JP7338154B2 - Active energy ray-curable resin composition and laminate - Google Patents

Description

TECHNICAL FIELD The present invention relates to an active energy ray-curable resin composition having high adhesion to inorganic materials and excellent storage stability, a paint containing the same, and a coating film and laminate using the paint.

Inorganic material thin films made of inorganic compounds such as various metals, glasses, _SiOx , _Al2O3 , _TiO2 , and ITO are used in various applications such as optical films, _packaging materials, semiconductors, insulators, electrodes, and wiring. ing. These inorganic material thin films are usually formed on some substrate by methods such as vacuum deposition, plasma-assisted method (CVD), and sputtering. Examples of the substrate include those made of various materials such as glass, metal, and plastic. Among these, a technique of using a plastic film as a substrate and laminating an inorganic material thin film, a resin coating film, etc. as a functional film has been widely studied. In such a technique, the adhesion between the inorganic material thin film layer and the plastic film layer or the resin coating layer is important, but in practice the adhesion between the two is often insufficient. Development of materials is required.

As a resin material having excellent adhesion to various substrates, for example, Patent Document 1 contains acrylic resin, dipentaerythritol hexaacrylate, bis(2-methacryloyloxyethyl) acid phosphate and 3-acryloxypropyltrimethoxysilane. It is disclosed that the active-energy-ray-curable resin composition to be used has excellent adhesion to glass substrates. However, even the active energy ray-curable resin composition described in Patent Document 1 does not have sufficient adhesion to glass or other inorganic materials, and the development of a more excellent resin material has been desired. In addition, the active energy ray-curable resin composition described in Patent Document 1 does not have sufficient storage stability, and turbidity and the like tend to occur over time.

JP 2014-74158 A

Therefore, the problem to be solved by the present invention is to provide an active energy ray-curable resin composition that has high adhesion to various inorganic materials and excellent storage stability, a coating material containing the same, and a coating film using the coating material. and to provide a laminate.

The inventors of the present application have made intensive studies to solve the above problems, and found that a resin composition containing a (meth)acryloyl group-containing compound, a phosphoric acid ester compound and a silane coupling agent, wherein the (meth)acryloyl Those using (poly)ester (meth)acrylate resin as a group-containing compound include various metals, inorganic material thin films made of inorganic compounds such as SiO _x , Al ₂ O ₃ , TiO ₂ , and ITO, as well as glass and silicon wafers. In addition to exhibiting high adhesiveness to, etc., it has been found to be excellent in storage stability, and the present invention has been completed.

That is, the present invention contains a (meth)acryloyl group-containing compound (A), a phosphate ester compound (B) and a silane coupling agent (C), and the (meth)acryloyl group-containing compound (A) is (poly) The present invention relates to an active energy ray-curable resin composition containing an ester (meth)acrylate resin (A1) as an essential component.

The present invention further relates to a paint containing the active energy ray-curable resin composition.

The invention further relates to a coating film comprising said paint.

The present invention further relates to a laminate having a layer comprising the coating film and an inorganic material layer adjacent thereto.

ADVANTAGE OF THE INVENTION According to this invention, the active-energy-ray-curable resin composition which has high adhesion with respect to various inorganic materials and is excellent in storage stability, the coating containing the same, and the coating film and laminated body which use the said coating are provided. be able to.

The active energy ray-curable resin composition of the present invention contains a (meth)acryloyl group-containing compound (A), a phosphate ester compound (B) and a silane coupling agent (C), and the (meth)acryloyl group-containing The compound (A) is characterized by containing a (poly)ester (meth)acrylate resin (A1) as an essential component.

In the present invention, the (meth)acryloyl group means either or both of an acryloyl group and a methacryloyl group. (Meth)acrylate is a generic term for acrylate and methacrylate.

The (poly)ester (meth)acrylate resin (A1) is not particularly limited as long as it is a (meth)acrylate compound having a (poly)ester structure in its molecular structure, and a wide variety of compounds can be used. Examples of such compounds include a lactone-modified urethane (meth)acrylate resin that is a reaction product of a polyisocyanate compound (x1) and a lactone-modified hydroxy (meth)acrylate compound (x2), and a hydroxyl group-containing polyester resin ( Polyester (meth)acrylate resins, which are meth)acrylic acid adducts, and polyester (meth)acrylate resins, which are glycidyl (meth)acrylate adducts of carboxy group-containing polyester resins, and the like.

Regarding the lactone-modified urethane (meth)acrylate resin, the polyisocyanate compound (x1) is, for example, butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate. Alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1, Aromatic diisocyanate compounds such as 5-naphthalene diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (1); . Each of these may be used alone, or two or more of them may be used in combination.

［式中、Ｒ^１はそれぞれ独立に水素原子、炭素原子数１～６の炭化水素基の何れかである。Ｒ^２はそれぞれ独立に炭素原子数１～４のアルキル基、又は構造式（１）で表される構造部位と＊印が付されたメチレン基を介して連結する結合点の何れかである。ｌは０又は１～３の整数であり、ｍは１以上の整数である。］

[In the formula, each R ¹ is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Each R ² is independently either an alkyl group having 1 to 4 carbon atoms, or a bonding point connecting the structural site represented by the structural formula (1) via a methylene group marked with *. l is 0 or an integer of 1 to 3, and m is an integer of 1 or more. ]

Among the polyisocyanate compounds (x1), the aliphatic diisocyanate compound, the alicyclic diisocyanate compound, or isocyanurate-modified thereof, because the active energy ray-curable resin composition has even better adhesion to inorganic materials. body is preferred.

The lactone-modified hydroxy(meth)acrylate compound (x2) includes, for example, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and ditrimethylolpropane. Examples include those obtained by adding a lactone compound to aliphatic hydroxy(meth)acrylate compounds such as tri(meth)acrylate and dipentaerythritol penta(meth)acrylate, or (poly)oxyalkylene modified products thereof. The lactone compounds include, for example, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, ε-methylcaprolactone, ε-ethylcaprolactone, ε-propylcaprolactone, 3-pentene-4-olide, 12- dodecanolide, γ-dodecanolactone and the like. Each of these may be used alone, or two or more of them may be used in combination.

Among the lactone-modified hydroxy (meth) acrylate compounds (x2), the aliphatic hydroxy (meth) acrylate compound is hydroxyethyl (meth) because it becomes an active energy ray-curable resin composition with even better adhesion to inorganic materials. ) acrylate, hydroxypropyl (meth)acrylate and other mono(meth)acrylate compounds are preferably used. Also, ε-caprolactone is particularly preferable as the lactone compound. The average number of added moles of the lactone compound is preferably in the range of 1-10, more preferably in the range of 1-5. The average number of added moles of the lactone compound is a value calculated from the reaction ratio between the aliphatic hydroxy(meth)acrylate compound or (poly)oxyalkylene modified product thereof and the lactone compound.

In addition to the polyisocyanate compound (x1) and the lactone-modified hydroxy(meth)acrylate compound (x2), the lactone-modified urethane (meth)acrylate resin contains other compounds such as a polyol compound as part of the reaction raw materials. You can When other compounds are included in the reaction raw materials, the active energy ray-curable resin composition has high adhesion to inorganic materials and excellent moisture and heat resistance. In contrast, the total mass of the polyisocyanate compound (x1) and the lactone-modified hydroxy (meth)acrylate compound (x2) is preferably 70% by mass or more, more preferably 90% by mass or more.

The lactone-modified urethane (meth)acrylate resin can be produced under the same reaction conditions as for a general urethanization reaction. As an example of the reaction conditions, the molar ratio [(NCO)/(OH)] between the isocyanate group and the hydroxyl group is 1/0.95 to 1/1.05. C. degree temperature conditions, the method of making it react using a well-known and commonly used urethanization catalyst as needed, etc. are mentioned.

The lactone-modified urethane (meth)acrylate resin preferably has a weight average molecular weight (Mw) of 600 to 5,000, more preferably 1,000 to 4,800. Further, the theoretical value of the (meth)acryloyl group equivalent calculated from the charging ratio of the raw materials is preferably in the range of 300 to 2,500 g/equivalent, more preferably in the range of 300 to 800 g/equivalent.

In the present invention, the weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mn/Mw) are values measured by gel permeation chromatography (GPC) under the following conditions.

Measuring device; HLC-8220 manufactured by Tosoh Corporation
Column; guard column _HXL -H manufactured by Tosoh Corporation
+ TSKgel G5000H _XL manufactured by Tosoh Corporation
+ TSKgel G4000H _XL manufactured by Tosoh Corporation
+ TSKgel G3000H _XL manufactured by Tosoh Corporation
+ TSKgel G2000H _XL manufactured by Tosoh Corporation
Detector; RI (differential refractometer)
Data processing: SC-8010 manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40°C
Solvent Tetrahydrofuran
Flow rate 1.0 ml/min Standard; Polystyrene Sample; A tetrahydrofuran solution of 0.4% by mass in terms of resin solid content filtered through a microfilter (100 μl)

Regarding the polyester (meth)acrylate resin which is the (meth)acrylic acid adduct of the hydroxyl group-containing polyester resin and the polyester (meth)acrylate resin which is the glycidyl (meth)acrylate adduct of the carboxyl group-containing polyester resin, the hydroxyl group-containing polyester resin Alternatively, the carboxyl group-containing polyester resin includes those using a polybasic acid and a polyhydric alcohol as reaction raw materials, and the specific structure thereof is not particularly limited, and a wide variety of resins can be used.

Specific examples of polybasic acid raw materials include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Acid compounds and their acid anhydrides, acid halides, derivatives such as alkyl esters;

Alicyclic dicarboxylic acid compounds such as tetrahydrophthalic acid, hexahydrophthalic acid and methyltetrahydrophthalic acid, and derivatives such as acid anhydrides, acid halides and alkyl esters thereof;

Aromatic dicarboxylic acid compounds such as phthalic acid, isophthalic acid and terephthalic acid, and derivatives such as acid anhydrides, acid halides and alkyl esters thereof;

Tri- or more functional aliphatic polycarboxylic acid compounds such as 1,2,5-hexanetricarboxylic acid, and derivatives such as acid anhydrides, acid halides and alkyl esters thereof;

Tri- or more functional alicyclic polycarboxylic acid compounds such as 1,2,4-cyclohexanetricarboxylic acid, and derivatives such as acid anhydrides, acid halides and alkyl esters thereof;

Tri- or higher functional aromatic polycarboxylic acid compounds such as trimellitic acid, trimellitic anhydride, 1,2,5-benzenetricarboxylic acid and 2,5,7-naphthalenetricarboxylic acid, and their acid anhydrides and acid halogens compounds, derivatives such as alkyl esters, and the like. Each of these may be used alone, or two or more of them may be used in combination.

Specific examples of the polyol raw material include ethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1 linear aliphatic diol compounds such as ,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol;

propylene glycol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-ethyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2-ethyl-2-methyl-1, 3-propanediol, 2-ethylbutane-14-butanediol, 2,3-dimethyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol , 3,3-dimethylpentane-1,5-diol, 2,2-diethyl-1,3-propanediol, 3-propylpentane-1,5-diol, 2,2-diethyl-1,4-butanediol , 2,4-diethyl-1,5-pentanediol, 2,2-dipropyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,5-diethyl-1, Diol compounds of branched aliphatic hydrocarbons such as 6-hexanediol;

Alicyclic structure-containing diol compounds such as cyclohexanediol and cyclohexanedimethanol;

Aromatic ring-containing diol compounds such as biphenols and bisphenols;

tri- or higher functional aliphatic polyol compounds such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol;

Tri- or higher functional aromatic polyol compounds such as trihydroxybenzene;

By ring-opening polymerization of the various diols or trifunctional or higher polyol compounds and cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether Polyether-modified polyol compound obtained;

Examples include polycarbonate polyols. Each of these may be used alone, or two or more of them may be used in combination.

The polyester (meth)acrylate resin which is the (meth)acrylic acid adduct of the hydroxyl group-containing polyester resin and the polyester (meth)acrylate resin which is the glycidyl (meth)acrylate adduct of the carboxyl group-containing polyester resin have storage stability. It is preferably 20 mgKOH/g or less because it becomes an active energy ray-curable resin composition excellent in heat and humidity resistance.

In addition, the polyester (meth)acrylate resin that is the (meth)acrylic acid adduct of the hydroxyl group-containing polyester resin and the polyester (meth)acrylate resin that is the glycidyl (meth)acrylate adduct of the carboxyl group-containing polyester resin are It is preferred that the weight average molecular weight (Mw) is in the range of 1,000 to 10,000. Also, the theoretical value of the (meth)acryloyl group equivalent is preferably in the range of 300 to 2,000 g/equivalent.

The (meth)acryloyl group-containing compound (A) used in the present invention may contain a (meth)acrylate compound other than the (poly)ester (meth)acrylate resin (A1). The other (meth)acrylate compounds include, for example, dendrimer-type (meth)acrylate resin (A2), (meth)acryloyl group-containing acrylic resin (A3), urethane (meth)acrylate resin (A4), and epoxy (meth)acrylate. Resin (A5), mono(meth)acrylate compound and its modified form (A6), aliphatic hydrocarbon type poly(meth)acrylate compound and its modified form (A7), alicyclic poly(meth)acrylate compound and its modified form (A8), aromatic poly(meth)acrylate compounds and modified products thereof (A9), and the like. Each of these may be used alone, or two or more of them may be used in combination.

The dendrimer-type (meth)acrylate resin (A2) refers to a resin having a regular multi-branched structure and having a (meth)acryloyl group at the end of each branched chain. It is called branch type or star polymer. Examples of such compounds include, but are not limited to, those represented by the following structural formulas (2-1) to (2-8). Any resin can be used as long as it has a (meth)acryloyl group at the end of each branched chain.

（式中Ｒ^３は水素原子又はメチル基であり、Ｒ^４は炭素原子数１～４の炭化水素基である。）

(In the formula, R ³ is a hydrogen atom or a methyl group, and R ⁴ is a hydrocarbon group having 1 to 4 carbon atoms.)

As such a dendrimer-type (meth)acrylate resin (A2), "Viscoat #1000" manufactured by Osaka Organic Chemical Co., Ltd. [weight average molecular weight (Mw) 1,500 to 2,000, average (meth)acryloyl per molecule Base number 14], “Viscoat 1020” [weight average molecular weight (Mw) 1,000 to 3,000], “SIRIUS501” [weight average molecular weight (Mw) 15,000 to 23,000], MIWON “SP-1106” "[weight average molecular weight (Mw) 1,630, average (meth) acryloyl group number per molecule 18], SARTOMER "CN2301", "CN2302" [average (meth) acryloyl group number per molecule 16], " CN2303" [average number of (meth)acryloyl groups per molecule 6], "CN2304" [average number of (meth)acryloyl groups per molecule 18], Nippon Steel & Sumikin Chemical Co., Ltd. "Esdrimer HU-22", Shin-Nakamura Chemical Co., Ltd. Commercially available products such as "A-HBR-5" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., "New Frontier R-1150" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and "Hypertech UR-101" manufactured by Nissan Chemical Industries, Ltd. may also be used.

The dendrimer type (meth)acrylate resin (A2) preferably has a weight average molecular weight (Mw) in the range of 1,000 to 30,000. Further, it is preferable that the average number of (meth)acryloyl groups per molecule is in the range of 5 to 30.

The (meth)acryloyl group-containing acrylic resin (A3) is obtained by polymerizing a (meth)acrylate monomer (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group as an essential component. Those obtained by further reacting the obtained acrylic resin intermediate with a (meth)acrylate monomer (β) having a reactive functional group capable of reacting with these functional groups to introduce a (meth)acryloyl group include: be done.

The (meth)acrylate monomer (α) having a reactive functional group includes, for example, hydroxyl group-containing (meth)acrylate monomers such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate; Group-containing (meth) acrylate monomer; isocyanate group-containing (meth) acrylate monomer such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate; glycidyl (meth) acrylate and glycidyl group-containing (meth)acrylate monomers such as 4-hydroxybutyl acrylate glycidyl ether. Each of these may be used alone, or two or more of them may be used in combination.

The acrylic resin intermediate may be obtained by copolymerizing the (meth)acrylate monomer (α) and, if necessary, other polymerizable unsaturated group-containing compounds. The other polymerizable unsaturated group-containing compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like (meth) Acrylic acid alkyl esters; Cycloring-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate; Phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl acrylate silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, α-methylstyrene and chlorostyrene; Each of these may be used alone, or two or more of them may be used in combination.

When the acrylic resin intermediate is obtained by copolymerizing the (meth)acrylate monomer (α) and the other polymerizable unsaturated group-containing compound, the reaction ratio of the two is excellent in curability. Since the (meth)acryloyl group-containing acrylic resin (A3) is obtained, the ratio of the (meth)acrylate monomer (α) to the total of both is preferably in the range of 20 to 70% by mass, and 30 to 60% by mass. It is more preferably in the range of part %.

The acrylic resin intermediate can be produced in the same manner as for general acrylic resins. As an example of production conditions, for example, it can be produced by polymerizing various monomers in the presence of a polymerization initiator in a temperature range of 60°C to 150°C. Polymerization methods include, for example, bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Moreover, the polymerization mode includes, for example, random copolymers, block copolymers, graft copolymers, and the like. In the case of solution polymerization, for example, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and glycol ether solvents such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether are preferably used. can be done.

The (meth)acrylate monomer (β) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate monomer (α). From the viewpoint of reactivity, the following combinations are preferred: is preferred. That is, when the hydroxyl group-containing (meth)acrylate is used as the (meth)acrylate monomer (α), it is preferable to use an isocyanate group-containing (meth)acrylate as the (meth)acrylate monomer (β). When the carboxy group-containing (meth)acrylate is used as the (meth)acrylate monomer (α), it is preferable to use the glycidyl group-containing (meth)acrylate as the (meth)acrylate monomer (β). When the isocyanate group-containing (meth)acrylate is used as the (meth)acrylate monomer (α), it is preferable to use the hydroxyl group-containing (meth)acrylate as the (meth)acrylate monomer (β). When the glycidyl group-containing (meth)acrylate is used as the (meth)acrylate monomer (α), it is preferable to use the carboxy group-containing (meth)acrylate as the (meth)acrylate monomer (β).

The reaction between the acrylic resin intermediate and the (meth)acrylate monomer (β) is carried out, for example, when the reaction is an esterification reaction, in a temperature range of 60 to 150° C. with an esterification catalyst such as triphenylphosphine. is used as appropriate. Further, when the reaction is a urethanization reaction, a method of reacting the acrylic resin intermediate while dropping the compound (α) at a temperature in the range of 50 to 120° C. can be used.

The (meth)acryloyl group-containing acrylic resin (A3) preferably has a weight average molecular weight (Mw) in the range of 5,000 to 80,000. Also, the (meth)acryloyl group equivalent is preferably in the range of 200 to 500 g/equivalent.

Examples of the urethane (meth)acrylate resin (A4) include those obtained by reacting various polyisocyanate compounds, hydroxyl group-containing (meth)acrylate compounds, and, if necessary, various polyol compounds. Examples of the polyisocyanate compound include various polyisocyanate compounds such as those exemplified as the polyisocyanate compound (x1).

The hydroxyl group-containing (meth)acrylate compounds include, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth) hydroxyl group-containing (meth)acrylate compounds such as acrylates and dipentaerythritol penta(meth)acrylate; A (poly)oxyalkylene modified product into which a (poly)oxyalkylene chain such as a poly)oxytetramethylene chain is introduced can be mentioned.

Examples of the polyol compound include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; Polyol compounds: (poly)oxyalkylenes in which (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains are introduced into the molecular structure of the above-mentioned various polyol compounds Modified forms and the like can be mentioned.

Examples of the epoxy (meth)acrylate resin (A5) include those obtained by reacting an epoxy resin with (meth)acrylic acid or its anhydride. Examples of the epoxy resin include diglycidyl ethers of dihydric phenols such as hydroquinone and catechol; diglycidyl ethers of biphenol compounds such as 3,3'-biphenyldiol and 4,4'-biphenyldiol; bisphenol A type epoxy resins; Bisphenol type epoxy resins such as bisphenol B type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin; 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 2,6-naphthalene Polyglycidyl ethers of naphthol compounds such as diols, 2,7-naphthalenediol, binaphthol, bis(2,7-dihydroxynaphthyl)methane; triglycidyl ethers such as 4,4′,4″-methylidinetrisphenol; phenol Novolac epoxy resins such as novolac epoxy resins and cresol novolak resins; ) a (poly)oxyalkylene modified product into which an oxyalkylene chain is introduced; and a lactone modified product into which a (poly)lactone structure is introduced into the molecular structure of the above various epoxy resins.

The mono (meth) acrylate compound and its modified form (A6) are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, propyl (meth) acrylate, hydroxypropyl (meth) acrylate, Alicyclic mono (meth) acrylate compounds such as butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; ) acrylate compounds; heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate , phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenylphenol (meth)acrylate, phenylphenolalkyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxybenzyl (meth)acrylate , benzylbenzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, paracumylphenol (meth)acrylate, and other aromatic mono(meth)acrylate compounds; the following structural formula (3)

（式中Ｒ^３は水素原子又はメチル基である。）
で表される化合物等のモノ（メタ）アクリレート化合物：前記各種のモノ（メタ）アクリレート化合物の分子構造中に（ポリ）オキシエチレン鎖、（ポリ）オキシプロピレン鎖、（ポリ）オキシテトラメチレン鎖等の（ポリ）オキシアルキレン鎖を導入した（ポリ）オキシアルキレン変性体；前記各種のモノ（メタ）アクリレート化合物の分子構造中に（ポリ）ラクトン構造を導入したラクトン変性体等が挙げられる。

(In the formula, ^R3 is a hydrogen atom or a methyl group.)
Mono (meth) acrylate compounds such as compounds represented by: (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain, etc. in the molecular structure of the various mono (meth) acrylate compounds a (poly)oxyalkylene modified product in which a (poly)oxyalkylene chain is introduced; and a lactone modified product in which a (poly)lactone structure is introduced into the molecular structure of the above-mentioned various mono(meth)acrylate compounds.

The aliphatic hydrocarbon-type poly(meth)acrylate compound and its modified form (A7) are, for example, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, Aliphatic di(meth)acrylate compounds such as (meth)acrylate and neopentyl glycol di(meth)acrylate; trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylol Aliphatic tri(meth)acrylate compounds such as propane tri(meth)acrylate and dipentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate Tetrafunctional or higher aliphatic poly(meth)acrylate compounds such as acrylates, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate; molecules of the various aliphatic hydrocarbon type poly(meth)acrylate compounds (Poly)oxyalkylene modified products in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain, etc. is introduced into the structure; the aforementioned various aliphatic hydrocarbons Examples thereof include lactone-modified products obtained by introducing a (poly)lactone structure into the molecular structure of a type poly(meth)acrylate compound.

The alicyclic poly(meth)acrylate compound and its modified form (A8) are, for example, 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornanedimethanol di(meth)acrylate, di Alicyclic di(meth)acrylate compounds such as cyclopentanyl di(meth)acrylate and tricyclodecanedimethanol di(meth)acrylate; ) (poly)oxyalkylene modified products introduced with (poly)oxyalkylene chains such as oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains; the various alicyclic poly(meth)acrylate compounds lactone modified products in which a (poly)lactone structure is introduced into the molecular structure of

Aromatic poly (meth) acrylate compounds and their modified products (A9) are, for example, biphenol di (meth) acrylate, bisphenol di (meth) acrylate, the following structural formula (4)

［式中Ｒ^５はそれぞれ独立に（メタ）アクリロイル基、（メタ）アクリロイルオキシ基、（メタ）アクリロイルオキシアルキル基の何れかである。］
で表されるビカルバゾール化合物、下記構造式（５－１）又は（５－２）

[In the formula, each ^R5 is independently a (meth)acryloyl group, a (meth)acryloyloxy group, or a (meth)acryloyloxyalkyl group. ]
A bicarbazole compound represented by the following structural formula (5-1) or (5-2)

［式中Ｒ^５はそれぞれ独立に（メタ）アクリロイル基、（メタ）アクリロイルオキシ基、（メタ）アクリロイルオキシアルキル基の何れかである。］
で表されるフルオレン化合物等の芳香族ジ（メタ）アクリレート化合物；前記各種の芳香族ポリ（メタ）アクリレート化合物の分子構造中に（ポリ）オキシエチレン鎖、（ポリ）オキシプロピレン鎖、（ポリ）オキシテトラメチレン鎖等の（ポリ）オキシアルキレン鎖を導入した（ポリ）オキシアルキレン変性体；前記各種の芳香族ポリ（メタ）アクリレート化合物の分子構造中に（ポリ）ラクトン構造を導入したラクトン変性体等が挙げられる。

[In the formula, each ^R5 is independently a (meth)acryloyl group, a (meth)acryloyloxy group, or a (meth)acryloyloxyalkyl group. ]
Aromatic di(meth)acrylate compounds such as fluorene compounds represented by: (poly)oxyethylene chain, (poly)oxypropylene chain, (poly) (poly)oxyalkylene modified products into which a (poly)oxyalkylene chain such as an oxytetramethylene chain is introduced; lactone modified products in which a (poly)lactone structure is introduced into the molecular structure of the various aromatic poly(meth)acrylate compounds etc.

When the (meth)acryloyl group-containing compound (A) contains a (meth)acrylate compound other than the (poly)ester (meth)acrylate resin (A1), the present invention exhibits high adhesion to inorganic materials. , Since the effect of excellent storage stability is sufficiently exhibited, the content of the (poly)ester (meth)acrylate resin (A1) with respect to the total mass of the (meth)acryloyl group-containing compound (A) is 5 to It is preferably in the range of 80% by mass.

In particular, when the (poly)ester (meth)acrylate resin (A1) is the lactone-modified urethane (meth)acrylate resin, the lactone-modified urethane ( The content of the meth)acrylate resin is preferably in the range of 5 to 80% by mass, more preferably in the range of 5 to 60% by mass. As the (meth)acrylate compound other than the lactone-modified urethane (meth)acrylate resin, it is preferable to use the aliphatic hydrocarbon type poly(meth)acrylate compound or its modified product (A7). At this time, the mass ratio of both [(lactone-modified urethane (meth)acrylate resin) / (aliphatic hydrocarbon-type poly(meth)acrylate compound or its modified product (A7)) is in the range of 5/95 to 80/20. It is preferably in the range of 5/95 to 60/40.

Furthermore, the (meth)acryloyl group-containing compound (A) preferably contains 2 to 30% by mass of the structural site derived from the lactone compound of the lactone-modified urethane (meth)acrylate resin, and preferably 2 to 20% by mass. % range is preferable. The lactone structure ratio (% by mass) in the (meth)acryloyl group-containing compound (A) is [total mass of structural sites derived from the lactone compound in the lactone-modified urethane (meth)acrylate resin]/[(meth)acryloyl group-containing It is a value calculated by [total mass of compound (A) component] x 100 (% by mass), and the [total mass of structural sites derived from the lactone compound in the lactone-modified urethane (meth)acrylate resin] is the total mass of the resin. It is a value calculated from the raw material preparation ratio at the time of production, or a value calculated from the published structural formula of the manufacturer. Further, when the (meth)acryloyl group-containing compound (A) contains a component containing a structural site derived from a lactone compound in addition to the lactone-modified urethane (meth)acrylate resin, the (meth)acryloyl group-containing compound (A ) is preferably in the range of 2 to 30% by mass, more preferably in the range of 2 to 20% by mass.

Further, the (poly)ester (meth)acrylate resin (A1) is a polyester (meth)acrylate resin which is a (meth)acrylic acid adduct of the hydroxyl group-containing polyester resin, or glycidyl (meth) of the carboxy group-containing polyester resin. When the polyester (meth)acrylate resin is an acrylate adduct, the content of the polyester (meth)acrylate resin with respect to the total mass of the (meth)acryloyl group-containing compound (A) is in the range of 5 to 80% by mass. preferably in the range of 5 to 50% by mass. Further, as the (meth)acrylate compound other than the polyester (meth)acrylate resin, it is preferable to use the aliphatic hydrocarbon type poly(meth)acrylate compound or its modified product (A7). At this time, the mass ratio of both [(polyester (meth)acrylate resin) / (aliphatic hydrocarbon type poly(meth)acrylate compound or modified product thereof (A7))] is in the range of 5/95 to 80/20. more preferably in the range of 5/95 to 50/50.

The phosphate ester compound (B) may be any compound without any particular limitation as long as it has a phosphate ester structure in its molecular structure. A compound having both a phosphate ester structure and a (meth)acryloyl group in its molecular structure is classified as the phosphate ester compound (B) in the present invention.

Specific examples of the phosphate ester compound (B) include the following structural formula (6)

で表される化合物等が挙げられる。リン酸エステル化合物（Ｂ）はそれぞれ単独で用いてもよいし、二種類以上を併用してもよい。

Compounds represented by and the like. The phosphate ester compound (B) may be used alone, or two or more of them may be used in combination.

R ⁶ in the structural formula (6) is not particularly limited and may be any structural moiety. Specific examples of ^R6 include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a (meth)acryloyl group, a glycidyl group, a (poly)oxyalkylene structure, a (poly)thioalkylene structure, and a (poly)ester structure. , a structural site consisting of a combination of these, and the like. Moreover, ^R6 may have a functional group such as a hydroxyl group, an amino group, a carboxy group, or a halogen atom. Among them, it is a compound having a polymerizable group such as a (meth)acryloyl group or an allyl group in the molecular structure because it becomes an active energy ray-curable resin composition with even better adhesion to inorganic materials and storage stability. is preferred.

Examples of commercial products of the phosphate ester compound (B) include, for example, “Kayamer PM-2” and “Kayamer PM-2” manufactured by Nippon Kayaku Co., Ltd., which are phosphate ester compounds having a (meth)acryloyl group in the molecular structure. PM-21”, Kyoeisha Chemical Co., Ltd. “Light Ester P-1M”, “Light Ester P-2M”, “Light Acrylate P-1A (N)”, SOLVAY “SIPOMER PAM 100”, “SIPOMER PAM 200” , "SIPOMER PAM 300", "SIPOMER PAM 4000", "Viscoat #3PA" and "Viscoat #3PMA" manufactured by Osaka Organic Chemical Industry Co., Ltd., "New Frontier S-23A" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.; allyl in the molecular structure Examples include "SIPOMER PAM 5000" manufactured by SOLVAY, which is a phosphate ester compound having an ether group.

In the active energy ray-curable resin composition of the present invention, the content of the phosphate ester compound (B) is appropriately adjusted according to desired performance and the like. In particular, since it becomes an active energy ray-curable resin composition that has high adhesion to inorganic materials and excellent storage stability, it is 0.5 to 0.5 with respect to the total of components other than the solvent of the active energy ray-curable resin composition. It is preferably in the range of 10% by mass, more preferably in the range of 1 to 5% by mass.

The silane coupling agent (C), for example, [(meth)acryloyloxyalkyl]trialkylsilane, [(meth)acryloyloxyalkyl]dialkylalkoxysilane, [(meth)acryloyloxyalkyl]alkyldialkoxysilane, [(meth) ) (Meth)acryloyloxy-based silane coupling agents such as acryloyloxyalkyl]trialkoxysilane; , vinyl-based silane coupling agents such as trialkoxyallylsilane; styrene-based silane coupling agents such as styryltrialkyl, styryldialkylalkoxysilane, styrylalkyldialkoxysilane, styryltrialkoxysilane; (glycidyloxyalkyl)trialkylsilane, (glycidyloxyalkyl)dialkylalkoxysilane, (glycidyloxyalkyl)alkyldialkoxysilane, (glycidyloxyalkyl)trialkoxysilane, [(3,4-epoxycyclohexyl)alkyl]trimethoxysilane, [(3,4-epoxy Cyclohexyl)alkyl]trialkylsilane, [(3,4-epoxycyclohexyl)alkyl]dialkylalkoxysilane, [(3,4-epoxycyclohexyl)alkyl]alkyldialkoxysilane, [(3,4-epoxycyclohexyl)alkyl] epoxy-based silane coupling agents such as trialkoxysilane; isocyanate-based silane coupling agents such as (isocyanatoalkyl)trialkylsilane, (isocyanatoalkyl)dialkylalkoxysilane, (isocyanatoalkyl)alkyldialkoxysilane, and (isocyanatoalkyl)trialkoxysilane ring agents and the like. Each of these may be used alone, or two or more of them may be used in combination.

Among the silane coupling agents (C), a (meth)acryloyloxy-based silane coupling agent is preferred because it provides an active energy ray-curable resin composition that exhibits even better adhesion to inorganic materials and storage stability. Particularly preferred are [(meth)acryloyloxyalkyl]trialkoxysilanes such as -(meth)acryloyloxypropyltrimethoxysilane and 3-(meth)acryloyloxypropyltriethoxysilane.

The content of the silane coupling agent (C) in the active energy ray-curable resin composition of the present invention is appropriately adjusted according to desired performance and the like. In particular, since it becomes an active energy ray-curable resin composition that has high adhesion to inorganic materials and excellent storage stability, it is 1 to 15 masses relative to the total of components other than the solvent of the active energy ray-curable resin composition. %, more preferably 2 to 8 mass %.

Furthermore, since the active energy ray-curable resin composition of the present invention has a higher adhesion to inorganic materials, the phosphoric acid ester compound (B) and the silane coupling agent The total with (C) is preferably in the range of 2 to 20% by mass, more preferably in the range of 4 to 10% by mass. Further, the mass ratio [(B)/(C)] of the phosphate ester compound (B) and the silane coupling agent (C) is preferably in the range of 1/1.1 to 1/10, It is more preferably in the range of 1/1.2 to 1/7.

The active energy ray-curable resin composition of the present invention contains other components in addition to the (meth)acryloyl group-containing compound (A), the phosphate ester compound (B) and the silane coupling agent (C). You may have The other components include, for example, other resin components other than the (meth)acryloyl group-containing compound (A), inorganic fine particles, photopolymerization initiators, solvents, ultraviolet absorbers, antioxidants, silicon additives, Fluorinated additives, antistatic agents, organic beads, quantum dots (QD), rheology control agents, defoaming agents, antifogging agents, coloring agents, and the like.

The other resin components are added for the purpose of improving the desired properties of the active energy ray-curable resin composition, such as substrate adhesion, gas barrier properties, moist heat resistance, and flexibility. can be used. Examples include acrylic resins, polyester resins, urethane resins, and petroleum resins. Each of these may be used alone, or two or more of them may be used in combination. When other resin components are used, the amount added is preferably in the range of 0.5 to 100% by mass relative to the total mass of the (meth)acryloyl group-containing compound (A).

The inorganic fine particles are added for the purpose of adjusting the hardness, refractive index, etc. of the cured coating film of the active energy ray-curable resin composition, and various known and commonly used inorganic fine particles can be used. Examples include fine particles of silica, alumina, zirconia, titania, barium titanate, antimony trioxide, and the like. Each of these may be used alone, or two or more of them may be used in combination. Of these, silica particles that are particularly versatile include various types such as fumed silica, wet-process silica called precipitation silica, gel silica, sol-gel silica, etc., and any of them may be used. Moreover, the surfaces of the inorganic fine particles may be modified with a silane coupling agent or the like. The particle diameter of the inorganic fine particles is appropriately adjusted depending on the desired coating film performance and the like, but the value measured by the dynamic light scattering method is preferably in the range of 10 to 250 nm. When inorganic fine particles are used, the amount added is preferably in the range of 0.1 to 60 mass % with respect to the total of components other than the solvent in the active energy ray-curable resin composition.

As for the photopolymerization initiator, an appropriate one may be selected and used according to the type of active energy ray to be irradiated. Further, it may be used in combination with a photosensitizer such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound and a nitrile compound. Specific examples of photopolymerization initiators include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino) -2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and other alkylphenone photoinitiators; 2,4,6-trimethylbenzoyl-diphenyl- acylphosphine oxide-based photopolymerization initiators such as phosphine oxide; intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds; Each of these may be used alone, or two or more of them may be used in combination.

Commercial products of the photopolymerization initiator, for example, manufactured by BASF "IRGACURE127", "IRGACURE184", "IRGACURE250", "IRGACURE270", "IRGACURE290", "IRGACURE369E", "IRGACURE379EG", "IRGACURE500", "IRGACURE651" , “IRGACURE754”, “IRGACURE819”, “IRGACURE907”, “IRGACURE1173”, “IRGACURE2959”, “IRGACURE MBF”, “IRGACURE TPO”, “IRGACURE OXE 01”, “IRGACURE OXE 02” and the like.

The amount of the photopolymerization initiator added is preferably in the range of 0.05 to 15% by mass with respect to the total of components other than the solvent of the active energy ray-curable resin composition, and 0.1 to 10% by mass. A range is more preferred.

The solvent is added for the purpose of adjusting the coating viscosity of the active energy ray-curable resin composition, and the type and amount added are appropriately adjusted according to the desired performance. Generally, it is used in the range of 10 to 90% by mass based on the total active energy ray-curable resin composition. Specific examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; esters such as methyl acetate, ethyl acetate and butyl acetate; Solvents; Alicyclic solvents such as cyclohexane and methylcyclohexane; Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene Glycol ether solvents such as glycol monopropyl ether can be used. Each of these may be used alone, or two or more of them may be used in combination.

The ultraviolet absorber is, for example, 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1, 3,5-triazine, 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3 ,5-triazine and other triazine derivatives, 2-(2′-xanthenecarboxy-5′-methylphenyl)benzotriazole, 2-(2′-o-nitrobenzyloxy-5′-methylphenyl)benzotriazole, 2- xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone and the like. Each of these may be used alone, or two or more of them may be used in combination.

Examples of the antioxidant include hindered phenol antioxidants, hindered amine antioxidants, organic sulfur antioxidants, phosphate ester antioxidants, and the like. Each of these may be used alone, or two or more of them may be used in combination.

Examples of the silicon-based additive include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, fluorine-modified dimethyl Examples include polyorganosiloxane having an alkyl group or a phenyl group such as polysiloxane copolymer, amino-modified dimethylpolysiloxane copolymer, polydimethylsiloxane having a polyether-modified acrylic group, polydimethylsiloxane having a polyester-modified acrylic group, and the like. be done. Each of these may be used alone, or two or more of them may be used in combination.

Examples of the fluorine-based additive include "Megaface" series manufactured by DIC Corporation. Each of these may be used alone, or two or more of them may be used in combination.

The antistatic agent includes, for example, pyridinium, imidazolium, phosphonium, ammonium, or lithium salts of bis(trifluoromethanesulfonyl)imide or bis(fluorosulfonyl)imide. Each of these may be used alone, or two or more of them may be used in combination.

Examples of the organic beads include polymethylmethacrylate beads, polycarbonate beads, polystyrene beads, polyacrylicstyrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, Polyester resin beads, polyamide resin beads, polyimide resin beads, polyethylene fluoride resin beads, polyethylene resin beads and the like can be mentioned. Each of these may be used alone, or two or more of them may be used in combination. The average particle size of these organic beads is preferably in the range of 1 to 10 μm.

The quantum dots (QDs) are group II-V semiconductor compounds, group II-VI semiconductor compounds, group III-IV semiconductor compounds, group III-V semiconductor compounds, group III-VI semiconductor compounds, group IV-VI semiconductor compounds, I-III-VI group semiconductor compounds, II-IV-VI group semiconductor compounds, II-IV-V group semiconductor compounds, I-II-IV-VI group semiconductor compounds, IV group elements or compounds containing these, etc. . The II-VI group semiconductor compound is, for example, binary compounds such as ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe; Ternary compounds such as CdSeTe, CdSTe, CdHgS, CdHgSe, CdHgTe, HgSeS, HgSeTe, HgSTe, HgZnS, HgZnSe, HgZnTe; CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgST Quaternary such as e, CdHgZnTe, HgZnSeS, HgZnSeTe, HgZnSTe compounds and the like. Examples of the III-IV group semiconductor compounds include B ₄ C ₃ , Al ₄ C ₃ , Ga ₄ C ₃ and the like. The III-V group semiconductor compounds are, for example, binary compounds such as BP, BN, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb; Ternary compounds such as GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP; NP , InAlNAs, InAlNSb, InAlPAs, and InAlPSb. The III-VI group semiconductor compounds are, for example, Al ₂ S ₃ , Al ₂ Se ₃ , Al ₂ Te ₃ , Ga 2 S 3 , Ga ₂ Se ₃ , _{Ga 2 Te 3 ,} GaTe, In ₂ S ₃ , In _{2 Se3} , _In2Te3 , _InTe , etc. are mentioned. The IV-VI group semiconductor compounds include, for example, binary compounds such as SnS, SnSe, SnTe, PbS, PbSe, and PbTe; ternary compounds such as SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, and SnPbTe quaternary compounds such as SnPbSSe, SnPbSeTe and SnPbSTe; Examples of the I-III-VI group semiconductor compounds include CuInS ₂ , CuInSe _{2 , CuInTe 2} , CuGaS ₂ , CuGaSe ₂ , CuGaSe ₂ , AgInS ₂ , AgInSe ₂ , AgInTe ₂ , AgGaSe ₂ , AgGaS _{2 ,} AgGaTe ₂ and the like. mentioned. Examples of the Group IV element or a compound containing it include C, Si, Ge, SiC, SiGe and the like. A quantum dot may consist of a single semiconductor compound, or may have a core-shell structure consisting of a plurality of semiconductor compounds. Moreover, the surface thereof may be modified with an organic compound.

The active energy ray-curable resin composition of the present invention is produced by mixing each of the above ingredients. The mixing method is not particularly limited, and a paint shaker, disper, roll mill, bead mill, ball mill, attritor, sand mill, bead mill or the like may be used.

Although the application of the active energy ray-curable resin composition of the present invention is not particularly limited, it can be widely used for paints, for example. The paint containing the active energy ray-curable resin composition of the present invention has excellent adhesion to plastic films, resin moldings, and the like, as well as various metals, glasses, SiO _x , Al ₂ O ₃ , TiO ₂ , ITO, and the like. It also has excellent adhesion to inorganic compounds. Applications utilizing such characteristics include laminate applications having a coating film layer using the coating material of the present invention and an inorganic material layer adjacent thereto.

Regarding the laminate, more specifically, for example, when it is desired to provide a resin coating film on a glass or metal substrate, a coating film made of the coating composition of the present invention is placed between the glass or metal substrate and the resin coating film. By installing it, both can be made to adhere more firmly. Alternatively, when it is desired to laminate an inorganic material thin film such as a metal vapor deposition film and a resin coating film, a coating film made of the coating material of the present invention is placed between the inorganic material thin film and the resin coating film, whereby lamination that does not easily peel off. you can get a body Especially, when the inorganic material layer is made of a silicon-based compound such as silicate glass or a _SiOx film, particularly high adhesion is exhibited.

As an example of the laminate, a method for producing a laminate in which a coating film made of the coating material of the present invention is placed between an inorganic material thin film and a resin coating film will be described. Examples of the inorganic material thin film include vapor deposition films of metals or inorganic compounds, but since such vapor deposition films are difficult to form independently, for example, the vapor deposition films are formed on plastic films. is preferred. Examples of the plastic film include triacetylcellulose film, polyester film, acrylic film, cycloolefin polymer film, polyamide film, polyimide film, polystyrene film, polycarbonate film, and polypropylene film. The thickness of these plastic films is appropriately adjusted according to the material thereof and the application of the laminate, but in general, those having a thickness of about 30 to 300 μm are used.

Examples of inorganic materials forming the inorganic material thin film include BN, MgFe ₂ , Al, Al ₂ O ₃ , Si, SiO, SiO ₂ , SiC, Si ₃ N ₄ , Ti, TiN, TiO ₂ , Cr—SiO, Mn—Zn, Fe, Fe—Si—Al, Co—Cr, Co—Cr—Ta, Ni, Ni—Zn, Ni—Cr, Ni—Fe—Mo, Cu, ZnO, GaAs—Al, SeTiO ₃ , Ag , SnO ₂ , Ta, TaN, Ta ₂ O ₅ , Ta—Si, Ta—Al, W, Au, PbTiO ₃ , Bi ₂ O ₃ , ITO, GZO, AZO, PZT and the like. The inorganic material thin film may be formed by any method, for example, plasma assisted method (CVD), new and old vapor deposition (MBE method, flash method, etc.), sputtering, anodization, electroless plating, electroplating, etc. method. The thickness of the inorganic material thin film is appropriately adjusted according to the material and the use of the laminate, but generally it is preferably about 30 nm to 3 μm.

The coating method for coating the coating material of the present invention on the inorganic material thin film is not particularly limited, and may be bar coater coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing. , flexographic printing, screen printing, and the like.

Examples of the active energy ray irradiated to cure the paint of the present invention include ultraviolet rays and electron beams. When curing with ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, an LED lamp, etc. is used as a light source, and the amount of light, arrangement of the light source, etc. are adjusted as necessary. When a high-pressure mercury lamp is used, it is preferable to carry out curing at a conveying speed of 5 to 50 m/min for one lamp having a light quantity usually in the range of 80 to 160 W/cm. On the other hand, in the case of curing with an electron beam, it is preferable to cure with an electron beam accelerator having an acceleration voltage generally in the range of 10 to 300 kV at a conveying speed in the range of 5 to 50 m/min. When the paint contains an organic solvent, it is dried at a temperature of about 50 to 100° C. for several tens of seconds to several minutes, and then irradiated with active energy rays. The thickness of the coating film made of the paint of the present invention is appropriately adjusted according to the use and desired performance of the laminate, but generally it is preferably about 1 μm to 100 μm.

A wide variety of resin coating films can be used as the resin coating film to be superimposed on the layer composed of the coating material of the present invention, depending on the application and desired performance of the laminate. Examples of the form of the resin material for forming the resin coating film include thermosetting materials, active energy ray-curable materials, and lacquers. Among these, as the active energy ray-curable resin material, a matrix resin similar to the compound exemplified as the (meth)acryloyl group-containing compound (A) is used as the matrix resin, and depending on the desired performance, the other resin or the above Examples thereof include those in which inorganic fine particles, the organic beads, the quantum dots (QDs), and other additives are blended. When an active energy ray-curable resin material is used, the resin material may be applied before curing the coating material of the present invention, and both may be cured at once by irradiating the active energy ray. The thickness of the resin coating film is appropriately adjusted according to the use and desired performance of the laminate, but generally it is preferably about 1 μm to 100 μm.

The present invention will be described in more detail below with specific production examples and examples, but the present invention is not limited to these examples. All parts and percentages in the examples are based on mass unless otherwise specified.

In the examples of the present invention, weight average molecular weight (Mw) and gel permeation chromatography (GPC) are used and measured under the following conditions.

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

In the examples of the present application, the lactone structural ratio (% by mass) in the (meth)acryloyl group-containing compound (A) is defined as [total mass of structural sites derived from lactone compounds in the lactone-modified urethane (meth)acrylate resin, etc.]/[ (Meth) acryloyl group-containing compound (A) component total mass] × 100 (% by mass), the total number of structural sites derived from the lactone compound of the lactone-modified urethane (meth) acrylate resin, etc. Mass] is a value calculated from the ratio of raw materials charged when producing the resin, or a value calculated from the published structural formula of the manufacturer.

Production Example 1 Production of Lactone-Modified Hydroxy(Meth)acrylate Compound (x2-1) In a reactor equipped with a stirrer, 400 parts by mass of ε-caprolactone, 208 parts by mass of hydroxyethyl acrylate, 0.1 parts by mass of dibutyltin dilaurate and 0.1 part by mass of methoquinone was added and reacted at 130° C. for 8 hours while stirring to obtain a lactone-modified hydroxy(meth)acrylate compound (x2-1).

Production Example 2 Production of (poly)ester (meth)acrylate resin (A1-1) Into a reactor equipped with a stirring device, a polyisocyanate compound (manufactured by DIC Corporation "Barnock DN-901S" isocyanurate modified form of hexamethylene diisocyanate , an isocyanate group content of 23.5% by mass), 2 parts by mass of dibutyltin dilaurate and 2 parts by mass of methoquinone were added, and the temperature was raised to 60° C. while stirring. Then, 658 parts by mass of the lactone-modified hydroxy(meth)acrylate compound (x2-1) was added in portions over about one hour. The mixture was heated to 80° C. and reacted for further 3 hours. After confirming that the absorption of the isocyanate group at 2250 cm ⁻¹ disappeared in the infrared spectrum, the reaction was terminated and the (poly)ester (meth)acrylate resin (A1-1) was obtained. Obtained. The weight average molecular weight (Mw) of the (poly)ester (meth)acrylate resin (A1-1) was 4,000, and the theoretical value of the (meth)acryloyl group equivalent calculated from the feed ratio of the raw materials was 523 g/equivalent. .

Production Example 3 Production of (poly)ester (meth)acrylate resin (A1-2) 252 parts by mass of dicyclohexylmethane-4,4'-diisocyanate, 2 parts by mass of dibutyltin dilaurate and 2 parts by mass of metoquinone were added to a reactor equipped with a stirring device. Parts by mass were added, and the temperature was raised to 60° C. while stirring. Then, 757 parts by mass of the lactone-modified hydroxy(meth)acrylate compound (x2-1) was added in portions over about one hour. Heated to 80 ° C. and further reacted for 3 hours, after confirming that the absorption of the isocyanate group at 2250 cm ^-1 disappeared in the infrared spectrum, the reaction was terminated, and the (poly)ester (meth)acrylate resin (A1-2) got The weight average molecular weight (Mw) of the (poly)ester (meth)acrylate resin (A1-2) was 1,500, and the theoretical value of the (meth)acryloyl group equivalent calculated from the feed ratio of the raw materials was 460 g/equivalent. .

Examples 1 to 6 and Comparative Example 1 Production and evaluation of active energy ray-curable resin composition An active energy ray-curable resin composition and a laminated film were produced in the following manner, and various evaluation tests were conducted. Tables 1 and 2 show the results.

Details of each component in Tables 1 and 2 are as follows.
・ (Poly)ester (meth)acrylate resin (A1-3): “Aronix M-8030” manufactured by Toagosei Co., Ltd., polyester (meth)acrylate resin which is an acrylic acid adduct of hydroxyl group-containing polyester resin and other poly( A composition with a meth)acrylate compound, an acid value of 7 mgKOH/g or less, and a polyester (meth)acrylate resin content of 16% measured using gel permeation chromatography (GPC) under the same conditions as the molecular weight measurement.
・ (Poly)ester (meth)acrylate resin (A1-4): “Aronix M-8060” manufactured by Toagosei Co., Ltd., polyester (meth)acrylate resin which is an acrylic acid adduct of hydroxyl group-containing polyester resin and other poly( A composition with a meth)acrylate compound, an acid value of 16 mgKOH/g or less, and a polyester (meth)acrylate resin content of 13% measured using gel permeation chromatography (GPC) under the same conditions as the molecular weight measurement.
Aliphatic hydrocarbon-type poly(meth)acrylate compound (A7-1): "DPA-600" manufactured by Toagosei Co., Ltd., containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate at a molar ratio of 40/60 Composition / Acrylic resin: DIC's "Acrydic WXU-880" non-volatile content 50% by mass
• Phosphate ester compound (B-1): Nippon Kayaku Co., Ltd. "KAYAMER PM-2", a mixture of compounds represented by the following structural formula, in which a and b are different. The average values of a and b are each about 1.5.

（式中ａ及びｂはそれぞれ０又は１～３の整数であり、ａ＋ｂは３である。）

(In the formula, a and b are each an integer of 0 or 1 to 3, and a+b is 3.)

· Silane coupling agent (C-1): Shin-Etsu Chemical Co., Ltd. "KBE-503", 3-methacryloxypropyltriethoxysilane · Photopolymerization initiator: BASF "Irgacure # 184"

Production of active energy ray-curable resin composition Each component was blended in the ratio shown in Table 1, and ethyl acetate was added to adjust the non-volatile content to 30% by mass to obtain an active energy ray-curable resin composition.

Storage Stability Evaluation The active energy ray-curable resin composition was stored at 40° C. for 3 days, and changes in appearance and acid value of the composition were evaluated. Also, using the active energy ray-curable resin composition after storage for 3 days at 40° C., a laminated film was prepared under the following conditions, and the presence or absence of cissing defects in the coating film layer was evaluated.
A: No cissing defects B: Slight cissing defects seen C: cissing defects seen throughout the coating film (manufacture of laminated film)
On the SiO ₂ thin film of the polyethylene terephthalate film on which the SiO ₂ thin film with a thickness of 100 nm was formed, the active energy ray-curable resin composition was applied with a bar coater so that the film thickness after curing was 2 μm, and was heated at 90 ° C. Allow to dry for 3 minutes. A laminate film having a coating layer was obtained by irradiating ultraviolet rays of 500 mJ/cm ² using a high-pressure mercury lamp in a nitrogen atmosphere.

Adhesion evaluation (manufacture of laminated film)
On the SiO ₂ thin film of the polyethylene terephthalate film on which the SiO ₂ thin film with a thickness of 100 nm was formed, the active energy ray-curable resin composition was applied with a bar coater so that the film thickness after curing was 2 μm, and was heated at 90 ° C. Allow to dry for 3 minutes. A laminate film having a coating layer was obtained by irradiating ultraviolet rays of 500 mJ/cm ² using a high-pressure mercury lamp in a nitrogen atmosphere.
(Test method)
On the coating layer side of the laminated film, 100 grids of 4 mm ² were made by cutting 10×10 grids at intervals of 1 mm with a cutter knife. Then, after sticking a cellophane tape on the grid, a rapid peeling test was performed, and the adhesion between the _SiO2 thin film and the coating was evaluated by the number of grids that did not peel off out of 100 grids.
Further, the same test was performed using the laminated film after exposure to conditions of 65° C. and 90% humidity for 72 hours, and the adhesion after the wet heat test was evaluated.

Claims (7)

(Meth)acryloyl group-containing compound (A), a phosphate ester compound (B) and a silane coupling agent (C), wherein the (meth)acryloyl group-containing compound (A) is a (poly)ester (meth)acrylate An active energy ray-curable resin composition comprising a resin (A1) and an aliphatic hydrocarbon-type poly(meth)acrylate compound or a modified product thereof (A7) as essential components,
The content of the (meth)acryloyl group-containing compound (A) is in the range of 80 to 98% by mass in the solid content of the active energy ray-curable resin composition,
The total content of the phosphate ester compound (B) and the silane coupling agent (C) is in the range of 2 to 20% by mass in the solid content of the active energy ray-curable resin composition,
The phosphate ester compound (B) has a phosphate ester structure and a (meth)acryloyl group in its molecular structure,
The silane coupling agent (C) contains a (meth)acryloyloxy-based silane coupling agent,
(Meth)acryloyl group-containing compound (A) does not contain a phosphate ester structure and a silicon atom in the molecule,
The (poly)ester (meth)acrylate resin (A1) contains a polyester (meth)acrylate resin which is a (meth)acrylic acid adduct of a hydroxyl group-containing polyester resin ,
The (poly)ester (meth)acrylate resin (A1) is a lactone-modified urethane (meth)acrylate resin which is a reaction product of a polyisocyanate compound (x1) and a lactone-modified hydroxy (meth)acrylate compound (x2). An active energy ray-curable resin composition characterized by: The active energy ray-curable resin composition according to claim 1, wherein the proportion of the (poly)ester (meth)acrylate resin (A1) in the (meth)acryloyl group-containing compound (A) is in the range of 5 to 80% by mass. thing. Mass ratio of the (poly)ester (meth)acrylate resin (A1) and the aliphatic hydrocarbon-type poly(meth)acrylate compound or modified product thereof (A7) [(poly)ester (meth)acrylate resin (A1)/ The active energy ray-curable resin composition according to claim 1, wherein the aliphatic hydrocarbon-type poly(meth)acrylate compound or modified product thereof (A7)] ranges from 5/95 to 50/50. A paint containing the active energy ray-curable resin composition according to any one of claims 1 to 3 . A coating film comprising the coating material according to claim 4 . A laminate comprising a layer comprising the coating film according to claim 5 and an inorganic material layer adjacent thereto. 7. The laminate according to claim 6 , wherein said inorganic material layer is a silicate glass or SiOx film.