pentaacrylate, and the like. Further, an epoxy acrylate obtained by (meth)acrylating an epoxy group, such as a bisphenol A epoxy resin, a bisphenol F epoxy resin, or a phenol novolak epoxy resin, can also be used. These can be used alone or in combination.

The amine ester (meth) acrylate of the present invention can be combined by a conventional method to make. It can be synthesized by, for example, feeding a predetermined amount of the component (A) and the component (B) once, and reacting it at 70 to 80 ° C until it reaches a predetermined amount of free isocyanate, and then hydroquinone The polymerization inhibitor such as a group ether is fed to the component (C) in the next step, and heated and stirred at 70 to 80 ° C until the free isocyanate disappears. At this time, a tin-based catalyst such as dibutyltin dilaurate can also be added in order to promote the reaction.

Examples of the radiation include ultraviolet rays, thunder rays, alpha rays, beta rays, gamma rays, X rays, electron beams, and the like. Further, when ultraviolet rays are used as the radiation, a photopolymerization initiator is added. The photopolymerization initiator may be any one that is capable of generating a radical or a cation by irradiating an ultraviolet ray of an appropriate wavelength capable of initiating a polymerization reaction thereof depending on the type of the radiation reaction component.

The photoradical polymerization initiator may, for example, be benzoin, benzoin methyl ether, benzoin ethyl ether, methyl ortho-benzoylbenzoate-benzoic acid ethyl ether, benzoin isopropyl ether, α-methylbenzoin Benzoin; benzyl ketal, trichloroacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone and other acetophenones; 2-hydroxy-2 -propiophenone such as methyl phenyl ketone or 2-hydroxy-4'-isopropyl-2-methylpropiophenone; benzophenone, methyl benzophenone, p-chlorobenzophenone, p-dimethylene a benzophenone such as a carbamide benzophenone; a thioxanthone such as 2-chlorothioxanthone, 2-ethylthioxanthone or 2-isopropylthioxanthone; 2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 2,4,6-trimethyl Tertylphosphine oxides such as benzamidine-ethoxy-phenylphosphine oxide; benzil; dibenzosuberone; α-fluorenyl Ester ester and the like.

The photocationic polymerization initiator may, for example, be an anthracene salt such as an aromatic diazonium salt, an aromatic onium salt or an aromatic onium salt; an iron-propadiene complex, a titanocene complex, or an aryl sterol; - an organic metal complex such as an aluminum complex; nitrobenzyl ester; a sulfonic acid derivative; a phosphate; a phenolsulfonate; a diazonaphthoquinone; an N-hydroxy quinone sulfonate;

The photopolymerization initiator is usually formulated in an amount of 0.1 to 10 parts by weight, preferably 0.2 to 7 parts by weight, based on 100 parts by weight of the active energy ray-curable resin.

It is also possible to further use a photopolymerization initiation aid such as an amine. The photopolymerization initiation aid may, for example, be 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate or p-dimethylaminobenzene. Isoamyl formate and the like. Two or more kinds of the above-mentioned photopolymerization initiation aids can also be used in combination.

The active energy ray-curable resin of the present invention can be obtained by disposing a predetermined amount of an antistatic agent in a raw material of the active energy ray-curable resin and polymerizing it.

In addition to the above-mentioned polymerization initiator and polymerization initiation aid, the active energy ray-curable resin of the present invention may be added as needed: a diluent solvent, a lubricant, a leveling agent, a filler, and the like.

The surface resistance of the active energy ray-curable resin of the present invention is preferably 10 ¹² Ω or less, more preferably 10 ¹⁰ Ω or less. When the surface resistance value exceeds 10 ¹² Ω, there is a problem that dust adheres due to charging.

[Examples]

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited by the examples. In the examples and comparative examples, the parts and % are based on weight unless otherwise specified.

1. Synthesis of active energy ray-curable resin

[Synthesis Example 1]

In the flask, 3445 g (3.3 mol) of acrylate of bisphenol A type epoxy propyl ether (epoxy equivalent = 450), 1.81 g of hydroquinone monomethyl ether, and 188 g (1 mol) of xylene diisocyanate were fed at 70 The reaction was carried out under the conditions of ~80 ° C until the residual isocyanate concentration became 0.1%, and an active energy ray-curable resin was obtained.

[Synthesis Example 2]

In the flask, 3,455 g (3.3 mol) of acrylate of bisphenol A type epoxy propyl ether (epoxy equivalent = 450), 1.81 g of hydroquinone monomethyl ether, 2422 g of phenoxyethyl acrylate, and xylene were fed. 188 g (1 mol) of an isocyanate was reacted at 70 to 80 ° C until the residual isocyanate concentration became 0.1%, and an active energy ray-curable resin was obtained.

2. Adjustment of active energy ray-curable resin

In the synthesis example 1 or 2 obtained above, the antistatic agents shown in the following Table 1 were formulated in the proportions (parts by weight) shown in Table 2, and the α-hydroxyalkane as a photopolymerization initiator was formulated. A phenyl ketone (product name: Irgacure 184, manufactured by BASF Corporation) was added in an amount of 3 wt%, and ethyl acetate was 50 wt% as a diluent to obtain an active energy ray-curable resin.

3. Evaluation of active energy ray-curable resin

<Production of evaluation samples>

The active energy ray-curable resin obtained above was spin-coated (500 rpm, 5 sec) 1500 rpm, 15 sec) on a PET film (LUMIRROR manufactured by Toray) (corona treated surface), and dried at 80 ° C for 10 minutes, and then irradiated with ultraviolet rays of 200 mJ/cm ² by a high pressure mercury lamp to prepare an evaluation sample.

<Surface resistance measurement conditions>

The measurement was carried out under the conditions of a temperature of 20 ° C and a humidity of 65% using R8340 ULTRA HIGH RESISTANCE METER manufactured by ADVANTEST Co., Ltd. The evaluation results are shown in Table 1 above.

As is clear from the results shown in Table 2, when R and n in the general formula (1) are outside the predetermined range (Comparative Examples 2 to 3) and when the structure is different from the general formula (1) (Comparative Examples 5 to 7) The surface resistance of the antistatic agent will exceed 10 ¹² Ω.

The antistatic agent of the present invention and the active energy ray-curable resin obtained by using the antistatic agent can be suitably used for a hard coat film for an optical film, an optical film, and an antistatic protective film.

The present invention has been described in detail above with reference to the specific embodiments of the present invention, and various modifications and changes can be made without departing from the spirit and scope of the invention. And easy to know.

The present application is based on a Japanese patent application filed on Apr. 7, 2011 (Japanese Patent Application No. 2011-085008).

Claims (2)

An active energy ray-curable resin which is used for a hard coat film for an optical film, an optical film, or an antistatic protective film, characterized in that it is characterized by the following general formula (1) and/or (2) An active energy ray-curable resin comprising an antistatic agent, an acrylic polymer, and a photopolymerization initiator, wherein the acrylic polymer is an acrylate having an alkyl group having 1 to 14 carbon atoms; / or one or more of methacrylate as a main component: (wherein R represents an alkyl group having 8 to 13 carbon atoms, and 0≦n≦6). The active energy ray-curable resin according to claim 1, wherein the surface resistance of the cured product is 10 ¹² Ω or less.