JP6972577B2 - Active energy ray-curable resin composition and laminated film - Google Patents

Description

The present invention relates to an active energy ray-curable resin composition, a paint, a coating film, and a laminated film, which are excellent in appearance and moisture permeability in a cured coating film.

The active energy ray-curable resin composition has excellent transparency and high surface hardness, and is mainly used as a hard coat agent for optical films for displays. In recent years, various optical films have been made thinner as the display has become thinner. Of these, the triacetyl cellulose film, which is widely used for polarizing plates, is originally a material with high moisture permeability, but since the moisture permeability becomes more remarkable due to the thinning, there is a concern that the members may deteriorate due to moisture. In order to prevent this, the development of a hard coat agent having excellent moisture permeability is required.

As a coating agent having excellent moisture permeability resistance, an active energy ray-curable resin composition containing a hydroxyl group-containing petroleum resin and a polyacrylate compound is known (see Patent Document 1). Although the coating agent described in Patent Document 1 has high moisture permeability as compared with the active energy ray-curable resin composition containing no petroleum resin, the transparency and smoothness of the coating film are not sufficient.

Japanese Unexamined Patent Publication No. 2004-323751

Therefore, an object to be solved by the present invention is to provide an active energy ray-curable resin composition, a paint, a coating film, and a laminated film having excellent appearance and moisture permeability in a cured coating film.

As a result of diligent studies to solve the above problems, the present inventors have obtained a cured coating of an active energy ray-curable resin composition containing a petroleum resin having a hydroxyl value of 10 mgKOH / g or less and a (meth) acrylate compound. We have found that the film is excellent in transparency and smoothness in addition to moisture permeability resistance, and have completed the present invention.

That is, the present invention relates to an active energy ray-curable resin composition comprising a petroleum resin (A) having a hydroxyl value of 10 mgKOH / g or less and a (meth) acrylate compound (B) as essential components. ..

The present invention further relates to a coating material containing the resin composition.

The present invention further relates to a coating film made of the above-mentioned paint.

The present invention further relates to a laminated film having a layer composed of the coating film.

According to the present invention, it is possible to provide an active energy ray-curable resin composition, a paint, a coating film, and a laminated film having excellent appearance and moisture permeability in a cured coating film.

The active energy ray-curable resin composition of the present invention is characterized by containing a petroleum resin (A) having a hydroxyl value of 10 mgKOH / g or less and a (meth) acrylate compound (B) as essential components.

In the present invention, the (meth) acryloyl group refers to one or both of an acryloyl group and a methacryloyl group. Further, (meth) acrylate is a general term for acrylate and methacrylate.

In the active energy ray-curable resin composition of the present invention, the mass ratio of the petroleum resin (A) to the (meth) acrylate compound (B) is an active energy ray having further excellent appearance and moisture permeability in a cured coating film. Since it is a curable resin composition, it is preferably in the range of 5/95 to 50/50, and more preferably in the range of 15/85 to 40/60.

Specifically, the petroleum resin (A) is produced by polymerizing an olefin compound or a diolefin compound produced by thermal decomposition of naphtha. Further, it may be further hydrogenated if necessary. The olefin compound or the diolefin compound is, for example, an aliphatic monomer such as isoprene or piperylene called a C5-based monomer, an aromatic monomer such as indene, styrene or vinyltoluene called a C9-based monomer, cyclopentadiene or dicyclo. Examples include pentadiene. In addition, a monomer having a functional group such as allyl alcohol may be copolymerized for the purpose of introducing a functional group such as a hydroxyl group into the resin. One type of petroleum resin (A) may be used alone, or two or more types may be used in combination.

Among the petroleum resins (A), those containing dicyclopentadiene and the aromatic monomer as main components are preferable because they are active energy ray-curable resin compositions having further excellent moisture permeability resistance in the cured coating film. Further, it is more preferably hydrogenated. Further, in the present invention, the petroleum resin (A) having a hydroxyl value of 10 mgKOH / g or less is used, but it is an active energy ray-curable resin composition having further excellent appearance and moisture permeability in a cured coating film. The hydroxyl value and acid value of the petroleum resin (A) are both more preferably 10 mgKOH / g or less, and particularly preferably 5 mgKOH / g or less. When a plurality of types of petroleum resin (A) are used in combination, both the hydroxyl value and the acid value of the petroleum resin (A) are preferably 10 mgKOH / g or less, and more preferably 5 mgKOH / g or less.

The softening point of the petroleum resin (A) is preferably in the range of 70 to 150 ° C. because of its excellent compatibility with the (meth) acrylate compound (B). Further, the weight average molecular weight (Mw) of the petroleum resin (A) is preferably in the range of 350 to 1,500.

In the present invention, the molecular weight and the molecular weight distribution of the resin are values measured under the following conditions using a gel permeation chromatograph (GPC).

Measuring device; HLC-8220 manufactured by Tosoh Corporation
Column; Guard column H _XL- 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 velocity 1.0 ml / min Standard; Polystyrene sample; 0.4% by mass in terms of resin solid content Tetrahydrofuran solution filtered through a microfilter (100 μl)

As the petroleum resin (A), a commercially available product may be used. Specifically, "T-REZ HA085" manufactured by Tonen General Oil Co., Ltd. [monomer: dicyclopentadiene, hydrogenation: yes, softening point 86.6 ° C (measured according to TSTM 4027), hydroxyl value, acid value Both less than 1 mgKOH / g], "T-REZ HA103" [monomer: dicyclopentadiene, hydrogenation: yes, softening point 103.7 ° C (measured according to TSTM 4027), hydroxyl value and acid value both 1 mgKOH / g Less than], "T-REZ HA105" [monomer: dicyclopentadiene, hydrogenation: yes, softening point 105.4 ° C (measured according to TSTM 4027), hydroxyl value and acid value both less than 1 mgKOH / g], " T-REZ HA125 "[monomer: dicyclopentadiene, hydrogenation: yes, softening point 124.6 ° C (measured according to TSTM 4027), hydroxyl value and acid value both less than 1 mgKOH / g]," T-REZ HB103 " [Polymer: dicyclopentadiene and aromatic monomer, hydrogenation: Yes, softening point 102.5 ° C (measured according to TSTM 4027), hydroxyl value and acid value are both less than 1 mgKOH / g], "T-REZ HB125" [Polymer: dicyclopentadiene and aromatic monomer, hydrogenation: Yes, softening point 123.8 ° C (measured according to TSTM 4027), hydroxyl value and acid value are both less than 1 mgKOH / g], manufactured by Idemitsu Kosan Co., Ltd. "Imarb S-100" [monomer: dicyclopentadiene and aromatic monomer, hydrogen addition: yes, softening point 100 ° C (measured according to JIS K2207), hydroxyl value and acid value both less than 1 mgKOH / g], "Imarb S-110 "[monomer: dicyclopentadiene and aromatic monomer, hydrogenation: yes, softening point 110 ° C (measured according to JIS K2207), hydroxyl value and acid value both less than 1 mgKOH / g]", "Imarb P -100 "[Semiconductor: dicyclopentadiene and aromatic monomer, hydrogenation: Yes, softening point 100 ° C (measured according to JIS K2207), hydroxyl value and acid value both less than 1 mgKOH / g]," Imarb P-125 [Polymer: dicyclopentadiene and aromatic monomer, hydrogenation: Yes, softening point 125 ° C (measured according to JIS K2207), hydroxyl value and acid value are both less than 1 mgKOH / g], "Imarb P-140" [ Monomer: Dicyclopentadiene and aromatic monomer, Hydrogenation: Yes, Softening point 140 ° C (according to JIS K2207) Measurement), hydroxyl value, acid value are both less than 1 mgKOH / g] and the like.

The (meth) acrylate compound (B) has a (meth) acryloyl group in its molecular structure, and other specific structures are not particularly limited as long as it can cause a curing reaction by irradiation with active energy rays. A wide variety of things can be used. In the present invention, the (meth) acryloyl group refers to one or both of an acryloyl group and a methacryloyl group. Further, (meth) acrylate is a general term for acrylate and methacrylate.

Examples of the (meth) acrylate compound (B) include the following.
-Alphatic hydrocarbon type mono (meth) acrylate compound and its modified product (B1)
-Alicyclic mono (meth) acrylate compound and its modified product (B2)
-Heterocyclic mono (meth) acrylate compound and its modified product (B3)
-Aromatic mono (meth) acrylate compound and its modified product (B4)
-Alphatic hydrocarbon type poly (meth) acrylate compound and its modified product (B5)
-Alicyclic poly (meth) acrylate compound and its modified product (B6)
-Aromatic poly (meth) acrylate compound and its modified product (B7)
-Urethane (meth) acrylate resin (B8)
-Epoxy (meth) acrylate resin (B9)
・ Dendrimer type (meth) acrylate resin (B10)
(Meta) Acryloyl group-containing acrylic resin (B11)
These may be used alone or in combination of two or more.

The aliphatic hydrocarbon type mono (meth) acrylate compound and its modified form (B1) are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, propyl (meth) acrylate, hydroxypropyl. An aliphatic mono (meth) acrylate compound such as (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxypropylene chain in these molecular structures. Examples include (poly) oxyalkylene modified products having a (poly) oxyalkylene chain introduced such as a poly) oxytetramethylene chain; and lactone modified products having a (poly) lactone structure introduced into these molecular structures.

The alicyclic mono (meth) acrylate compound and its modified product (B2) are, for example, an alicyclic mono (meth) acrylate compound such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl mono (meth) acrylate. (Poly) oxyalkylene modified product in which (poly) oxyalkylene chain such as (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain is introduced into these molecular structures; these molecules Examples thereof include a lactone modified product in which a (poly) lactone structure is introduced into the structure.

The heterocyclic mono (meth) acrylate compound and its modified product (B3) are, for example, heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; (Poly) oxyalkylene modified product introduced with (poly) oxyalkylene chain such as (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain; (poly) lactone structure in these molecular structures. Examples thereof include a lactone-modified product into which the above-mentioned substance has been introduced.

The aromatic mono (meth) acrylate compound and its modified product (B4) are, for example, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxyethoxyethyl (meth). ) Acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenylphenol (meth) acrylate, phenylphenol alkyl (meth) acrylate, phenylbenzyl (meth) acrylate, phenoxybenzyl (meth) acrylate, benzylbenzyl (meth) Aromatic mono (meth) acrylate compounds such as acrylates, phenylphenoxyethyl (meth) acrylates and paracumylphenol (meth) acrylates; the following structural formula (1)

（式中Ｒ^１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：これらの分子構造中に（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；これらの分子構造中に（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。

(R ^{1 in the} formula is a hydrogen atom or a methyl group.)
Mono (meth) acrylate compounds such as compounds represented by: (Poly) oxyethylene chains, (poly) oxypropylene chains, (poly) oxytetramethylene chains and other (poly) oxyalkylene chains in these molecular structures. Introduced (poly) oxyalkylene modified product; a lactone modified product in which a (poly) lactone structure is introduced into these molecular structures can be mentioned.

The aliphatic hydrocarbon type poly (meth) acrylate compound and its modified product (B5) are, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di. Aliphatic di (meth) acrylate compounds such as (meth) acrylate and neopentyl glycol di (meth) acrylate; trimethylol propantri (meth) acrylate, glycerintri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylol. An aliphatic tri (meth) acrylate compound such as propanetri (meth) acrylate and dipentaerythritol tri (meth) acrylate; pentaerythritol tetra (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, dipentaerythritol tetra (meth). Tetrafunctional or higher functional aliphatic poly (meth) acrylate compounds such as acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; molecules of the various aliphatic hydrocarbon type poly (meth) acrylate compounds. A (poly) oxyalkylene modified product having a (poly) oxyalkylene chain introduced into the structure, such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain; Examples thereof include a lactone modified product in which a (poly) lactone structure is introduced into the molecular structure of a type poly (meth) acrylate compound.

The alicyclic poly (meth) acrylate compound and its modified form (B6) include, for example, 1,4-cyclohexanedimethanol di (meth) acrylate, norbornandi (meth) acrylate, norbornan dimethanol di (meth) acrylate, and di. Alicyclic di (meth) acrylate compounds such as cyclopentanyldi (meth) acrylates and tricyclodecanedimethanol di (meth) acrylates; in the molecular structure of the various alicyclic poly (meth) acrylate compounds (poly). ) (Poly) oxyalkylene modified product introduced with (poly) oxyalkylene chain such as (poly) oxypropylene chain, (poly) oxytetramethylene chain; the various alicyclic poly (meth) acrylate compounds. Examples thereof include a lactone modified product in which a (poly) lactone structure is introduced into the molecular structure of the above.

The aromatic poly (meth) acrylate compound and its modified product (B7) are, for example, biphenol di (meth) acrylate, bisphenol di (meth) acrylate, and the following structural formula (2).

［式中Ｒ^２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（３−１）又は（３−２）

[In the formula, R ² is independently one of a (meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloyloxyalkyl group. ]
The bicarbazole compound represented by the following structural formula (3-1) or (3-2).

［式中Ｒ^３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, R ³ is independently one of a (meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloyloxyalkyl group. ]
Aromatic di (meth) acrylate compounds such as fluorene compounds represented by; (poly) oxyethylene chains, (poly) oxypropylene chains, (poly) in the molecular structure of the various aromatic poly (meth) acrylate compounds. (Poly) oxyalkylene modified product having a (poly) oxyalkylene chain introduced such as an oxytetramethylene chain; a lactone modified product having a (poly) lactone structure introduced into the molecular structure of the various aromatic poly (meth) acrylate compounds. And so on.

Examples of the urethane (meth) acrylate resin (B8) include those obtained by reacting various polyisocyanate compounds, hydroxyl group-containing (meth) acrylate compounds, and various polyol compounds as needed.

The polyisocyanate compound is an aliphatic diisocyanate compound such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate; norbornan diisocyanate, isophorone diisocyanate, water. Alicyclic diisocyanate compounds such as supplemented xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, and 1,5-naphthalenedi isocyanate; Polymethylene polyphenyl polyisocyanate having a repeating structure represented by (4); examples thereof include isocyanurate-modified products, biuret-modified products, and allophanate-modified products. These may be used alone or in combination of two or more.

［式中、Ｒ^４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^５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（４）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, R ⁴ is either a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, respectively. R ⁵ is either an alkyl group having 1 to 4 carbon atoms independently, or a bond point linked to a structural site represented by the structural formula (4) via a methylene group marked with *. l is an integer of 0 or 1 to 3, and m is an integer of 1 or more. ]

The hydroxyl group-containing (meth) acrylate compound may be, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, or trimethylolpropane tri (meth). Hydroxyl-containing (meth) acrylate compounds such as acrylates and dipentaerythritol penta (meth) acrylates; (poly) oxyethylene chains, (poly) oxypropylene chains, (poly) oxypropylene chains, etc. A (poly) oxyalkylene modified product having a (poly) oxyalkylene chain introduced such as a poly) oxytetramethylene chain; a lactone modified product having a (poly) lactone structure introduced into the molecular structure of the various hydroxyl group-containing (meth) acrylate compounds. The body and the like can be mentioned.

The polyol compound is, for example, an aliphatic polyol compound such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol; aromatic polyols such as biphenol and bisphenol. Compound; (Poly) oxyalkylene modification in which (poly) oxyalkylene chain such as (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain is introduced into the molecular structure of the various polyol compounds. Body; Examples thereof include a lactone modified product in which a (poly) lactone structure is introduced into the molecular structure of the various polyol compounds.

Examples of the epoxy (meth) acrylate resin (B9) include those obtained by reacting an epoxy resin with (meth) acrylic acid or an anhydride thereof. The epoxy resin is, for example, a diglycidyl ether of a dihydric phenol such as hydroquinone or catechol; a diglycidyl ether of a biphenol compound such as 3,3'-biphenyldiol or 4,4'-biphenyldiol; a bisphenol A type epoxy resin. Bisphenol type epoxy resin 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-naphthalene diols, binaphthols, bis (2,7-dihydroxynaphthyl) methane; triglycidyl ethers such as 4,4', 4 "-methyridintrisphenol; phenols. Novolak type epoxy resin such as novolak type epoxy resin and cresol novolak resin; (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain and the like (poly) in the molecular structure of the various epoxy resins. ) Oxyalkylene chain-introduced (poly) oxyalkylene modified product; examples thereof include a lactone modified product in which a (poly) lactone structure is introduced into the molecular structure of the various epoxy resins.

The dendrimer type (meth) acrylate resin (B10) is a resin having a regular multi-branched structure and a (meth) acryloyl group at the end of each branched chain, and is a dendrimer type or hyper. It is called a branch type or a star polymer. Examples of such a compound include those represented by the following structural formulas (5-1) to (5-8), but the compound is not limited thereto, and has a regular multi-branched structure. Any resin having a (meth) acryloyl group at the end of each branched chain can be used.

（式中Ｒ^６は水素原子又はメチル基であり、Ｒ^７は炭素原子数１〜４の炭化水素基である。）

(In the formula, R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is a hydrocarbon group having 1 to 4 carbon atoms.)

As such a dendrimer type (meth) acrylate resin (B10), "Viscoat # 1000" manufactured by Osaka Organic Chemical Co., Ltd. [Weight average molecular weight (Mw) 1,500 to 2,000, average (meth) acryloyl per molecule Number of groups 14], "Viscort 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 18 per molecule], SARTOMER "CN2301", "CN2302" [average (meth) acryloyl group number 16 per molecule], " CN2303 "[Average (meth) acryloyl group number per molecule 6]," CN2304 "[Average (meth) acryloyl group number 18 per molecule]," Esdrimer HU-22 "manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation, Shin-Nakamura Chemical Co., Ltd. Commercially available products such as "A-HBR-5" manufactured by the company, "New Frontier R-1150" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and "Hypertech UR-101" manufactured by Nissan Chemical Co., Ltd. may be used.

The dendrimer type (meth) acrylate resin (B10) preferably has a weight average molecular weight (Mw) in the range of 1,000 to 30,000. Further, it is preferable that the average (meth) acryloyl group number per molecule is in the range of 5 to 30.

The (meth) acryloyl group-containing acrylic resin (B11) is polymerized with, for example, a (meth) acrylate monomer (α) having a reactive functional group such as a hydroxyl group, a carboxy group, an isocyanate group, or a glycidyl group as an essential component. Examples thereof are those obtained by introducing a (meth) acryloyl group 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. Be done.

The (meth) acrylate monomer (α) having a reactive functional group is, for example, a hydroxyl group-containing (meth) acrylate monomer such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; and carboxy such as (meth) acrylic acid. Group-containing (meth) acrylate monomer; isocyanate group-containing (meth) acrylate monomer such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1,1-bis (acryloyloxymethyl) ethyl isocyanate; glycidyl (meth) acrylate. , 4-Hydroxybutyl acrylate glycidyl group-containing (meth) acrylate monomer such as glycidyl ether and the like can be mentioned. These may be used alone or in combination of two or more.

The acrylic resin intermediate may be a copolymer of the (meth) acrylate monomer (α) and other polymerizable unsaturated group-containing compounds, if necessary. The other polymerizable unsaturated group-containing compound is (meth) such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like. Acrylic acid alkyl ester; Cyclo ring-containing (meth) acrylate such as cyclohexyl (meth) acrylate, isoboronyl (meth) acrylate, dicyclopentanyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl acrylate Aromatic ring-containing (meth) acrylates and the like; silyl group-containing (meth) acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, α-methylstyrene and chlorostyrene. These may be used alone or in combination of two or more.

When the acrylic resin intermediate is obtained by copolymerizing the (meth) acrylate monomer (α) with the other polymerizable unsaturated group-containing compound, the reaction ratio between the two is excellent in curability. Since the (meth) acryloyl group-containing acrylic resin (B11) is used, the ratio of the (meth) acrylate monomer (α) to the total of both is preferably in the range of 20 to 70 parts by mass, preferably 30 to 60 parts by mass. It is more preferably in the range of parts%.

The acrylic resin intermediate can be produced in the same manner as a general acrylic resin. As an example of the production conditions, for example, it can be produced by polymerizing various monomers in a temperature range of 60 ° C to 150 ° C in the presence of a polymerization initiator. Examples of the polymerization method include a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsification polymerization method and the like. In addition, examples of the polymerization mode include random copolymers, block copolymers, graft copolymers, and the like. When the solution polymerization method is used, for example, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone or a glycol ether solvent such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether is 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), but the combination is as follows from the viewpoint of reactivity. Is preferable. That is, when the hydroxyl group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), it is preferable to use the 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, for example, an esterification catalyst such as triphenylphosphine in a temperature range of 60 to 150 ° C. when the reaction is an esterification reaction. Can be mentioned as appropriate. When the reaction is a urethanization reaction, a method of reacting the compound (α) while dropping the compound (α) onto the acrylic resin intermediate in a temperature range of 50 to 120 ° C. can be mentioned.

The (meth) acryloyl group-containing acrylic resin (B11) preferably has a weight average molecular weight (Mw) in the range of 5,000 to 80,000. Further, it is preferable that the (meth) acryloyl group equivalent is in the range of 200 to 500 g / equivalent.

These (meth) acrylate compounds (B) may be used alone or in combination of two or more. Above all, since the active energy ray-curable resin composition having further excellent moisture permeability in the cured coating film is obtained, 60% by mass or more, more preferably 80% by mass or more of the (meth) acrylate compound (B) is an alicyclic. It is preferably a mono (meth) acrylate compound and a modified product thereof (B2) or an alicyclic poly (meth) acrylate compound and a modified product thereof (B6). Further, among the alicyclic mono (meth) acrylate compound and its modified form (B2) and the alicyclic poly (meth) acrylate compound and its modified form (B6), the (poly) oxyalkylene modification and the lactone modification An alicyclic (meth) acrylate compound that has not been used is preferable. Further, since the active energy ray-curable resin composition is more excellent in curability and appearance of the coating film in addition to moisture permeability, it is an alicyclic mono (meth) acrylate compound and its modified product (B2) and an alicyclic type. It is preferable to use a poly (meth) acrylate compound and a modified product thereof (B6) in combination. At this time, the mass ratio [(B2) / (B6)] of both is preferably in the range of 5/95 to 50/50, and preferably in the range of 10/90 to 35/65.

The active energy ray-curable resin composition of the present invention may contain other components other than the petroleum resin (A) and the (meth) acrylate compound (B) depending on the desired performance. The other components include, for example, other resin components other than the petroleum resin (A) and the (meth) acrylate compound (B), inorganic fine particles, a photopolymerization initiator, a solvent, an ultraviolet absorber, an antioxidant, and silicon. Examples thereof include system additives, fluorine-based additives, antistatic agents, silane coupling agents, adhesion aids, organic beads, quantum dots (QD), rhology control agents, defoaming agents, antifoaming agents, colorants and the like. ..

The other resin components are added for the purpose of improving desired performance such as substrate adhesion and flexibility of the active energy ray-curable resin composition, and various known and commonly used resins can be used. can. Examples thereof include acrylic resin, polyester resin, urethane resin and the like. These may be used alone or in combination of two or more. When other resin components are used, the addition amount thereof is preferably in the range of 0.5 to 100% by mass with respect to the total mass of the petroleum resin (A) and the (meth) acrylate compound (B).

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. These may be used alone or in combination of two or more. Among these, there are various types of silica particles having particularly high versatility, such as fumed silica, wet silica called precipitation method silica, gel silica, sol-gel silica and the like, and any of them may be used. Further, the surface of the inorganic fine particles may be modified with a silane coupling agent or the like. The particle size of the inorganic fine particles is appropriately adjusted according to the desired coating film performance and the like, but the measured value by the dynamic light scattering method is preferably in the range of 10 to 250 nm. When the inorganic fine particles are used, the addition amount thereof is preferably in the range of 0.1 to 60% by mass with respect to the total of the components other than the solvent of the active energy ray-curable resin composition.

As the photopolymerization initiator, an appropriate one may be selected and used depending on the type of active energy ray to be irradiated and the like. 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 the photopolymerization initiator include, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino). Alkylphenone-based photopolymerization initiators such as -2- [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; 2,4,6-trimethylbenzoyl-diphenyl- Acylphosphine oxide-based photopolymerization initiators such as phosphinoxide; Intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds and the like can be mentioned. These may be used alone or in combination of two or more.

Commercially available products of the photopolymerization initiator are, for example, "IRGACURE127", "IRGACURE184", "IRGACURE250", "IRGACURE270", "IRGACURE290", "IRGACURE369E", "IRGACURE359EG", "IRGACURE500", "IRGACURE500" manufactured by BASF. , "IRGACURE 754", "IRGACURE819", "IRGACURE907", "IRGACURE1173", "IRGACURE2959", "IRGACURE MBF", "IRGACURE TPO", "IRGACURE OXE 01", "IRGACURE OX 02", etc.

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

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 thereof are appropriately adjusted according to the desired performance. Generally, it is used in the range of 10 to 90% by mass with respect to the total amount of the 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 dioxolan; esters such as methyl acetate, ethyl acetate and butyl acetate; aromatics such as toluene and xylene. Solvents; Alicyclic solvents such as cyclohexane and methylcyclohexane; Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene Examples thereof include glycol ether-based solvents such as glycol monopropyl ether. Each of these may be used alone or in combination of two or more.

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 derivatives such as triazine, 2- (2'-xanthencarboxy-5'-methylphenyl) benzotriazole, 2- (2'-o-nitrobenzyloxy-5'-methylphenyl) benzotriazole, 2- Examples thereof include xanthencarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone and the like. Each of these may be used alone or in combination of two or more.

Examples of the antioxidant include a hindered phenol-based antioxidant, a hindered amine-based antioxidant, an organic sulfur-based antioxidant, a phosphoric acid ester-based antioxidant, and the like. Each of these may be used alone or in combination of two or more.

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

Examples of the fluorine-based additive include DIC Corporation's "Mega Fuck" series. Each of these may be used alone or in combination of two or more.

Examples of the antistatic agent include pyridinium, imidazolium, phosphonium, ammonium, or lithium salt of bis (trifluoromethanesulfonyl) imide or bis (fluorosulfonyl) imide. These may be used alone or in combination of two or more.

The silane coupling agent is, for example, [(meth) acryloyloxyalkyl] trialkylsilane, [(meth) acryloyloxyalkyl] dialkylalkoxysilane, [(meth) acryloyloxyalkyl] alkyldialkoxysilane, [(meth). Acryloyloxyalkyl] (meth) acryloyloxy-based silane coupling agents such as trialkoxysilane; trialkylvinylsilane, dialkylalkoxyvinylsilane, alkyldialkoxyvinylsilane, trialkoxyvinylsilane, trialkylallylsilane, dialkylalkoxyallylsilane, alkyldialkoxyallylsilane, Vinyl-based silane coupling agents such as trialkoxyallylsilane; styrene-based silane coupling agents such as styryltrialkyl, styryldialkylalkoxysilane, styrylalkyldialkoxysilane, and styryltrialkoxysilane; (glycidyloxyalkyl) trialkylsilane, ( Glysidyloxyalkyl) Dialkylalkoxysilane, (Glysidyloxyalkyl) Alkyldialkoxysilane, (Glysidyloxyalkyl) Trialkoxysilane, [(3,4-Epoxycyclohexyl) Alkyl] Trimethoxysilane, [(3,4-Epoxycyclohexyl) ) Alkyl] trialkylsilane, [(3,4-epoxycyclohexyl) alkyl] dialkylalkoxysilane, [(3,4-epoxycyclohexyl) alkyl] alkyldialkoxysilane, [(3,4-epoxycyclohexyl) alkyl] tri Epoxy-based silane coupling agents such as alkoxysilanes; isocyanate-based silane coupling agents such as (isocyanaylalkyl) trialkylsilanes, (isocyanaylalkyl) dialkylalkoxysilanes, (isocyanisalkyl) alkyldialkoxysilanes, and (isocyanoxidealkyl) trialkoxysilanes. Agents 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 adhesion aid is, for example, the following structural formula (6).

で表されるリン酸エステル化合物等が挙げられる。前記構造式（６）中のＲ^８は特に限定されず、どのような構造部位であってもよい。Ｒ^８の具体例としては、例えば、脂肪族炭化水素基、芳香族炭化水素基、（メタ）アクリロイル基、グリシジル基、（ポリ）オキシアルキレン構造、（ポリ）チオアルキレン構造、（ポリ）エステル構造、これらの組み合わせからなる構造部位等が挙げられる。また、Ｒ^８は水酸基やアミノ基、カルボキシ基、ハロゲン原子等の官能基を有していてもよい。このようなリン酸エステル化合物の市販品の例としては、例えば、日本化薬株式会社製「カヤマーＰＭ−２」、「カヤマーＰＭ−２１」、共栄社化学株式会社製「ライトエステルＰ−１Ｍ」「ライトエステルＰ−２Ｍ」、「ライトアクリレートＰ−１Ａ（Ｎ）」、ＳＯＬＶＡＹ社製「ＳＩＰＯＭＥＲ ＰＡＭ １００」、「ＳＩＰＯＭＥＲ ＰＡＭ ２００」、「ＳＩＰＯＭＥＲ ＰＡＭ ３００」、「ＳＩＰＯＭＥＲ ＰＡＭ ４０００」、大阪有機化学工業社製「ビスコート＃３ＰＡ」、「ビスコート＃３ＰＭＡ」、第一工業製薬社製「ニューフロンティア Ｓ−２３Ａ」；ＳＯＬＶＡＹ社製「ＳＩＰＯＭＥＲ ＰＡＭ ５０００」等が挙げられる。

Examples thereof include a phosphoric acid ester compound represented by. Wherein R ⁸ in formula (6) is not particularly limited, it may be any structural moiety. Specific examples of R ⁸ are, for example, aliphatic hydrocarbon group, aromatic hydrocarbon group, (meth) acryloyl group, a glycidyl group, (poly) oxyalkylene structure, (poly) thioalkylene structure, (poly) ester structure , Structural parts composed of these combinations and the like. Further, R ⁸ may have a functional group such as a hydroxyl group, an amino group, a carboxy group or a halogen atom. Examples of commercially available products of such phosphoric acid ester compounds include, for example, "Kayamer PM-2" and "Kayamer PM-21" manufactured by Nippon Kayaku Co., Ltd., and "Light Ester P-1M" and "Light Ester P-1M" manufactured by Kyoeisha Chemical Co., Ltd. Light Ester P-2M "," Light Acrylate P-1A (N) ", SOLVAY" SIPOMER PAM 100 "," SIPOMER PAM 200 "," SIPOMER PAM 300 "," SIPOMER PAM 4000 ", Osaka Organic Chemical Industry Co., Ltd. Examples thereof include "Viscoat # 3PA" and "Viscoat # 3PMA" manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; "SIPOMER PAM 5000" manufactured by SOLVAY.

The organic beads include, for example, polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacrylic styrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, and polyolefin resin beads. Examples thereof include polyester resin beads, polyamide resin beads, polyimide resin beads, polyfluoroethylene resin beads, and polyethylene resin beads. Each of these may be used alone or in combination of two or more. The average particle size of these organic beads is preferably in the range of 1 to 10 μm.

The quantum dots (QDs) include II-V group semiconductor compounds, II-VI group semiconductor compounds, III-IV group semiconductor compounds, III-V group semiconductor compounds, III-VI group semiconductor compounds, and IV-VI group semiconductor compounds. Examples thereof include 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 them. .. The quantum dots may be composed of a single semiconductor compound or may have a core-shell structure composed of a plurality of semiconductor compounds. Further, 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 the above-mentioned compounding components. The mixing method is not particularly limited, and a paint shaker, a disper, a roll mill, a bead mill, a ball mill, an attritor, a sand mill, a bead mill and the like may be used.

The use of the active energy ray-curable resin composition of the present invention is not particularly limited, but it can be widely used, for example, for paints. Since the paint containing the active energy ray-curable resin composition of the present invention is excellent in appearance and moisture permeability in a cured coating film, it is used for applications requiring moisture permeability, specifically, deterioration due to moisture or moisture. It can be used as a coating agent for articles that may malfunction or malfunction. Examples of such articles include display members, electronic devices, automobile members, building materials, furniture and the like. The coating film made of the coating film of the present invention may be installed on the outermost surface of an article, or may be installed as an under or middle layer of a multilayer coating film.

As an example of the use of the coating material of the present invention, a laminated film using a plastic film as a base material will be described. Since the paint of the present invention has excellent moisture permeability, the moisture permeability can be improved by laminating it as a plastic film with a film having high moisture permeability such as a triacetyl cellulose film. Further, when the laminated film contains an inorganic material thin film, a quantum dot (QD) -containing layer, or the like, it has an effect of protecting these layers from moisture and moisture.

Examples of the plastic film include triacetyl cellulose film, polyester film, acrylic film, cycloolefin polymer film, polyamide film, polyimide film, polystyrene film, polycarbonate film, polypropylene film and the like. The thickness of these plastic films is appropriately adjusted depending on the material and the use of the laminate, but generally, those having a thickness of about 20 to 300 μm are used.

The coating method for applying the paint of the present invention is not particularly limited, and is bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing. The law etc. can be mentioned.

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

The laminated film may have a coating film layer made of a plastic film and the coating material of the present invention, or may have another layer structure. Examples of other layers include glass, an inorganic material thin film, a resin coating layer, a polarizing film, a reflective film, an antireflection film, a gas barrier film, a functional film layer such as a decorative film, and the like. In the laminated film of the present invention, the laminating method of each layer is not particularly limited, and each layer may be laminated directly or may be laminated via adhesion or the like.

The inorganic material thin film may be, for example, 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, and for example, plasma support method (CVD), old and new vapor deposition (MBE method, flash method, etc.), sputtering, anodic oxidation, electroless plating, electroplating, etc. The method can be mentioned. The thickness of the inorganic material thin film is appropriately adjusted depending on the material and the use of the laminate, but is generally preferably about 30 nm to 3 μm.

A wide variety of resin coating films can be used depending on the use of the laminate and the desired performance. Examples of the form of the resin material forming the resin coating film include thermosetting ones, active energy ray curable ones, lacquers and the like. Among these, as the active energy ray-curable resin material, the same compound as the compound exemplified as the (meth) acrylate compound (B) is used as a matrix resin, and the other resin and the inorganic fine particles are used according to desired performance. , The organic beads, the quantum dots (QD), and other additives are blended. The thickness of the resin coating film is appropriately adjusted according to the application of the laminate and the desired performance, but is generally preferably about 1 μm to 100 μm.

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

In the embodiment of the present invention, the weight average molecular weight (Mw) is a value measured under the following conditions using a gel permeation chromatograph (GPC).

Measuring device; HLC-8220 manufactured by Tosoh Corporation
Column; Guard column H _XL- 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 velocity 1.0 ml / min Standard; Polystyrene sample; 0.4% by mass in terms of resin solid content Tetrahydrofuran solution filtered through a microfilter (100 μl)

Examples 1-5 and Comparative Example 1
Each component was blended in the ratio shown in Table 1, the non-volatile content was adjusted to 40% by mass with cyclohexanone to obtain an active energy ray-curable resin composition, and various evaluations were carried out as follows. The results are shown in Table 1.

Details of each component in Table 1 are as follows.
-Petroleum resin (A-1): "Idemitsu P-100" manufactured by Idemitsu Kosan Co., Ltd. [Monomer: Dicyclopentadiene and aromatic monomer, hydrogenation: Yes, softening point 100 ° C (measured according to JIS K2207), Weight average molecular weight (Mw) 660, hydroxyl value, acid value less than 1 mgKOH / g],
-Petroleum resin (A-2): "Idemitsu S-100" manufactured by Idemitsu Kosan Co., Ltd. [Monomer: Dicyclopentadiene and aromatic monomer, hydrogenation: Yes, softening point 100 ° C (measured according to JIS K2207), Weight average molecular weight (Mw) 700, hydroxyl value, acid value less than 1 mgKOH / g]
-Petroleum resin (A-3): manufactured by Idemitsu Kosan Co., Ltd. [Monomer: dicyclopentadiene and aromatic monomer, hydrogenation: Yes, softening point 125 ° C (measured according to JIS K2207), weight average molecular weight (Mw) 820, hydroxyl value, acid value less than 1 mgKOH / g]
-Petroleum resin (A'): "KR-1842" manufactured by Arakawa Chemical Industry Co., Ltd. (softening point 120 ° C., hydroxyl value 190 mgKOH / g)
-Photopolymerization initiator: "Irgacure # 184" manufactured by Ciba Specialty Chemicals, Inc.

Appearance evaluation of the active energy ray-curable resin composition The appearance of the active energy ray-curable resin composition was visually evaluated according to the following criteria.
A: No turbidity or coloring, colorless and transparent B: turbidity or coloring

Preparation of Laminated Film The active energy ray-curable resin composition obtained above was applied on a TAC film having a thickness of 40 μm with a bar coater, and dried at 80 ° C. for 1 minute. Next, under a nitrogen atmosphere, ultraviolet rays were ^{irradiated at 200 mJ / cm 2} with an 80 W high-pressure mercury lamp to obtain a laminated film having a cured coating film having a film thickness of 5 μm on the TAC film.

Evaluation of Transparency of Laminated Film The transparency of the laminated film was visually evaluated according to the following criteria.
A: There is no fogging or coloring, and it is colorless and transparent. B: There is fogging or coloring. Further, the HAZE value of the laminated film was measured using "Haze Computer HZ-V3" manufactured by Suga Test Instruments Co., Ltd.

Evaluation of Smoothness of Cured Coating Film The smoothness of the cured coating film layer of the laminated film was visually evaluated according to the following criteria.
A: The surface of the coating film is smooth with no bumps or craters.
B: There are bumps and craters on a part of the coating film surface.
C: There are bumps and craters on the entire surface of the coating film.

Evaluation of substrate adhesion of cured coating film Make cuts with a cutter knife on the cured coating film layer side of the laminated film at 1 mm intervals in a 10 x 10 grid pattern, ^{create 100 1 mm 2} grids, and acrylic in advance. The above laminated film was attached to the double-sided tape attached on the substrate. Then, after the cellophane tape was attached on the grid, a rapid peeling test was performed, and the adhesion between the TAC film and the cured coating film was evaluated according to the following criteria.
A: All 100 of the 100 Gobans remain B: Of the 100 Gobans, 99 or less remain

^{Moisture vapor transmission rate evaluation of laminated film Moisture vapor transmission rate (MVTR) [g / m 2} ] when left for 24 hours under 90 ° C. and 90% RH conditions using "L80-5000 type water vapor transmission rate meter" manufactured by LYSSY. Was measured.

Claims (4)

An active energy ray-curable resin composition containing a petroleum resin (A) having a hydroxyl value of less than 1 mgKOH / g and a (meth) acrylate compound (B) as essential components.
The mass ratio [(A) / (B)] of the petroleum resin (A) to the (meth) acrylate compound (B) is in the range of 20/80 to 35/65.
The petroleum resin (A) is a polymer which dicyclopentadiene and aromatic monomer polymerization component,
The petroleum resin (A) is hydrogenated.
The softening point of the petroleum resin (A) is in the range of 70 to 150 ° C.
The weight average molecular weight (Mw) of the petroleum resin (A) is in the range of 350 to 1,500.
Wherein the (meth) acrylate compound (B), isobornyl (meth) acrylate bets (B2), and a dicyclopentanyl (meth) acrylate bets (B6),
And the isobornyl (meth) acrylate bets (B2), the mass ratio of dicyclopentanyl (meth) acrylate bets (B6) [(B2) / (B6)] is in the range of 5 / 95-50 / 50 An active energy ray-curable resin composition characterized by being. Claim 1 Symbol placement of the active energy ray-curable coating material containing the resin composition. A coating film comprising the paint according to claim 2. A laminated film having a layer composed of the coating film according to claim 3.