JP2016139134A - Photosensitive resin composition, cured film formed from the photosensitive resin composition, and image display device comprising the cured film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which can form a cured film having excellent sensitivity and reactivity, a low curing shrinkage, and excellent adhesion.SOLUTION: A photosensitive resin composition comprises a polymerizable compound having at least one structure in which a (meth)acryloyloxy group is bonded to a nitrogen atom of an amide with a carbon chain, and a carbon atom at α position bonded to the nitrogen atom is substituted by a hydrogen atom.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition, a cured film formed from the photosensitive resin composition, and an image display device including the cured film. More specifically, the present invention has excellent sensitivity and reactivity, and has a curing shrinkage rate. The present invention relates to a photosensitive resin composition capable of forming a cured film that is small and excellent in adhesion and hardness, a cured film formed from the photosensitive resin composition, and an image display device including the cured film.

  In the display field, inorganic protective films such as silicon nitride have been conventionally used as protective films for protecting and insulating TFT (Thin Film Transistor) circuits in display devices such as liquid crystal display devices. However, since the dielectric constant is high and it is difficult to improve the aperture ratio, the demand for organic insulating films having a low dielectric constant is increasing in order to solve this problem.

  As such an organic insulating film, a photosensitive resin that is a polymer compound that undergoes a chemical reaction by light and an electron beam and changes its solubility in a specific solvent is generally used. This is due to a change in the polarity of the polymer caused by the photoreaction of the film and a crosslinking reaction. In particular, the organic insulating film material utilizes a change characteristic of solubility in a solvent such as an alkaline aqueous solution after exposure.

  In particular, in the structure of an insulating film of a liquid crystal display device using such an organic insulating film, the insulating film not only has excellent insulating properties, but also reduces stress at the interface when coated on a substrate. Must have low thermal expansibility.

  In addition, many characteristics such as high sensitivity and high permeability, film elongation after development, and low loss due to the developer are required.

  Furthermore, the insulating film, the protective film, and the like inevitably form an interface with a metal, a silicone compound, and the like. At that time, excellent interfacial adhesive force is a very important factor in terms of device reliability.

  US Pat. No. 4,139,391 discloses a photosensitive resin organic insulating film composition prepared by using a copolymer of an acrylic acid compound and an acrylate compound as a binder resin and using an acrylate compound as a polyfunctional monomer. Is disclosed. However, there is a problem that the difference in solubility between the exposed portion and the non-exposed portion is not sufficient, so that the development characteristics are not excellent and the overall remaining film ratio is lowered.

U.S. Pat. No. 4,139,391

  An object of this invention is to provide the photosensitive resin composition excellent in the sensitivity and reactivity.

  Another object of the present invention is to provide a photosensitive resin composition that can form an insulating film with improved adhesion to a substrate, a low shrinkage in curing and excellent hardness.

  Moreover, an object of this invention is to provide the image display apparatus provided with the cured film formed with the said photosensitive resin composition, and the cured film.

  1. A photosensitive compound comprising a polymerizable compound having a structure in which a (meth) acryloyloxy group is bonded to a nitrogen atom of an amide with a carbon chain, and the α-position carbon atom bonded to the nitrogen atom is substituted with a hydrogen atom; Resin composition.

  2. 2. The photosensitive resin composition according to item 1, wherein the amide is glycoluril or isocyanurate.

（式中、Ｒ_１は、水素又はメチル基である。） 3. In the item 1, the photosensitive compound is a photosensitive resin composition, wherein the polymerizable compound is a compound represented by the following [Chemical Formula 1].

(In the formula, R ₁ is hydrogen or a methyl group.)

  4). In the said item 1, the photosensitive resin composition which further contains alkali-soluble resin, a photoinitiator, and a solvent.

（式中、Ｒ_２は、水素又はメチル基である。） 5. In item 4, the alkali-soluble resin is a photosensitive resin composition having a repeating unit represented by the following [Chemical Formula 2].

(In the formula, R ₂ is hydrogen or a methyl group.)

  6). In the said item 4, the photosensitive resin composition whose weight average molecular weights of the said alkali-soluble resin are 2,000-20,000.

（式中、Ｒ_３及びＲ_４は、互いに独立して、水素又はメチル基であり、
Ｒ_５は、下記［化４］の単量体に由来する構造であり、

Ｒ_６は、（メタ）アクリル酸、２−（メタ）アクリロイルオキシエチルスクシネート、２−（メタ）アクリロイルオキシエチルヘキサヒドロフタレート、２−（メタ）アクリロイルオキシエチルフタレート、及び２−（メタ）アクリロイルオキシエチルスクシネートからなる群から選択される単量体に由来する構造であり、
ａ＝４０〜９５ｍｏｌ％、ｂ＝５〜６０ｍｏｌ％である。） 7). In the item 1, the alkali-soluble resin is a photosensitive resin composition having a repeating unit represented by the following [Chemical Formula 3].

(Wherein R ₃ and R ₄ are each independently hydrogen or a methyl group,
R ₅ is a structure derived from the monomer of the following [Chemical Formula 4],

R ₆ is (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, and 2- (meth) A structure derived from a monomer selected from the group consisting of acryloyloxyethyl succinate,
It is a = 40-95 mol% and b = 5-60 mol%. )

（式中、Ｒ_６及びＲ_７は、互いに独立して、水素又はメチル基であり、ｃ＝４０〜９５ｍｏｌ％、ｄ＝５〜６０ｍｏｌ％である。） 8). In the item 4, the alkali-soluble resin is a photosensitive resin composition having a repeating unit represented by the following [Chemical Formula 5].

(In the formula, R ₆ and R ₇ are each independently hydrogen or a methyl group, and c = 40 to 95 mol% and d = 5 to 60 mol%.)

  9. In said item 4, the said alkali-soluble resin is a photosensitive resin composition contained in the quantity of 15-80 mass parts with respect to the total 100 mass parts of the photosensitive resin composition on the basis of solid content.

  10. In the item 4, the polymerizable compound is contained in an amount of 15 to 80 parts by mass with respect to 100 parts by mass of the photosensitive resin composition based on the solid content.

  11. The cured film formed with the photosensitive resin composition as described in any one of said items 1-10.

  12 An image display device comprising the cured film as described in 11 above.

  The photosensitive resin composition of the present invention is excellent in sensitivity and reactivity, and a cured film produced therefrom has a small curing shrinkage rate, excellent adhesion to a substrate, and excellent hardness.

  The present invention relates to a polymerizable compound having at least one structure in which a (meth) acryloyloxy group is bonded to a nitrogen atom of an amide with a carbon chain, and the α-position carbon atom bonded to the nitrogen atom is substituted with a hydrogen atom. It is related with the photosensitive resin composition which can form the cured film which was excellent in the sensitivity and reactivity, the cure shrinkage rate was small, and was excellent in hardness and adhesiveness.

  Hereinafter, the present invention will be described in detail.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention has a structure in which a (meth) acryloyloxy group is bonded to a nitrogen atom of an amide with a carbon chain, and the α-position carbon atom bonded to the nitrogen atom is substituted with a hydrogen atom. Contains one polymerizable compound.

[Polymerizable compound]
In the polymerizable compound used in the photosensitive resin composition of the present invention, the (meth) acryloyloxy group is bonded to the nitrogen atom of the amide with a carbon chain, and the α-position carbon atom bonded to the nitrogen atom is a hydrogen atom. By including a polymerizable compound having at least one substituted structure, the reactivity of the photosensitive resin composition is remarkably improved to promote the polymerization reaction, and the crosslink density during the preparation process is increased.

  In the present invention, “(meth) acryloyloxy group” refers to “(meth) acryloyloxy group”, “acryloyloxy group” or both.

  Generally, when a radical polymerization reaction of an unsaturated polymerization monomer is performed in the presence of oxygen, the polymerization reaction is stopped by reacting the active species with oxygen to form peroxy radicals that are inert radical species. ,finish.

  However, the polymerizable compound according to the present invention has a structure in which a (meth) acryloyloxy group is bonded to the nitrogen atom of the amide with a carbon chain, and the α-position carbon atom bonded to the nitrogen atom is substituted with a hydrogen atom. By including one polymerizable compound, the polymerization reaction can be promoted.

  The polymerizable compound according to the present invention has at least one structure in which a (meth) acryloyloxy group is bonded to a nitrogen atom of an amide with a carbon chain, and a carbon atom at the α-position bonded to the nitrogen atom is substituted with a hydrogen atom. The hydrogen atom can be turned into an acid positive atom by attracting the electron of the hydrogen atom, thereby generating a radical and enabling regeneration of the radical species inactivated by oxygen To do. Thus, the polymerizable compound according to the present invention not only promotes the development of the polymerization reaction by relaxing the effect of oxygen inhibiting the polymerization reaction, but also further promotes the polymerization reaction by slowing the polymerization termination rate. It is judged.

  In the polymerizable compound according to the present invention, the carbon chain connecting the nitrogen atom and the (meth) acryloyloxy group is not particularly limited, but may be an alkylene having 1 to 6 carbon atoms.

  The polymerizable compound according to the present invention has at least one structure in which a (meth) acryloyloxy group is bonded to a nitrogen atom of an amide with a carbon chain, and a carbon atom at the α-position bonded to the nitrogen atom is substituted with a hydrogen atom. As long as it has, the reactivity and desired physical properties of the photosensitive resin composition are ensured without any particular limitation, so that three or more nitrogen atoms having a (meth) acryloyloxy group bonded by a carbon chain are secured. It is preferable to have. In this aspect, the amide of the polymerizable compound according to the present invention may be glycoluril or isocyanurate, preferably glycoluril.

（式中、Ｒ_１は、水素又はメチル基である。） From the aspect of further promoting the reactivity of the photosensitive resin composition, the polymerizable compound according to the present invention preferably contains a compound represented by the following [Chemical Formula 6].

(In the formula, R ₁ is hydrogen or a methyl group.)

  If necessary, the photosensitive resin composition of the present invention may further contain a polymerizable compound used in the art. Furthermore, the polymerizable compound that may be included may be used without any particular limitation, and is, for example, a monofunctional monomer, a bifunctional monomer, and other polyfunctional monomers. Although not limited, the following compound is mentioned as the example.

  Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone and the like. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bisphenol Examples thereof include bis (acryloyloxyethyl) ether of A and 3-methylpentanediol di (meth) acrylate. Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) An acrylate etc. are mentioned. Among these, a polyfunctional monomer having two or more functions is preferably used.

  Although content of the said polymeric compound is not specifically limited, For example, 15-80 mass parts with respect to 100 mass parts of alkali-soluble resin on the basis of solid content in the photosensitive resin composition, Preferably it is 23-60 masses. It may be used in the range of parts. When a polymeric compound is contained in the said content range, it can have the outstanding durability of a cured film, and can improve hardness.

[Alkali-soluble resin]
The alkali-soluble resin used in the present invention is a component that imparts solubility to an alkali developer used in the development processing step, and has a repeating unit represented by the following [Chemical Formula 7].

（式中、Ｒ_２は、水素又はメチル基である。） Since the alkali-soluble resin according to the present invention has a repeating unit represented by the following [Chemical Formula 7], a thermosetting reaction occurs by a ring-opening polymerization reaction between an epoxy functional group and a carboxylic acid at the post-baking stage. It is judged that the cured film formed with the photosensitive resin composition plays a role of ensuring adhesion and hardness with the substrate.

(In the formula, R ₂ is hydrogen or a methyl group.)

  The alkali-soluble resin according to the present invention may further have a repeating unit formed of another monomer known in the art in addition to the repeating unit of the above [Chemical Formula 7]. It may be formed of only repeating units.

（式中、Ｒ_３及びＲ_４は、互いに独立して、水素又はメチル基であり、
Ｒ_５は、下記［化９］の単量体に由来する構造であり、

Ｒ_６は、（メタ）アクリル酸、２−（メタ）アクリロイルオキシエチルスクシネート、２−（メタ）アクリロイルオキシエチルヘキサヒドロフタレート、２−（メタ）アクリロイルオキシエチルフタレート、及び２−（メタ）アクリロイルオキシエチルスクシネートからなる群から選択される単量体に由来する構造であり、
ａ＝４０〜９５ｍｏｌ％、ｂ＝５〜６０ｍｏｌ％である。） The alkali-soluble resin according to the present invention is not particularly limited as long as it has a repeating unit represented by the above [Chemical Formula 7], and may have a repeating unit represented by the following [Chemical Formula 8], for example.

(Wherein R ₃ and R ₄ are each independently hydrogen or a methyl group,
R ₅ is a structure derived from the monomer of the following [Chemical 9],

R ₆ is (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, and 2- (meth) A structure derived from a monomer selected from the group consisting of acryloyloxyethyl succinate,
It is a = 40-95 mol% and b = 5-60 mol%. )

  In the present invention, “(meth) acryl” refers to “methacryl”, “acryl”, or both.

（式中、Ｒ_６及びＲ_７は、互いに独立して、水素又はメチル基であり、ｃ＝４０〜９５ｍｏｌ％、ｄ＝５〜６０ｍｏｌ％である。） Preferable examples of the repeating unit represented by [Chemical Formula 8] according to the present invention include the following repeating unit of [Chemical Formula 10].

(In the formula, R ₆ and R ₇ are each independently hydrogen or a methyl group, and c = 40 to 95 mol% and d = 5 to 60 mol%.)

  In the present invention, each repeating unit represented by [Chemical Formula 8] and [Chemical Formula 10] should not be construed as limited as represented by [Chemical Formula 8] and [Chemical Formula 10]. Can be freely located at any position of the chain within the defined mol% range. That is, each bracket in [Chemical Formula 8] and [Chemical Formula 10] is displayed as one block in order to express mol%, but each repeating subunit is not limited as long as it is within the corresponding resin. Or may be separated from each other.

  From the viewpoint of further improving the adhesion and hardness with the substrate, the weight average molecular weight of the alkali-soluble resin is preferably 2,000 to 20,000.

  If necessary, the alkali-soluble resin according to the present invention may further have a repeating unit formed of another monomer known in the art in addition to the repeating unit of [Chemical Formula 8]. It may be formed only by the repeating unit of formula (8).

  The monomer that forms a repeating unit that can be further added to [Chemical Formula 8] is not particularly limited, but examples thereof include monocarboxylic acids such as crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, itaconic acid, and the like. Anhydrides; mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate; vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene Fragrance such as p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether Group vinyl compound N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N- N-substituted maleimide compounds such as m-methylphenylmaleimide, Np-methylphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide; methyl (meth) Acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, etc. Al Kill (meth) acrylates; finger ring (meth) acrylates such as cyclopentyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate; phenyl (meth) acrylate, etc. Aryl (meth) acrylates; 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxy) Unsaturated oxetane compounds such as methyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane; methyl glycidyl (meth) ac Unsaturated oxirane compound rate like; cycloalkane or di cycloalkane ring having 4 to 16 carbon atoms which is substituted in the (meth) acrylate; and the like. These can be used individually or in mixture of 2 or more types.

  The alkali-soluble resin preferably has an acid value in the range of 20 to 200 (KOHmg / g). If the acid value is within the above range, excellent developability and stability over time can be obtained.

  Although content of alkali-soluble resin is not specifically limited, For example, it is 15-80 mass parts with respect to the total 100 mass parts of the photosensitive resin composition on the basis of solid content, Preferably it is the quantity of 25-60 mass parts. May be included. When contained within the above numerical range, the solubility in the developer is sufficient, so that the developability is good and a cured film having excellent hardness can be formed.

(Photopolymerization initiator)
The photopolymerization initiator according to the present invention is a component capable of polymerizing the polymerizable compound, and can be used without any particular limitation, for example, acetophenone compound, benzophenone compound, triazine compound, biimidazole. At least one compound selected from the group consisting of a series compound, a thioxanthone series compound, and an oxime ester series compound can be used, and an oxime ester series compound is preferably used.

  Specific examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy). Phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, 2- (4-methylbenzyl)- 2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one and the like can be mentioned.

  Specific examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butyl). Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

  Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4 -Methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2 , 4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4- Diethylamino-2-methylphenol Nyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like. .

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl). ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2 '-Bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'- Examples thereof include tetraphenyl-1,2′-biimidazole or an imidazole compound in which the phenyl group at the 4,4 ′, 5,5 ′ position is substituted with a carboalkoxy group, preferably 2,2′-bis (2 − Lorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 -Bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole and the like.

  Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

  Specific examples of the oxime ester compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and 1,2-octadion-1- (4-phenylthio) phenyl-2- (o-benzoyl). Oxime) or ethanone, 1- (9-ethyl) -6- (2-methylbenzoyl-3-yl) -1- (o-acetyloxime) and the like, and CGI-124 (Ciba Geigy) as a commercial product , CGI-224 (Ciba Geigy), Irgacure OXE-01 (BASF), Irgacure OX-02 (BASF), N-1919 (Adeka), NCI-831 (Adeka) and the like.

  Further, the photopolymerization initiator may further contain a photopolymerization initiation auxiliary agent in order to improve the sensitivity of the photosensitive resin composition of the present invention. When the photosensitive resin composition according to the present invention contains a photopolymerization initiation assistant, the sensitivity is further increased and the productivity can be improved.

  Examples of the photopolymerization initiation aid include one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and organic sulfur compounds having a thiol group.

  Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid-2-ethylhexyl, benzoic acid-2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4'- Examples thereof include bis (diethylamino) benzophenone, and it is preferable to use an aromatic amine compound.

  Specific examples of the carboxylic acid compound are preferably aromatic heteroacetic acids such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthiol. Examples include acetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

  Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl). -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol Examples include tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate).

  Although content of the said photoinitiator is not specifically limited, For example, it is contained in the quantity of 0.1-20 mass parts with respect to the total 100 mass parts of the photosensitive resin composition on the basis of solid content. Preferably, it may be contained in an amount of 0.1 to 10 parts by mass. When the numerical value range is satisfied, the exposure time is shortened by increasing the sensitivity of the photosensitive resin composition, so that productivity can be improved and high resolution can be maintained, and the strength of the formed pixel portion and the pixel portion It is preferable at the point from which the smoothness in the surface of becomes favorable.

〔solvent〕
Any solvent can be used without limitation as long as it is usually used in the art.

  Specific examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl. Diethylene glycol dialkyl ethers such as ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol monoalkyl ethers such as propylene glycol monopropyl ether and propylene glycol monobutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl Propylene glycol dialkyl ethers such as ether and propylene glycol ethyl propyl ether; propylene glycol alkyl such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate Ether propionates; Butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol, butoxybutyl alcohol; Butanediol monoalkyl such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, butoxybutyl acetate Alkyl ether acetates; methoxybu Butanediol monoalkyl ether propionates such as tilpropionate, ethoxybutylpropionate, propoxybutylpropionate, butoxybutylpropionate; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl Dipropylene glycol dialkyl ethers such as ethers; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone; ethanol, propanol, butanol, hexanol , Cyclohexanol, ethylene glycol, methyl ethyl diethylene glycol, glycerin and other alcohols; methyl acetate Ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, Methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, Methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate Propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl-2-methoxypropionate, 2-methoxypropion Acid butyl, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxypropionic acid Propyl, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3-ethoxyprop Methyl pionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxypropion Esters such as butyl acid, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate and butyl 3-butoxypropionate; cyclic ethers such as tetrahydrofuran and pyran; cyclic such as γ-butyrolactone Examples include esters. The solvent illustrated here can be used individually or in mixture of 2 or more types, respectively.

  In consideration of coating properties and drying properties, the solvent is alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate Esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc. May be used.

  The content of the solvent may be included in an amount of 30 to 95 parts by mass, preferably 40 to 85 parts by mass with respect to 100 parts by mass of the entire photosensitive resin composition. When the above range is satisfied, the coating property is improved when coating is performed with a coating apparatus such as a spin coater, a slit and spin coater, a slit coater (sometimes referred to as “die coater” or “curtain flow coater”), and an ink jet. Therefore, it is preferable.

〔Additive〕
The photosensitive resin composition according to the present invention includes a filler, other polymer compound, a curing agent, a leveling agent, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, a chain transfer agent, and the like as necessary. These additives may be further included.

  Specific examples of the filler include glass, silica, alumina and the like.

  Specific examples of the other polymer compounds include curable resins such as epoxy resins and maleimide resins; thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. Is mentioned.

  The said hardening | curing agent is used in order to raise deep part hardening and mechanical strength, and an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound etc. are mentioned as a specific example of a hardening | curing agent.

  Specific examples of the epoxy compound in the curing agent include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolac type epoxy resin, and other aromatic types. Epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, or bromo derivatives of such epoxy resins, epoxy resins and aliphatic, alicyclic or aromatic epoxy compounds other than bromo derivatives, Examples include butadiene (co) polymer epoxy compounds, isoprene (co) polymer epoxy compounds, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.

  Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

  The said hardening | curing agent can use together the hardening auxiliary compound which can carry out the ring-opening polymerization of the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound with the said hardening | curing agent. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, acid generators, and the like.

  What is marketed as an epoxy resin hardening | curing agent can be utilized for the said carboxylic acid anhydrides. Examples of the epoxy resin curing agent include trade name ADEKA HARDNER EH-700 (manufactured by ADEKA INDUSTRY CO., LTD.), Trade name RIKACID HH (manufactured by Shin Nippon Rika Co., Ltd.), trade name MH-700 (new Japan Rika ( Etc.). The curing agents exemplified above can be used alone or in admixture of two or more.

  As the leveling agent, commercially available surfactants can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, and amphoteric surfactants. You may use each individually or in combination of 2 or more types.

  Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. Other than the above, the product names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), MegaFuck (Dainippon Ink Chemical Co., Ltd.) Manufactured), FLORARD (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Geneca Corporation), EFKA (manufactured by EFKA CHEMICALS), PB821 (Ajinomoto Co., Inc.) Manufactured) and the like.

  The adhesion promoter is preferably a silane compound, and specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyl. Methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. That.

  Specific examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2- Hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy ] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, 3,9-bis [2- {3- (3-tert-butyl) -4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2′-methyl Renbis (6-tert-butyl-4-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 4,4′-thiobis (2-tert-butyl-5-methylphenol) ), 2,2′-thiobis (6-tert-butyl-4-methylphenol), dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3, 3′-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3 5-triazine-2,4,6 (1H, 3H, 5H) -trione, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2 , 6-di-tert-butyl-4-methylphenol and the like.

  Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.

  Specific examples of the anti-aggregation agent include sodium polyacrylate.

  Specific examples of the chain transfer agent include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.

  The content of the additive is 0.001-1 parts by mass, preferably 0.01-0.8 parts by mass with respect to the total 100 parts by mass of the photosensitive resin composition based on the solid content. It may be.

<Curing film and image display device>
An object of this invention is to provide the image display apparatus provided with the cured film manufactured with the said photosensitive resin composition, and the said cured film.

  The cured film manufactured with the said photosensitive resin composition is excellent in a cure shrinkage rate and adhesiveness with a base material. Thereby, in an image display device, for example, it can be used for an adhesive layer, an array flattening film, a protective film, an insulating film, etc., but is not limited thereto, and is particularly preferable as an insulating film.

  Examples of the image display device provided with such a cured film include a liquid crystal display device, an OLED, a flexible display, and the like, but are not limited to these, and all known image display devices in the applicable field can be used. Can be mentioned.

  The cured film comprises a step of applying the above-described photosensitive resin composition of the present invention on a substrate, a step of heating and drying the photosensitive resin composition, a step of exposing, a step of developing, and a post-bake if necessary. And a step of washing with water.

  First, a photosensitive resin composition is applied to a substrate and then dried by heating to remove a volatile component such as a solvent to obtain a smooth coating film.

  As the coating method, for example, spin coating, casting coating, roll coating, slit and spin coating, or slit coating may be used. After application, heat drying (pre-baking) or drying after reduced pressure heats to volatilize volatile components such as a solvent. Here, the heating temperature is 70 to 100 ° C., which is a relatively low temperature. The coating thickness after heat drying is usually about 1 to 8 μm. The coating film thus obtained is cured by irradiating with ultraviolet rays.

  As the ultraviolet rays, g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), or the like can be used. The irradiation amount of ultraviolet rays can be appropriately selected as necessary, and is not limited in the present invention. If the cured coating is developed by bringing it into contact with a developer as necessary, a desired cured film can be formed.

  As the developing method, any of a liquid addition method, a dipping method, a spray method and the like may be used. Further, the substrate may be inclined at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate. Potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Etc.

  These inorganic and organic alkaline compounds can be used alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

  As the surfactant in the alkaline developer, at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, or a cationic surfactant can be used.

  Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, and sorbitan fatty acids. Examples include esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, and the like.

  Specific examples of the anionic surfactant include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate and dodecyl sodium sulfate. And alkyl aryl sulfonates such as sodium naphthalene sulfonate.

  Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, quaternary ammonium salts, and the like. These surfactants can be used alone or in combination of two or more.

  The concentration of the surfactant in the developer is usually 0.01 to 10% by mass, preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass. After the development, it is washed with water and post-baked for 10 to 60 minutes at a relatively low temperature of 100 to 150 ° C.

  In order to facilitate the understanding of the present invention, preferred examples are shown below, but these examples are merely illustrative of the present invention and do not limit the scope of the appended claims. It will be apparent to those skilled in the art that various changes and modifications can be made to the embodiments within the scope of the scope and the technical idea, and such changes and modifications are claimed in the appended claims. Of course it belongs to.

Synthesis Example 1 Synthesis of alkali-soluble resin (A-1) In a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was allowed to flow at 0.02 L / min under a nitrogen atmosphere, and diethylene glycol methyl ethyl ether 150 g was charged and heated to 70 ° C. with stirring. Next, 210.2 g (0.95 mol) of a mixture of the following [Chemical 11] and [Chemical 12] (molar ratio 50:50) and 14.5 g (0.17 mol) of methacrylic acid were dissolved in 150 g of diethylene glycol methyl ethyl ether. To prepare a solution.

  The prepared solution was dropped into the flask using a dropping funnel, and then 27.9 g (0.11 mol) of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was added to 200 g of diethylene glycol methyl ethyl ether. The solution dissolved in was dropped into the flask over 4 hours using another dropping funnel. After completion of dropping of the polymerization initiator solution, the temperature was maintained at 70 ° C. for 4 hours, and then cooled to room temperature. The solid content was 41.6% by mass and the acid value was 65 mg-KOH / g (in terms of solid content). A solution of copolymer (resin A-1) was obtained. The obtained resin A-1 had a weight average molecular weight Mw of 8,300 and a molecular weight distribution of 1.85.

Synthesis Example 2 Synthesis of polymerizable compound (B-1) In a flask substituted with a nitrogen atmosphere as the reaction proceeds, 200 g of toluene and N, N ′, N ″, N ′ ″-tetra (2-hydroxyethyl) glycol After adding 10.0 g (31.4 mmol) of uril (N, N ′, N ″, N ″ ′-Tetra (2-hydroxyethyl) glycoluril) (Shikoku Kasei), para-toluenesulfonic acid ) (Manufactured by TCI) 0.54 g (3.1 mmol) and 18.1 g (251.3 mmol) of acrylic acid were further added. The reaction mixture was allowed to proceed for 10 hours under toluene reflux conditions, and water generated by the condensation reaction of alcohol and acrylic acid was removed using a Dean-stark trap.

  After the reaction mixture was cooled to 0 ° C., 100 g of 1N aqueous sodium hydrogen carbonate solution was added, the organic solution layer was separated with a separatory funnel, and then further washed with 100 g of 1N aqueous sodium hydrogen carbonate solution. The organic solution layer was further washed twice with distilled water. The remaining organic solution was dried under reduced pressure conditions to finally obtain 16.0 g (yield 95%) of polymerizable compound B-1. The purity analyzed by liquid chromatography was 98%.

Synthesis Example 3 Synthesis of polymerizable compound (B-2) In the same manner as in Synthesis Example 2, except that 21.6 g (251.3 mmol) of methacrylic acid was used instead of 18.1 g (251.3 mmol) of acrylic acid, 16.7 g (yield 90%) of the polymerizable compound (B-2) was obtained by the progress of the reaction. The purity analyzed by liquid chromatography was 98%.

[Examples and Comparative Examples]
The photosensitive resin composition which has a composition and content (mass part) described in the following [Table 1] was prepared.

〔Test method〕
A 2-inch square glass substrate (Eagle 2000, Corning) was sequentially washed with a neutral detergent, water, and alcohol and then dried. The glass substrate was spin-coated with the photosensitive resin compositions prepared in Examples and Comparative Examples, and prebaked at 90 ° C. for 125 seconds using a hot plate.

After cooling the pre-baked substrate at room temperature, the entire coating film was irradiated with light at an exposure amount of 50 mJ / cm ² (based on 365 nm) using an exposure machine (UX-1100SM; manufactured by Usio Co., Ltd.). After the light irradiation, the coating film was dipped in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 25 ° C. for 60 seconds to develop, and after washing in an oven, Post-baking was performed at 100 ° C. for 60 minutes. The thickness of the obtained coating film was 3.0 μm. From the cured film thus obtained, physical properties were evaluated as follows, and the results are shown in [Table 2] below.

(1) Pencil hardness evaluation The surface hardness of the obtained cured film was measured. The surface hardness is 50 mm / sec in a state where a Mitsubishi pencil (Mitsubishi Pencil) is brought into contact with the substrate using a pencil hardness measuring machine (Pencil Hardness Tester) and then a weight of 500 g is placed thereon to increase the load. The surface hardness was measured by scratching the surface of the substrate at a speed of and observing the surface. The measurement standard was evaluated based on the time when no surface wear, peeling, tearing, or scratched shape was observed at a level corresponding to pencil hardness.

(2) Evaluation of Development Residual Film Ratio The resin compositions of Examples and Comparative Examples were applied to substrates and spin coated, respectively, and then pre-baked at 90 ° C. for 125 seconds using a hot plate. After cooling the pre-baked substrate at room temperature, the entire surface of the coating film was irradiated with light at an exposure amount of 50 mJ / cm ² (based on 365 nm) using an exposure machine (UX-1100SM; manufactured by Usio Co., Ltd.).

  After light irradiation, the coating film was immersed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide for development for 60 seconds at 25 ° C., and the film thickness was measured after washing with water. Carried out. At that time, the film thickness after exposure and the film thickness after development were measured, and the development residual film ratio was measured using the following [Equation 1].

  The higher the remaining film ratio, the better the performance.

(3) Curing shrinkage rate evaluation After applying the resin composition of an Example and a comparative example to a board | substrate and spin-coating each, it prebaked at 90 degreeC for 125 second using the hotplate (Hot plate). After cooling the pre-baked substrate at room temperature, the whole surface of the coating film was irradiated with light using an exposure machine (UX-1100SM; manufactured by Ushi Co., Ltd.) at an exposure amount of 50 mJ / cm ² (365 nm standard).

  After light irradiation, the coating film was developed by immersing in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 25 ° C. for 60 seconds, washed with water, Measurements were performed. Subsequently, it was heated to 230 ° C. in an oven and baked for 30 minutes. At that time, the film thickness after development and the film thickness after heating at 230 ° C. for 30 minutes were measured, and the curing shrinkage was measured using the following [Equation 2].

  It is judged that the smaller the shrinkage rate, the better the performance.

(4) Adhesive evaluation After applying the resin composition of an Example and a comparative example to a board | substrate and spin-coating each, it prebaked at 90 degreeC for 125 second using the hotplate (Hot plate). After cooling the pre-baked substrate at room temperature, the whole surface of the coating film was irradiated with light using an exposure machine (UX-1100SM; manufactured by Ushi Co., Ltd.) at an exposure amount of 50 mJ / cm ² (365 nm standard).

  After light irradiation, the coating film was developed by immersing in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 25 ° C. for 60 seconds, washed with water, Measurements were performed. Subsequently, it was heated to 100 ° C. in an oven and baked for 60 minutes.

  The obtained cured film was checked for adhesion by a method in which a tape was applied to a surface cut with a cutter based on ASTM D-3359-08 standard test conditions and then peeled off.

  In the cutting / tape test after baking, it is determined that 5B has the most excellent performance based on the following criteria for the degree of peeling of the coating film.

<Evaluation criteria>
5B: 0% peeling
4B: Peeling less than 5% 3B: Peeling 5% or more and less than 15% 2B: Peeling 15% or more and less than 35% 1B: Peeling 35% or more and less than 65% 0B: Peeling 65% or more

  Referring to the above [Table 2], it was confirmed that the examples using the photosensitive resin composition according to the present invention showed a high residual film ratio and excellent sensitivity in the exposure stage. Moreover, it was confirmed that the adhesion to the substrate was excellent, the pencil hardness was excellent, and the cure shrinkage ratio was improved.

  However, in the case of the comparative example in which the compound of the present invention was not used, it was confirmed that the remaining film ratio was lower than that in the example and the sensitivity at the exposure stage was low. Moreover, it was confirmed that pencil hardness and the adhesiveness with respect to a board | substrate fell remarkably, especially in the case of the comparative example 2, the surface abnormality of the cured film arose.

Claims (12)

  A photosensitive compound comprising a polymerizable compound having a structure in which a (meth) acryloyloxy group is bonded to a nitrogen atom of an amide with a carbon chain, and the α-position carbon atom bonded to the nitrogen atom is substituted with a hydrogen atom; Resin composition.   The photosensitive resin composition according to claim 1, wherein the amide is glycoluril or isocyanurate. The photosensitive resin composition according to claim 1, wherein the polymerizable compound is a compound represented by the following [Chemical Formula 1].

(In the formula, R ₁ is hydrogen or a methyl group.)   The photosensitive resin composition according to claim 1, further comprising an alkali-soluble resin, a photopolymerization initiator, and a solvent. The photosensitive resin composition according to claim 4, wherein the alkali-soluble resin has a repeating unit represented by the following [Chemical Formula 2].

(In the formula, R ₂ is hydrogen or a methyl group.)   The photosensitive resin composition of Claim 4 whose weight average molecular weights of the said alkali-soluble resin are 2,000-20,000. The photosensitive resin composition according to claim 4, wherein the alkali-soluble resin has a repeating unit represented by the following [Chemical Formula 3].

(Wherein R ₃ and R ₄ are each independently hydrogen or a methyl group,
R ₅ is a structure derived from the monomer of the following [Chemical Formula 4],

R ₆ is (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, and 2- (meth) A structure derived from a monomer selected from the group consisting of acryloyloxyethyl succinate,
It is a = 40-95 mol% and b = 5-60 mol%. ) The photosensitive resin composition according to claim 4, wherein the alkali-soluble resin has a repeating unit represented by the following [Chemical Formula 5].

(In the formula, R ₆ and R ₇ are each independently hydrogen or a methyl group, and c = 40 to 95 mol% and d = 5 to 60 mol%.)   The photosensitive resin composition according to claim 4, wherein the alkali-soluble resin is contained in an amount of 15 to 80 parts by mass with respect to a total of 100 parts by mass of the photosensitive resin composition based on the solid content.   The photosensitive resin composition of Claim 4 in which the said polymeric compound is contained in the quantity of 15-80 mass parts with respect to 100 mass parts of the whole photosensitive resin composition on the basis of solid content.   The cured film formed from the photosensitive resin composition as described in any one of Claims 1-10.   An image display device comprising the cured film according to claim 11.