JP6379390B2 - Solvent-free photocurable resin composition - Google Patents

Description

  The present invention relates to a solvent-free photocurable resin composition.

  Currently, the use of film substrates instead of glass substrates is increasing due to transportation and storage requirements. The film substrate is stored in the form of a roll or the like at the time of storage. At this time, the substrate is curved, so that the material applied on the film substrate is required to have the same flexibility as the film.

  In addition, in a substrate in which an electrode is formed on a film such as an ITO film, when an adhesive is used for bonding the substrates, the silver wiring deteriorates due to the moisture of the adhesive, causing problems such as short-circuiting. There is a need for an overcoat material that protects the wiring.

  On the other hand, the conventional overcoat material is intended for application on a glass substrate and contains inorganic fine particles in order to increase the hardness (Patent Document 1). However, the conventional method such as the inclusion of inorganic fine particles improves the hardness, but is not flexible, for example, it causes inconveniences such as cracking when bent, so it is applicable to application to a film substrate. The current situation is not possible.

JP 2012-116975 A

  The present inventors have found that the above problem can be solved by a composition containing a specific (co) polymer, a silane coupling agent, a polyfunctional acrylate compound, a radical polymerization initiator, and a solvent. -004307. However, since the composition contains a solvent, firing is necessary when forming a cured film, and there is room for improvement in terms of energy saving and work efficiency.

  The present invention has been made in view of the above circumstances, and is useful as an overcoat material having high transmittance, high adhesion to an ITO film, high hardness, high flexibility, and long-term reliability. An object is to provide a solventless photocurable resin composition excellent in workability.

  As a result of intensive studies to solve the above problems, the present inventors use a reactive diluent instead of a solvent, that is, acrylic resin, silane coupling agent, polyfunctional acrylate compound, initiation of photopolymerization. The present inventors have found that the above problems can be solved by a solventless composition containing an agent and a reactive diluent, and have completed the present invention.

（式中、Ｒは水素原子又はメチル基を表す。Ｒ¹はアルキル基を表す。）
（Ｂ）シランカップリング剤０.００１〜１０質量部、
（Ｃ）１分子中に少なくとも３つの(メタ)アクリロキシ基を有する多官能(メタ)アクリレート化合物２０〜２００質量部、
（Ｄ）光重合開始剤、及び
（Ｅ）重合性炭素−炭素二重結合を１つ又は２つ有する反応性希釈剤１０〜２００質量部
を含有することを特徴とする無溶剤型光硬化性樹脂組成物。
２．（Ｂ）成分を（Ａ）成分１００質量部に対して０.００１〜５質量部、（Ｄ）成分を（Ａ）成分１００質量部に対して１〜２０質量部含有する１の無溶剤型光硬化性樹脂組成物。
３．（Ａ）下記式（１）で表される(メタ)アクリル酸エステル化合物に由来する繰り返し単位を少なくとも１種含有するアクリル系樹脂（ただし、水酸基含有（メタ）アクリレートに由来する繰り返し単位を含まない）１００質量部、

（式中、Ｒは水素原子又はメチル基を表す。Ｒ¹はアルキル基を表す。）
（Ｂ）シランカップリング剤０.００１〜１０質量部、
（Ｃ）１分子中に少なくとも３つの(メタ)アクリロキシ基を有する多官能(メタ)アクリレート化合物、
（Ｄ）ベンゾフェノン誘導体、Ｎ−アリールグリシン誘導体、有機アジド化合物、チタノセン化合物、アルミナート錯体、有機過酸化物、Ｎ−アルコキシピリジニウム塩及びチオキサントン誘導体から選ばれる光重合開始剤、及び
（Ｅ）重合性炭素−炭素二重結合を１つ又は２つ有する反応性希釈剤
を含有することを特徴とする無溶剤型光硬化性樹脂組成物。
４．（Ｂ）成分を（Ａ）成分１００質量部に対して０.００１〜５質量部、（Ｃ）成分を（Ａ）成分１００質量部に対して１０〜３００質量部、（Ｄ）成分を（Ａ）成分１００質量部に対して１〜２０質量部、（Ｅ）成分を（Ａ）成分１００質量部に対して１０〜２００質量部含有する３の無溶剤型光硬化性樹脂組成物。
５．（Ａ）アクリル系樹脂が、更に(メタ)アクリル酸に由来する繰り返し単位を含有する１〜４のいずれかの無溶剤型光硬化性樹脂組成物。
６．(メタ)アクリル酸に由来する繰り返し単位の含有率が、全繰り返し単位中３０モル％以下である５の無溶剤型光硬化性樹脂組成物。
７．（Ａ）アクリル系樹脂が、更にスチレン化合物に由来する繰り返し単位を含有する１〜６のいずれかの無溶剤型光硬化性樹脂組成物。
８．スチレン化合物に由来する繰り返し単位の含有量が、全繰り返し単位中５０モル％以下である７の無溶剤型光硬化性樹脂組成物。
９．（Ｅ）反応性希釈剤の粘度が、２５℃において２００ｍＰａ・ｓ以下である１〜８のいずれかの無溶剤型光硬化性樹脂組成物。
１０．（Ｅ）反応性希釈剤が、単官能(メタ)アクリレート類である１〜９のいずれかの無溶剤型光硬化性樹脂組成物。
１１．粘度が２５℃において１０,０００ｍＰａ・ｓ以下である１〜１０のいずれかの無溶剤型光硬化性樹脂組成物。
１２．１〜１１のいずれかの無溶剤型光硬化性樹脂組成物を用いて得られる硬化膜。
１３．オーバーコート材料である１２の硬化膜。
１４．１２の硬化膜をフィルム基板上に積層してなる積層体。
１５．１〜１１のいずれかの無溶剤型光硬化性樹脂組成物を基板に塗布し、紫外線を照射することを特徴とする硬化膜の製造方法。
That is, the present invention provides the following solvent-free photocurable resin composition.
1. (A) Acrylic resin containing at least one repeating unit derived from a (meth) acrylic acid ester compound represented by the following formula (1) (however, it does not include a repeating unit derived from a hydroxyl group-containing (meth) acrylate) ) 100 parts by mass ,

(In the formula, R represents a hydrogen atom or a methyl group. R ¹ represents an alkyl group.)
(B) 0.001 to 10 parts by mass of a silane coupling agent,
(C) 20 to 200 parts by mass of a polyfunctional (meth) acrylate compound having at least three (meth) acryloxy groups in one molecule;
(D) a photopolymerization initiator, and (E) polymerizable carbon - characterized Rukoto that Yusuke containing a reactive diluent from 10 to 200 parts by <br/> having one or two carbon double bonds Solvent-free photocurable resin composition.
2. 1) Solventless type containing 0.001 to 5 parts by mass of component (B) with respect to 100 parts by mass of component (A) and 1 to 20 parts by mass of component (D) with respect to 100 parts by mass of component (A) Photocurable resin composition.
3. (A) Acrylic resin containing at least one repeating unit derived from a (meth) acrylic acid ester compound represented by the following formula (1) (however, it does not include a repeating unit derived from a hydroxyl group-containing (meth) acrylate) ) 100 parts by mass ,

(In the formula, R represents a hydrogen atom or a methyl group. R ¹ represents an alkyl group.)
(B) 0.001 to 10 parts by mass of a silane coupling agent,
(C) a polyfunctional (meth) acrylate compound having at least three (meth) acryloxy groups in one molecule;
(D) a photopolymerization initiator selected from a benzophenone derivative, an N-arylglycine derivative, an organic azide compound, a titanocene compound, an aluminate complex, an organic peroxide, an N-alkoxypyridinium salt, and a thioxanthone derivative, and (E) a polymerizability A solventless photocurable resin composition comprising a reactive diluent having one or two carbon-carbon double bonds.
4). The component (B) is 0.001 to 5 parts by mass with respect to 100 parts by mass of the component (A), the component (C) is 10 to 300 parts by mass with respect to 100 parts by mass of the component (A), and the component (D) is ( 3) Solvent-free photocurable resin composition containing 1 to 20 parts by mass with respect to 100 parts by mass of component and 10 to 200 parts by mass of component (E) with respect to 100 parts by mass of component (A).
5. (A) The solvent-free photocurable resin composition according to any one of 1 to 4, wherein the acrylic resin further contains a repeating unit derived from (meth) acrylic acid.
6). The solvent-free photocurable resin composition of 5 whose content rate of the repeating unit derived from (meth) acrylic acid is 30 mol% or less in all repeating units.
7). (A) The solventless photocurable resin composition according to any one of 1 to 6, wherein the acrylic resin further contains a repeating unit derived from a styrene compound.
8). 7. The solventless photocurable resin composition according to 7, wherein the content of the repeating unit derived from the styrene compound is 50 mol% or less in all repeating units.
9. (E) The solventless photocurable resin composition according to any one of 1 to 8, wherein the reactive diluent has a viscosity of 200 mPa · s or less at 25 ° C.
10. (E) The solventless photocurable resin composition according to any one of 1 to 9, wherein the reactive diluent is a monofunctional (meth) acrylate.
11. The solventless photocurable resin composition according to any one of 1 to 10, which has a viscosity of 10,000 mPa · s or less at 25 ° C.
12. A cured film obtained using the solventless photocurable resin composition according to any one of 12.1 to 11.
13. 12 cured films which are overcoat materials.
14. A laminate obtained by laminating a cured film of 12.12 on a film substrate.
15. A method for producing a cured film, comprising applying the solvent-free photocurable resin composition according to any one of 15.1 to 11 to a substrate and irradiating with ultraviolet rays.

  Since the solvent-free photocurable resin composition of the present invention does not contain a solvent, it can be cured only by light irradiation without the need for baking when forming a cured film, saving energy, reducing environmental burden, and working efficiency. Can be improved. The cured film obtained using the composition of the present invention has excellent flexibility, high hardness, and excellent adhesion. Therefore, it is also useful as a material for forming a cured film such as a protective film, a planarizing film, and an insulating film in various displays such as an organic electroluminescence (EL) element, and is particularly suitable as an overcoat material for an ITO film. .

[Solvent-free photocurable resin composition]
The solventless photocurable resin composition of the present invention comprises (A) an acrylic resin, (B) a silane coupling agent, (C) a polyfunctional (meth) acrylate compound, (D) a photopolymerization initiator, and ( E) Contains a reactive diluent.

[(A) Acrylic resin]
The component (A) contained in the composition of the present invention is an acrylic resin containing at least one repeating unit derived from a (meth) acrylic acid ester compound represented by the following formula (1).

In the formula, R represents a hydrogen atom or a methyl group, and a methyl group is preferable. R ¹ represents an alkyl group. The alkyl group may be linear, branched or cyclic. Moreover, carbon number of the said alkyl group becomes like this. Preferably it is 1-4, More preferably, it is 1-3, More preferably, it is 1 or 2.

  Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a cyclobutyl group.

  Examples of the (meth) acrylic acid ester compound represented by the formula (1) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, tert-butyl (meth) An acrylate etc. are mentioned. Of these, methyl methacrylate, ethyl methacrylate and the like are particularly preferable.

  The acrylic resin (A) may further contain a repeating unit derived from (meth) acrylic acid. By containing a repeating unit derived from (meth) acrylic acid, an improvement in adhesion of the cured film to the substrate or the like can be expected.

  In this case, the content of the repeating unit derived from (meth) acrylic acid is preferably 30 mol% or less, more preferably 20 mol% or less in the total repeating units from the viewpoint of improving the hardness of the film. . Although the minimum of a content rate is not specifically limited, When considering fully exhibiting the adhesive improvement effect, it is preferable that it is 2 mol% or more, and it is more preferable that it is 5 mol% or more.

  The acrylic resin (A) may contain other repeating units besides the above repeating units. As other repeating units, repeating units derived from styrene compounds, (meth) acrylic acid ester compounds other than those represented by formula (1), acrylamide compounds, vinyl compounds, maleimide compounds, acrylonitrile, maleic anhydride, etc. Is mentioned.

  Of these, the acrylic resin (A) preferably contains a repeating unit derived from a styrene compound. Thereby, the properties of adhesion and hydrophobicity (low water absorption) can be imparted to the cured film.

As said styrene compound, what is represented by following formula (2) is preferable.

In formula, R < ² > -R < ⁶ > represents a hydrogen atom, a halogen atom, or an alkyl group each independently. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the alkyl group include the same ones as described above. Specific examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and 4-tert-butylstyrene.

The (meth) acrylic acid ester compound other than the repeating unit represented by the above formula (1) is not particularly limited, but those represented by the following formula (3) are preferable.

In the formula, R is the same as above. R ⁷ represents a substituted alkyl group, an epoxy group, a glycidyl group, an aryl group or an aralkyl group.

  The substituted alkyl group preferably has 1 to 6 carbon atoms in the alkyl portion. Some or all of the hydrogen atoms bonded to the carbon atoms in the alkyl part of the substituted alkyl group are substituted with a substituent such as a halogen atom, a hydroxy group, an amino group, a (block) isocyanato group, or a (meth) acryloxy group. May be. In addition, a part of the methylene group in the substituted alkyl group is -O-, -S-, -NH-, -NH-CO-O-, -O-CO-NH-, -NH-CO-NH-, Although it may be substituted with at least one selected from —CO—, —COO— and —OCO—, in this case, the methylene group is not a methylene group bonded to an oxygen atom.

  The aryl group preferably has 6 to 10 carbon atoms, and the aralkyl group preferably has 7 to 11 carbon atoms. In addition, some or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an amino group, and those having 1 to 4 carbon atoms. An alkyl group etc. are mentioned.

Specific examples of R ⁷ include 2,2,2-trifluoroethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, 4-hydroxybutyl group, 2-isocyanatoethyl. Group, 2-isocyanatopropyl group, 3-isocyanatopropyl group, 2-methyl-2-isocyanatopropyl group, 4-isocyanatobutyl group, 2- (meth) acryloxyethyl group, 2- (meth) acrylic group Roxypropyl group, 3- (meth) acryloxypropyl group, 2- (meth) acryloxybutyl group, 3- (meth) acryloxybutyl group, 4- (meth) acryloxybutyl group, 2- (meth) acrylic group Loxypentyl group, 3- (meth) acryloxypentyl group, 2- (meth) acryloxyhexyl group, 3- (meth) acryloxyhexyl group, 4- (meth) acryloxyhexyl group, 5 (Meth) acryloxyhexyl group, 6- (meth) acryloxyhexyl group, acetylaminomethyl group, acetylaminoethyl group, phenylacetylaminomethyl group, phenylacetylaminoethyl group, 2-hydroxy-3- (meth) acrylic group Roxypropyl group, 4- (meth) acryloxypentyl group, 5- (meth) acryloxypentyl group, 2-{[2- (meth) acryloxyethyl] oxy} ethyl group, 2,2-dimethyl-3- (Meth) acryloxypropyl group, 2-{[2- (meth) acryloxyethyl] carbamoyloxy} ethyl group, glycidyl group, methoxymethyl group, ethoxymethyl group, propoxymethyl group, isopropoxymethyl group, butoxymethyl group , Isobutoxymethyl group, pentyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-propoxy Siethyl group, 2-isopropoxyethyl group, 2-butoxyethyl group, 2-isobutoxyethyl group, pentyloxyethyl group, phenyl group, 4-chlorophenyl group, 4-bromophenyl group, 4-hydroxyphenyl group, 4- Examples include methylphenyl group, 4-ethylphenyl group, 1-naphthyl group, 2-naphthyl group, benzyl group, phenethyl group and the like.

  The (meth) acrylic acid ester compound represented by the formula (3) is preferably 2,2,2-trifluoroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate. 2,3-dihydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 2- (meth) acryloxyethyl (meth) acrylate, 3- (meth) acrylic Roxypropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropyl (meth) acrylate, 2-{[2- (meth) acryloxyethyl] carbamoyloxy} ethyl (meth) acrylate, butoxymethyl (meta ) Acrylate, pentyloxymethyl (meth) acrylate, and the like.

Although it does not specifically limit as said acrylamide compound, What is represented by following formula (4) is preferable.

In the formula, R is the same as above. R ⁸ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. The alkyl group may be linear, branched or cyclic, and preferably has 1 to 6 carbon atoms. The aryl group preferably has 6 to 10 carbon atoms. The aralkyl group preferably has 7 to 11 carbon atoms. In addition, some or all of the hydrogen atoms of these groups may be substituted with a substituent, and examples of the substituent include a halogen atom, a hydroxy group, and an amino group. Further, some of the methylene groups in the alkyl group are —O—, —S—, —NH—, —NH—CO—O—, —O—CO—NH—, —NH—CO—NH—, — Although it may be substituted with at least one selected from CO-, -COO- and -OCO-, in this case, the methylene group is not a methylene group bonded to a nitrogen atom.

Specific examples of R ⁸ include hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, pentyl group, hexyl. Group, hydroxymethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, methoxymethyl group, ethoxymethyl group, Propoxymethyl group, isopropoxymethyl group, butoxymethyl group, isobutoxymethyl group, pentyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-propoxyethyl group, 2-isopropoxyethyl group, 2- Butoxyethyl group, 2-isobutoxyethyl group, pentylo Shiechiru group, a phenyl group, 4-chlorophenyl group, 4-bromophenyl group, 4-hydroxyphenyl group, 1-naphthyl, 2-naphthyl, benzyl group, phenethyl group.

  The acrylamide compound is preferably N- (2,2,2-trifluoroethyl) (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide. N- (2,3-dihydroxypropyl) (meth) acrylamide, N- (4-hydroxybutyl) (meth) acrylamide, N- (butoxymethyl) (meth) acrylamide, N- (pentyloxymethyl) (meth) Examples include acrylamide.

  Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether, and the like.

  Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.

  These other repeating units can be used alone or in combination of two or more.

  The content of the other repeating units is preferably 50 mol% or less, more preferably 40 mol% or less in all repeating units. Although the minimum of a content rate is not specifically limited, It is preferable that it is 2 mol% or more, and it is more preferable that it is 5 mol% or more.

The acrylic resin (A) preferably has a weight average molecular weight (Mw) of 1,000 to 20,000, more preferably 2,000 to 15,000, and 3,000 to 10,000. More preferably, it is more preferably 3,000 to 9,000. When Mw exceeds 20,000, compatibility with other components may be reduced and handling properties may be reduced, and when Mw is less than 1,000, adhesion may be reduced.
In addition, Mw is a polystyrene conversion measured value by gel permeation chromatography (GPC).

  When the acrylic resin (A) is a copolymer, the copolymer may be a random copolymer, an alternating copolymer, or a block copolymer.

  The acrylic resin (A) can be synthesized by a conventionally known method. For example, it is produced by (co) polymerizing the monomer represented by the formula (1) and, if necessary, other monomers.

  As the polymerization method, radical polymerization, anionic polymerization, cationic polymerization and the like can be employed. Of these, radical polymerization is particularly preferred. Specifically, the above monomer may be heated and polymerized in a solvent in the presence of a polymerization initiator.

  The polymerization initiator can be appropriately selected from conventionally known ones. For example, peroxides such as benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide; persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate; azobisisobutyronitrile, azobismethylbutyrate Examples include azo compounds such as nitrile, azobisisovaleronitrile, 2,2′-azobis (isobutyric acid) dimethyl, and the like. These can be used alone or in combination of two or more.

  The amount of the polymerization initiator used is preferably about 0.005 to 0.05 mole per mole of monomer. What is necessary is just to set suitably the reaction temperature at the time of superposition | polymerization from 0 degreeC to the boiling point of the solvent to be used, but about 20-100 degreeC is preferable. The reaction time is preferably about 0.1 to 30 hours.

  The solvent used in the polymerization reaction is not particularly limited, and may be appropriately selected from various solvents generally used in the polymerization reaction. Specifically, water; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, i-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, alcohols such as i-pentanol, t-pentanol, 1-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzyl alcohol, cyclohexanol; diethyl ether , Ethers such as diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane; halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, carbon tetrachloride; methyl cellosolve, ethyl cellosolve, Ether alcohols such as isopropyl cellosolve, butyl cellosolve, diethylene glycol monobutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl propionate, cellosolve acetate; n-pentane, n -Aliphatic or aromatic hydrocarbons such as hexane, n-heptane, n-octane, n-nonane, n-decane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, anisole Acetals such as methylal and diethyl acetal; fatty acids such as formic acid, acetic acid and propionic acid; nitropropane, nitrobenzene, dimethylamine, monoethanolamine , Pyridine, N- methyl-2-pyrrolidone, N, N- dimethylformamide, dimethyl sulfoxide, acetonitrile and the like. These can be used individually by 1 type or in mixture of 2 or more types.

[(B) Silane coupling agent]
(B) A component is a silane coupling agent. As said silane coupling agent, the silane compound represented by following formula (5) is preferable.

In formula (5), R ⁹ represents a methyl group or an ethyl group. X represents a hydrolyzable group. Y represents a reactive functional group. m is an integer of 0-3. n is an integer of 0-3.

  Examples of the hydrolyzable group represented by X include a halogen atom, an alkoxy group having 1 to 3 carbon atoms, and an alkoxyalkoxy group having 2 to 4 carbon atoms. Examples of the halogen atom include a chlorine atom and a bromine atom. The alkoxy group having 1 to 3 carbon atoms is preferably linear or branched, and specifically includes a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group. Specific examples of the alkoxyalkoxy group having 2 to 4 carbon atoms include a methoxymethoxy group, a 2-methoxyethoxy group, an ethoxymethoxy group, and a 2-ethoxyethoxy group.

  Examples of the reactive functional group represented by Y include an amino group, a ureido group, a (meth) acryloxy group, a vinyl group, an epoxy group, a mercapto group, and the like, such as an amino group, a ureido group, and a (meth) acryloyloxy group. Is preferred. Particularly preferred is an amino group or a ureido group.

  Specific examples of the silane coupling agent (B) include 3-aminopropyltrichlorosilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropylmethyldisilane. Ethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxy Propyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxy Propyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, Examples include 3-mercaptopropylmethyldiethoxysilane.

Among these, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Triethoxysilane and the like are particularly preferable.
A commercial item can be used as said silane coupling agent.

  (B) 0.001-10 mass parts is preferable with respect to 100 mass parts of (A) component, as for content of (B) component, 0.01-5 mass parts is more preferable, and 0.05-1 mass part is further. preferable. If it is less than 0.001 part by mass, the adhesion may be lowered, and if it exceeds 10 parts by mass, the hardness may be lowered.

[(C) Polyfunctional (meth) acrylate compound]
Component (C) is a polyfunctional (meth) acrylate compound having at least three (meth) acryloxy groups in the molecule, and specific examples include esters of polyhydric alcohols and (meth) acrylic acid. . The number of (meth) acryloxy groups in one molecule is preferably 3 to 6, more preferably 3 or 4.

  Examples of the polyhydric alcohol include glycerol, erythritol, pentaerythritol, trimethylolethane, trimethylolpropane, dipentaerythritol, ditrimethylolpropane, and the like.

  Specific examples of the polyfunctional (meth) acrylate compound (C) include pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, Examples include trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate.

  The polyfunctional (meth) acrylate compound (C) can be easily obtained as a commercial product. Specific examples thereof include KAYARAD T-1420, DPHA, DPHA-2C, D-310, and the like. D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DPCA-120, DN-0075, DN-2475, R-526, NPGDA, PEG400DA, MANDA, R -167, HX-220, HX620, R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-240, M-6200, M 309, M-400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M-1310, M-1600, M- 1960, M-8100, M-8530, M-8560, M-8560, M-9050 (above, manufactured by Toagosei Co., Ltd.), Biscote 295, 300, 360, GPT, 3PA, 400, 260, 312 and 335HP (Osaka Organic Chemical Co., Ltd.).

  The content of component (C) is preferably 10 to 300 parts by mass, more preferably 20 to 200 parts by mass, and still more preferably 50 to 150 parts by mass with respect to 100 parts by mass of component (A). When this content is too small, the hardness characteristics of the cured film are lowered, and when this content is too large, the adhesion and flexibility characteristics are lowered, and cracks are likely to occur. A polyfunctional (meth) acrylate compound can be used 1 type or in combination of 2 or more types.

[(D) Photopolymerization initiator]
The component (D) is a photopolymerization initiator and contributes to the initiation or acceleration of the polymerization of the component (C).

Any photopolymerization initiator may be used as long as it can release a substance that initiates radical polymerization by light irradiation. Examples include benzophenone derivatives, imidazole derivatives, bisimidazole derivatives, N-aryl glycine derivatives, organic azide compounds, titanocene compounds, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, thioxanthone derivatives, and the like. More specifically, benzophenone, 1,3-di (tert-butyldioxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetrakis (tert-butyldioxycarbonyl) benzophenone, 3-phenyl-5- Isoxazolone, 2-mercaptobenzimidazole, bis (2,4,5-triphenyl) imidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651, manufactured by BASF), 1-hydroxy Cyclohexyl phenyl ketone (Irgacure 184, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (Irgacure 369, manufactured by BASF), bis (η ⁵ − 2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) Phenyl) titanium (although Irgacure 784, manufactured by BASF), and the like, but is not limited thereto.

  In addition to the above, commercially available products can be used. Specifically, Irgacure 500, Irgacure 907, Irgacure 379, Irgacure 819, Irgacure 127, Irgacure 500, Irgacure 754, Irgacure 250, Irgacure 1800, Irgacure 1870, Irgacure manufactured by BASF OXE01, DAROCUR TPO, DAROCUR 1173, Speedcure MBB, Speedcure PBZ, SpeedCure ITX, Speedcure CTX, SpeedKure EDB, Escure ONE made by Lambson , KAYACURE BMS, KAY ACURE DMBI etc. are mentioned.

  (D) As for content of a component, 1-20 mass parts is preferable with respect to 100 mass parts of (A) component, and 1-15 mass parts is more preferable.

[(E) Reactive diluent]
Unlike the solvent, the reactive diluent which is the component (E) is a component of a cured film by film formation. In the present invention, the reactive diluent has one or two polymerizable carbon-carbon double bonds, and conventionally known ones can be used, and in particular, one polymerizable carbon-carbon double bond is used. What has is preferable. In the present invention, the silane coupling agent having a polymerizable carbon-carbon double bond is not included in the reactive diluent.

  Specific examples of the reactive diluent having one polymerizable carbon-carbon double bond include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- Butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate Monofunctional (meth) acrylates such as 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; styrene, α- Methylstyrene, hydroxystyrene, vinyltoluene Aromatic vinyl compounds such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether and other alkyl vinyl ethers; methyl allyl ether, ethyl allyl ether, propyl allyl ether , Alkyl allyl ethers such as butyl allyl ether, 2-ethylhexyl allyl ether, lauryl allyl ether, cyclohexyl allyl ether, cyclohexyl methyl allyl ether; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate; allyl acetate, propionic acid Examples include allyl esters such as allyl and allyl butyrate.

  Specific examples of the reactive diluent having two polymerizable carbon-carbon double bonds include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di ( (Poly) alkylene glycol di (meth) acrylates such as (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate; 1,4-butanediol di Examples include alkanediol di (meth) acrylates such as acrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and 1,10-decanediol diacrylate.

  Of these, monofunctional (meth) acrylates are more preferred, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (Meth) acrylate, sec-butyl (meth) acrylate and the like are particularly preferable.

  The reactive diluent (E) preferably has a viscosity of 200 mPa · s or less, more preferably 50 mPa · s or less. When the viscosity exceeds 200 mPa · s, workability may be reduced. The lower limit of the viscosity is not particularly limited. In the present invention, the viscosity is a value measured at 25 ° C. with an E-type rotational viscometer (the same applies hereinafter).

  A reactive diluent (E) can be used individually by 1 type or in mixture of 2 or more types. When the reactive diluent is a mixture of two or more, one component alone may be out of the above viscosity range, but the viscosity of the mixture only needs to satisfy the above range.

  (E) As for content of a component, 10-200 mass parts is preferred to 100 mass parts of (A) component, and 30-100 mass parts is more preferred. If the amount is less than 10 parts by mass, the compatibility with other components may be reduced and the handling property may be deteriorated. If the amount exceeds 200 parts by mass, the adhesion may be deteriorated.

[Other ingredients]
The solventless photocurable resin composition of the present invention contains the above components (A) to (E), but if necessary, (F) an ion trap agent,
(G) A polyfunctional thiol compound and / or (H) a polymerization inhibitor may be included.

[(F) Ion trap agent]
The component (F) is an ion trap agent, and has an effect of preventing migration when the metal wiring is in contact with water when the metal wiring is formed on the substrate. As such an ion trapping agent, a compound having a chelate-forming ability having an unpaired electron in the structure is preferable. For example, N, N′-bis [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionyl] hydrazine (Irganox MD1024, manufactured by BASF), bis (benzylidene hydrazide) oxalate (Eastman Inhibitor OABH, manufactured by Eastman Chemical), benzotriazole, 5-methylbenzotriazole and the like. These are available as commercial products. Other commercially available products include Adecataps CDA-1 (Asahi Denka Co., Ltd.), Adekapuas CDA-6 (Asahi Denka Co., Ltd.), Quunox (Mitsui Toatsu Fine Co., Ltd.), Naugard XL-1 ( Uniroyal Co., Ltd.). Of these, 5-methylbenzotriazole is particularly preferable.

  The addition amount of the ion trapping agent is preferably 0.0001 to 20 parts by mass, and more preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the component (A). If the amount is less than 0.0001 parts by mass, the effect of protecting the metal wiring may not be obtained. If the amount exceeds 20 parts by mass, characteristics such as hardness and adhesion as a cured film may be reduced, and the cost may be reduced. May also be disadvantageous.

[(G) polyfunctional thiol compound]
The composition of this invention may contain the polyfunctional thiol compound which is (G) component as needed. The polyfunctional thiol compound used in the composition of the present invention is preferably a trifunctional or higher functional thiol compound. The polyfunctional thiol compound can be obtained as an addition reaction product of a polyhydric alcohol and a monofunctional and / or polyfunctional thiol compound. Specific compounds include 1,3,5-tris (3-mercaptopropionyloxyethyl) -isocyanurate, 1,3,5-tris (3-mercaptobutyryloxyethyl) -isocyanurate (Showa Denko K.K. ), Karenz MT (registered trademark) NR1), trifunctional thiol compounds such as trimethylolpropane tris (3-mercaptopropionate); pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto) Butyrate) (made by Showa Denko KK, Karenz MT (registered trademark) PEI) and the like; and hexafunctional thiol compounds such as dipentaerythritol hexakis (3-propionate).

  The content of the polyfunctional thiol compound in the composition of the present invention is preferably 0.1 to 8% by mass and more preferably 0.8 to 5% by mass in the total solid content. If the content is too large, the stability, odor, adhesion and the like of the composition may deteriorate.

[(H) Polymerization inhibitor]
The composition of this invention may contain a polymerization inhibitor as (H) component as needed. Examples of the polymerization inhibitor include 2,6-diisobutylphenol, 3,5-di-t-butylphenol, 3,5-di-t-butylcresol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, 4 -Methoxy-1-naphthol and the like can be mentioned.

  The content of the polymerization inhibitor (H) is preferably 1% by mass or less, more preferably 0.5% by mass or less, based on the total solid content. If the content exceeds 1% by mass, poor curing may occur and the reaction may become insufficient.

[Additive]
The composition of the present invention may further comprise a surfactant, an antifoaming agent, a rheology modifier, a pigment, a dye, a storage stabilizer, a polyhydric phenol or a polycarboxylic acid as long as the effects of the present invention are not impaired. A dissolution accelerator such as an acid can be contained.

  Although it does not specifically limit as surfactant, For example, a fluorine-type surfactant, a silicon-type surfactant, a nonionic surfactant, etc. are mentioned. As this type of surfactant, for example, commercially available products such as those manufactured by Sumitomo 3M Co., Ltd., DIC Corporation, and Asahi Glass Co., Ltd. can be used. Specific examples include F-top EF301, EF303, EF352 (Mitsubishi Materials Electronics Chemical Co., Ltd.), MegaFuck F171, F173 (DIC Corporation), Florard FC430, FC431 (Sumitomo 3M Co., Ltd.), Fluorosurfactants such as Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) can be used.

  Antifoaming agents include acetylene glycols, silicone fluids and emulsions, ethoxylated or propoxylated silicones, hydrocarbons, fatty acid ester derivatives, acetylated polyamides, poly (alkylene oxide) polymers and copolymers, etc. However, it is not limited to these.

  In view of workability, the composition of the present invention preferably has a viscosity of 10,000 mPa · s or less, more preferably 5,000 mPa · s or less. The lower limit of the viscosity is not particularly limited.

  The method for preparing the composition of the present invention is not particularly limited, and the components may be mixed and made uniform in an arbitrary order. The solvent-free photocurable resin composition thus prepared is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

When a film is formed using the solvent-free photocurable resin composition of the present invention, the composition is applied to a substrate (for example, a silicon / silicon dioxide-coated substrate; a silicon nitride substrate; a metal such as aluminum, molybdenum, or chromium). A glass substrate; a quartz substrate; an ITO substrate; an ITO film substrate; a resin film substrate such as a TAC film, a polyester film, and an acrylic film), etc., by spin coating, flow coating, roll coating, slit coating, A cured film can be formed by applying by spin coating following the slit, ink jet coating, printing, or the like, and then irradiating light to perform photocuring. The light preferably has a wavelength of 200 to 500 nm, and the exposure amount is preferably 100 to 5,000 mJ / cm ² .

  By curing the composition of the present invention under the above conditions, the step of the substrate can be sufficiently flattened, and a cured film having high transparency can be formed.

  Since the cured film of the present invention has at least the necessary level of flatness, hardness, adhesion and flexibility, the protective film and flattening film in various displays such as thin film transistor (TFT) type liquid crystal display elements and organic EL elements. It is also useful as a material for forming a cured film such as an insulating film, and is particularly suitable as an overcoat material for an ITO film.

In addition, the composition of the present invention can be used as an adhesive. Applications are not particularly limited, for example, bonding between glass, bonding of various display panel parts such as liquid crystal display and organic EL display, bonding of various display panels and cover glass for protecting them, resistive touch panel It can be preferably used for adhesion between the electrode substrate for electrostatic use or the electrode substrate for capacitive touch panel and a cover for protecting it.
Furthermore, the composition of the present invention can be preferably used as a sealing material and a space filler for organic EL.

EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.
In addition, the weight average molecular weight (Mw) of the copolymer obtained in the synthesis example was eluted using a GPC apparatus manufactured by JASCO Corporation (column: Shodex (registered trademark) KF803L and KF804L manufactured by Showa Denko KK). The measurement was performed under the condition that the solvent tetrahydrofuran was flowed through the column at a flow rate of 1 mL / min (column temperature: 40 ° C.) for elution. Mw is expressed in terms of polystyrene.

The reagents used in the following synthesis examples, examples and comparative examples are as follows.
MMA (methyl methacrylate), MAA (methacrylic acid), ST (styrene): manufactured by Tokyo Chemical Industry Co., Ltd.
MAIB: 2,2′-azobis (isobutyric acid) dimethyl, manufactured by Tokyo Chemical Industry Co., Ltd.
PGMEA: propylene glycol monomethyl ether acetate, PMA-P manufactured by Kyowa Hakko Chemical Co.
APS: 3-aminopropyltriethoxysilane, LS-3150 manufactured by Shin-Etsu Chemical Co., Ltd.
UPS: 3-ureidopropyltriethoxysilane, AY43-031 manufactured by Toray Dow Corning Co., Ltd.
MPMS: 3-methacryloxypropyltrimethoxysilane, A-174 manufactured by Momentive Performance Material Japan.
PET30: Pentaerythritol (tri / tetra) acrylate, KAYARAD PET-30 manufactured by Nippon Kayaku Co., Ltd.
DPHA: dipentaerythritol (hexa / penta) acrylate, KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.
NPGDA: Neopentyl glycol diacrylate, KAYARAD NPGDA manufactured by Nippon Kayaku Co., Ltd.
HDDA: 1,6-hexanediol diacrylate, SR238NS manufactured by Sartomer.
IRG500: Photopolymerization initiator, Irgacure 500 manufactured by BASF
IRG184: photopolymerization initiator, Irgacure 184 manufactured by BASF
EMA (ethyl methacrylate), iBuMA (isobutyl methacrylate): manufactured by Tokyo Chemical Industry Co., Ltd.

[Synthesis Example] Resin Synthesis [Synthesis Example 1]
In a 1,000 mL four-necked flask, 496 g of PGMEA was added and stirred at 110 ° C. (internal temperature) under a nitrogen atmosphere. A solution in which MMA 250.0 g, MAA 26.9 g, ST 32.6 g, and MAIB 21.6 g were mixed was slowly added dropwise over 2 hours. It was made to react for 20 hours after dripping and the resin solution was obtained. This resin solution was poured into 5,000 mL of hexane with stirring, and the resulting precipitate was separated by filtration. This precipitate was dried at 50 ° C. under reduced pressure to obtain resin powder P1. Mw = about 7,000.

[Synthesis Example 2]
In a 1,000 mL four-necked flask, 515.2 g of PGMEA was placed and stirred at 110 ° C. (internal temperature) under a nitrogen atmosphere. A solution prepared by mixing MMA 230.0 g, MAA 56.5 g, ST34.3 g, and MAIB 22.7 g was slowly added dropwise over 2 hours. It was made to react for 20 hours after dripping and the resin solution was obtained. This resin solution was poured into 5,000 mL of hexane with stirring, and the resulting precipitate was separated by filtration. This precipitate was dried at 50 ° C. under reduced pressure to obtain resin powder P2. Mw = about 7,000.

[Synthesis Example 3]
In a 1,000 mL four-necked flask, 513.1 g of PGMEA was added and stirred at 110 ° C. (internal temperature) under a nitrogen atmosphere. A solution in which 320.0 g of MMA and 22.1 g of MAIB were mixed was slowly added dropwise over 2 hours. It was made to react for 20 hours after dripping and the resin solution was obtained. This resin solution was poured into 5,000 mL of hexane with stirring, and the resulting precipitate was separated by filtration. This precipitate was dried at 50 ° C. under reduced pressure to obtain resin powder P3. Mw = about 7,000.

  Table 1 shows the composition ratio of each resin obtained in the above synthesis example.

[Example 1-13, Comparative Example 1-4] Preparation of solvent-free photocurable resin composition, preparation of cured film and evaluation thereof According to the composition shown in Table 2 below, (A) acrylic resin powder, (B) A silane coupling agent, (C) a polyfunctional (meth) acrylate compound, (D) a photopolymerization initiator, and (E) a reactive diluent were mixed and stirred at 40 ° C. for 24 hours to prepare a varnish.

[Preparation of cured film]
On the ITO film (resistance film (high transmittance) ITO film, resistance value: 400 ± 100Ω / sq, total light transmittance:> 90%) manufactured by Sanyo Vacuum Co., Ltd. A bar coater was applied to a thickness of 3 to 10 μm, followed by UV irradiation (400 mJ / cm ² ) to produce a cured film.
About the obtained film, pencil hardness, adhesiveness, and a softness | flexibility were evaluated by the following method.

[Evaluation of pencil hardness]
Based on JIS K 5400, the measurement was performed under a load of 1,000 g. The results are shown in Table 3.

[Evaluation of adhesion to ITO]
The cross-cut test method was used for evaluation. First, 100 grids were created on the coating film using a cutter guide. Next, a cellophane tape (registered trademark) manufactured by Nichiban Co., Ltd. was adhered onto the grid, and rubbed with an eraser from above to make it sufficiently adhere. Then, the cellophane tape (registered trademark) was peeled off, and at that time, it was evaluated how many of the 100 grids were peeled off. The results are shown in Table 3.
0B: 66 or more peeled 1B: 36 to 65 peeled 2B: 16 to 35 peeled 3B: 6 to 15 peeled 4B: 1 to 5 peeled 5B: No peeling

[Evaluation of flexibility]
The film was wound around a cylindrical test bar with the coat side facing outside, and it was visually confirmed whether or not a crack occurred in the cured film. In this case, the minimum diameter of the test bar that does not cause cracks was taken as the evaluation result. It shows that it is a cured film with high flexibility, so that the minimum diameter of a test rod is small. The results are shown in Table 3.

  The cured films obtained from the solventless photocurable resin composition of Example 1-13 all had high pencil hardness of 2H or higher, high adhesion of 3B or higher, and high flexibility of 4 cm or lower. On the other hand, Comparative Example 1 had high pencil hardness but low adhesion and flexibility. Comparative Examples 2 and 3 were not excellent in pencil hardness, adhesion, and flexibility. In Comparative Example 4, the adhesion and flexibility were good, but the pencil hardness was as low as less than H.

Claims (15)

(A) Acrylic resin containing at least one repeating unit derived from a (meth) acrylic acid ester compound represented by the following formula (1) (however, it does not include a repeating unit derived from a hydroxyl group-containing (meth) acrylate) ) 100 parts by mass ,

(In the formula, R represents a hydrogen atom or a methyl group. R ¹ represents an alkyl group.)
(B) 0.001 to 10 parts by mass of a silane coupling agent,
(C) 20 to 200 parts by mass of a polyfunctional (meth) acrylate compound having at least three (meth) acryloxy groups in one molecule;
(D) a photopolymerization initiator, and (E) polymerizable carbon - characterized Rukoto that Yusuke containing a reactive diluent from 10 to 200 parts by <br/> having one or two carbon double bonds Solvent-free photocurable resin composition. The component (B) is contained in an amount of 0.001 to 5 parts by mass with respect to 100 parts by mass of the component (A) and 1 to 20 parts by mass of the component (D) with respect to 100 parts by mass of the component (A). Solvent-free photocurable resin composition. (A) Acrylic resin containing at least one repeating unit derived from a (meth) acrylic acid ester compound represented by the following formula (1) (however, it does not include a repeating unit derived from a hydroxyl group-containing (meth) acrylate) ) 100 parts by mass ,

(In the formula, R represents a hydrogen atom or a methyl group. R ¹ represents an alkyl group.)
(B) 0.001 to 10 parts by mass of a silane coupling agent,
(C) a polyfunctional (meth) acrylate compound having at least three (meth) acryloxy groups in one molecule;
(D) a photopolymerization initiator selected from a benzophenone derivative, an N-arylglycine derivative, an organic azide compound, a titanocene compound, an aluminate complex, an organic peroxide, an N-alkoxypyridinium salt, and a thioxanthone derivative, and (E) a polymerizability A solventless photocurable resin composition comprising a reactive diluent having one or two carbon-carbon double bonds. The component (B) is 0.001 to 5 parts by mass with respect to 100 parts by mass of the component (A), the component (C) is 10 to 300 parts by mass with respect to 100 parts by mass of the component (A), and the component (D) is ( The solvent-free photocurable resin composition according to claim 3, comprising 1 to 20 parts by mass with respect to 100 parts by mass of component A) and 10 to 200 parts by mass of component (E) with respect to 100 parts by mass of component (A). object.   The solvent-free photocurable resin composition according to any one of claims 1 to 4, wherein the (A) acrylic resin further contains a repeating unit derived from (meth) acrylic acid.   The solvent-free photocurable resin composition according to claim 5, wherein the content of repeating units derived from (meth) acrylic acid is 30 mol% or less in all repeating units.   (A) The solventless photocurable resin composition according to any one of claims 1 to 6, wherein the acrylic resin further contains a repeating unit derived from a styrene compound.   The solventless photocurable resin composition according to claim 7, wherein the content of the repeating unit derived from the styrene compound is 50 mol% or less in all repeating units.   (E) The viscosity of a reactive diluent is 200 mPa * s or less in 25 degreeC, The solventless photocurable resin composition of any one of Claims 1-8.   (E) Reactive diluent is monofunctional (meth) acrylates, The solventless photocurable resin composition of any one of Claims 1-9.   The solvent-free photocurable resin composition according to any one of claims 1 to 10, which has a viscosity of 10,000 mPa · s or less at 25 ° C.   The cured film obtained using the solvent-free photocurable resin composition of any one of Claims 1-11.   The cured film according to claim 12, which is an overcoat material.   A laminate formed by laminating the cured film according to claim 12 on a film substrate.   The manufacturing method of the cured film characterized by apply | coating the solventless photocurable resin composition of any one of Claims 1-11 to a board | substrate, and irradiating an ultraviolet-ray.