JP2016003286A - Photosensitive resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that gives a cured product having sufficient surface hardness and excellent in electric characteristics and various physical properties such as adhesiveness, and to provide a cured film formed of the photosensitive resin composition, and a display device member and a display device which can achieve high definition by including the cured film.SOLUTION: The photosensitive resin composition comprises an alkali-soluble resin, a polyfunctional polymerizable compound, inorganic fine particles, and a photopolymerization initiator. The alkali-soluble resin has a weight average molecular weight of 15000 to 20000 and an acid value of 50 to 80 mgKOH/g. A solid content of the alkali-soluble resin is 20 to 30 mass% with respect to 100 mass% of the total solid content of the photosensitive resin composition. The photosensitive resin composition contains, with respect to 100 pts.mass of the solid content of the alkali-soluble resin, 30 to 50 pts.mass of the polyfunctional polymerizable compound, 90 to 110 pts.mass of the inorganic fine particles, and 60 to 80 pts.mass of the photopolymerization initiator (all in terms of solid contents).

Description

The present invention relates to a photosensitive resin composition and its use. More specifically, the present invention relates to a photosensitive resin composition useful for constituent members of various display devices, a cured film using the same, a display device member, and a display device.

The photosensitive resin composition having photoreactive characteristics can be applied to various components such as liquid crystal display devices, solid-state imaging devices, touch panel display devices, etc. by utilizing the characteristics. It is being considered. For example, a capacitive touch panel display generally has a structure in which a transparent conductive film such as ITO is formed on a substrate, and a protective film or an insulating film for protecting the transparent conductive film is formed. In general, constituent members such as a protective film and an insulating film are required to have high adhesion and surface hardness with a transparent conductive film. Recently, as display devices have higher definition, improvement in electrical characteristics has been demanded. Therefore, there is a demand for a photosensitive resin composition that can provide a cured product having excellent physical properties. As for the conventional photosensitive resin composition, for example, a composition described in Patent Document 1 has been proposed.

JP 2013-227485 A

As described above, the cured product of the photosensitive resin composition is required to have high adhesion and surface hardness and good electrical characteristics. Further, in recent years, with the high definition of display devices and the like, higher performance is strongly demanded for each member used. However, a photosensitive resin composition that can sufficiently meet these needs has not been developed yet. For example, the composition described in Patent Document 1 is a very useful composition for various applications because it can give a cured product that can stably exhibit excellent appearance, adhesion, surface hardness, and the like. There was room for improvement in order to improve the electrical properties of the cured product and to exhibit various physical properties in a more balanced manner.

This invention is made | formed in view of the said present condition, and has the sufficient surface hardness, and provides the photosensitive resin composition which can give the hardened | cured material which is excellent in various physical properties, such as an electrical property and adhesiveness. For the purpose. Another object of the present invention is to provide a cured film formed of such a photosensitive resin composition, and a display device member and a display device that can realize high definition by having the cured film.

As a result of various studies on the photosensitive resin composition, the present inventors have found that the resin composition containing an alkali-soluble resin, a polyfunctional polymerizable compound, inorganic fine particles, and a photopolymerization initiator has developability, photosensitivity, and adhesion. In addition, the physical properties of the resin composition are affected by the ratio of each component in the resin composition, the weight average molecular weight and the acid value of the alkali-soluble resin. I found out. Therefore, as a result of detailed studies, the weight-average molecular weight and acid value of the alkali-soluble resin, and the optimum range for each component ratio were found, and the resin composition satisfying this range has excellent adhesion ( In particular, it has been found that light resistance (adhesion resistance), low dielectric constant and high surface hardness can be exhibited in a well-balanced manner, and that storage stability is also good. Furthermore, such a photosensitive resin composition is particularly suitable as a resin composition for forming a protective film or an insulating film used for a touch panel display device, a color filter, and the like, and a cured film and a display device formed therefrom. It has been found that the structural member and the display device can sufficiently meet the recent demand for higher performance, and the inventors have arrived at the present invention by conceiving that the above-mentioned problems can be solved brilliantly.

That is, the present invention is a photosensitive resin composition comprising an alkali-soluble resin, a polyfunctional polymerizable compound, inorganic fine particles, and a photopolymerization initiator, and the alkali-soluble resin has a weight average molecular weight of 15,000 to 20000 and an acid value of 50. -80 mg KOH / g, and the solid content of the alkali-soluble resin is 20-30% by mass with respect to 100% by mass of the total solid content of the photosensitive resin composition, and the solid content of the alkali-soluble resin is 100 parts by mass. In contrast, a photosensitive resin composition containing 30 to 50 parts by mass of a polyfunctional polymerizable compound, 90 to 110 parts by mass of inorganic fine particles, and 60 to 80 parts by mass of a photopolymerization initiator (all having a solid content). is there.
The present invention is also a cured film formed from the photosensitive resin composition.
The present invention is also a member for a display device having the cured film.
The present invention is also a display device having the cured film.
The present invention is described in detail below. In addition, the form which combined each preferable form of this invention described below 2 or 3 or more is also a preferable form of this invention.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention (also simply referred to as a resin composition) includes an alkali-soluble resin, a polyfunctional polymerizable compound, inorganic fine particles, and a photopolymerization initiator. One or more components may be included. Each component can be used alone or in combination of two or more.

In the present specification, the “total amount of solids” means the total amount of components that form a cured product (components other than the solvent that volatilizes when the cured product is formed). Specifically, it means the total mass of the solid content of the photosensitive resin composition excluding the solvent.

<Alkali-soluble resin>
The photosensitive resin composition of the present invention contains an alkali-soluble resin, and the solid content of the alkali-soluble resin in the photosensitive resin composition is 20 with respect to 100% by mass of the total solid content of the photosensitive resin composition. -30 mass%. When it is 20% by mass or more, developability is improved and good patterning can be obtained, and the light-resistant adhesion of the cured product becomes more excellent, and when it is 30% by mass or less, curing is achieved. Since the surface hardness of the product is further improved, these properties can be satisfactorily exhibited in a balanced manner within the range of 20 to 30% by mass. Preferably it is 22 mass% or more, More preferably, it is 24 mass% or more, Preferably it is 29 mass% or less, More preferably, it is 28 mass% or less.

The alkali-soluble resin has a weight average molecular weight (Mw) of 15000 to 20000. By being 15000 or more, the surface hardness and light-resistant adhesiveness of hardened | cured material are improved. Moreover, by being 20000 or less, the solubility with respect to developing solutions, such as an alkaline agent, becomes sufficient, for example, and the residue at the time of image development can be reduced more. Preferably it is 16000 or more, More preferably, it is 17000 or more, More preferably, it is 18000 or more.
In this specification, a weight average molecular weight can be measured by the method as described in the Example mentioned later.

The acid value (AV) of the alkali-soluble resin is 50 to 80 mgKOH / g. When the acid value is 50 mgKOH / g or more, sufficient alkali solubility is exhibited, and a cured product having excellent developability can be obtained. Moreover, by being 80 mgKOH / g or less, the dielectric constant of hardened | cured material can be reduced and light-resistant adhesiveness can also be improved. Preferably it is 55 mgKOH / g or more, Preferably it is 75 mgKOH / g or less, More preferably, it is 70 mgKOH / g or less.
In the present specification, the acid value of the polymer (resin) is determined from the acid value of the solution and the solid content of the solution, after measuring the acid value of the polymer solution by the method described in the examples described later. It can obtain | require by calculating the acid value of. The solid content of the polymer solution can be determined by the method described in Examples described later.

As the alkali-soluble resin, for example, a polymer obtained by polymerizing a monomer component containing a monomer having an acid group and a polymerizable double bond (also referred to as a base polymer), as described later, A polymer obtained by reacting a base polymer with a compound having a functional group capable of binding to an acid group and a polymerizable double bond (a polymer having a double bond in a side chain or a polymer containing a side chain double bond) (Also referred to as coalescence) is preferred. More preferred is the latter side chain double bond-containing polymer from the viewpoint of improving curability. Each monomer (compound) can be used alone or in combination of two or more.

Particularly preferred as the alkali-soluble resin is a polymer having a ring structure in the main chain. When a polymer having a ring structure in the main chain is used, it is excellent in heat resistance, surface hardness and adhesion, and for example, curing that can suppress various changes with time after high temperature exposure and can develop various physical properties more stably. You can get things. Therefore, the monomer component that forms the base polymer includes one or two monomers capable of introducing a ring structure into the main chain skeleton of the polymer, together with a monomer having an acid group and a polymerizable double bond. It is preferable to include more than one species.

(I) Monomer having an acid group and a polymerizable double bond and a monomer having a polymerizable double bond include, for example, (meth) acrylic acid, crotonic acid, cinnamic acid, vinyl benzoic acid Unsaturated monocarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, etc .; succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxy) Unsaturated monocarboxylic acids having a chain extended between an unsaturated group such as ethyl) and a carboxyl group; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; Light ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.) And the like, and the like. Among these, it is preferable to use carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, unsaturated acid anhydrides) from the viewpoints of versatility and availability. More preferably, it is preferable to use unsaturated monocarboxylic acids (also referred to as unsaturated monocarboxylic acid monomers) in terms of reactivity, alkali solubility, etc., more preferably (meth) acrylic acid (that is, acrylic acid). And / or methacrylic acid), among which methacrylic acid is particularly preferred.

The content ratio of the acid group and the monomer having a polymerizable double bond in the base polymer component (monomer component forming the base polymer) is, for example, 5% by mass or more with respect to 100% by mass of the base polymer component. It is preferable that Thereby, the solubility with respect to an alkali becomes more sufficient, for example, it becomes a more useful photosensitive resin composition for the use for which developability is required. Moreover, it is preferable that it is 85 mass% or less at the point which can maintain the outstanding external appearance, adhesiveness, etc. of hardened | cured material after high temperature exposure (for example, post-baking). More preferably, it is 10-80 mass%, More preferably, it is 15-75 mass%.

(Ii) Monomer capable of introducing a ring structure into the main chain skeleton of the polymer As a monomer capable of introducing a ring structure into the main chain skeleton of the polymer, for example, it has a double bond-containing ring structure in the molecule. Examples thereof include monomers and monomers that form a polymer having a cyclic structure in the main chain by cyclopolymerization. It is preferable to use one or more of these. As such a monomer, at least one selected from the group consisting of an N-substituted maleimide monomer, an acrylic ether dimer, and an α- (unsaturated alkoxyalkyl) acrylate monomer is used. Is preferred. In this case, the alkali-soluble resin is a polymer having an N-substituted maleimide monomer unit, an acrylic ether dimer unit, and / or an α- (unsaturated alkoxyalkyl) acrylate monomer unit.

In particular, a resin (polymer) containing an N-substituted maleimide monomer unit and / or an acrylic ether dimer unit has heat resistance, dispersibility (for example, colorant dispersibility, inorganic compound dispersibility), hardness, and the like. It is possible to provide a cured film with more improved. In addition, resins containing α- (unsaturated alkoxyalkyl) acrylate monomer units can contribute to plate-making properties such as adhesion, curability, and dry redissolvability, colorant dispersibility, heat resistance, and transparency. It is possible to provide a cured film with improved properties and the like.
The resin (polymer) containing the above-mentioned monomer unit means a resin containing a structural unit derived from the monomer by, for example, a monomer polymerization reaction or a crosslinking reaction.

(Ii-1) N-substituted maleimide monomers As N-substituted maleimide monomers, for example, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N -T-butylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide, etc. are mentioned, These 1 type (s) or 2 or more types can be used. Among these, N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide are preferable, and N-benzylmaleimide is particularly preferable because of less coloring and excellent dispersibility of inorganic fine particles.

Examples of the N-benzylmaleimide include benzylmaleimide; alkyl-substituted benzylmaleimide such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl group-substituted benzylmaleimide such as p-hydroxybenzylmaleimide; o-chlorobenzylmaleimide Halogen-substituted benzylmaleimide such as o-dichlorobenzylmaleimide and p-dichlorobenzylmaleimide;

(Ii-2) Acrylic ether dimer As an acrylic ether dimer, for example, the following general formula (1):

(In the formula, R ¹ represents a hydrogen atom or an organic group having 1 to 25 carbon atoms which may have a substituent. R ² may have a hydrogen atom or a substituent. A compound represented by a good organic group having 1 to 25 carbon atoms is preferred.

In the general formula (1), R ¹ and R ² are the same or different and represent a hydrogen atom or an organic group having 1 to 25 carbon atoms which may have a substituent. Is preferably a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. For example, a linear or branched alkyl group; an aryl group; an alicyclic group; an alkyl group substituted with alkoxy; an alkyl substituted with an aryl group exemplified in JP2013-061599A [0037] Group; etc. are mentioned. Of these, primary or secondary carbon hydrocarbon groups which are difficult to be removed by acid or heat, such as methyl, ethyl, cyclohexyl, benzyl and the like, are preferable in terms of heat resistance.
Note that R ¹ and R ² may be the same type of organic group or different organic groups.

Among the acrylic ether dimers, dialkyl-2,2 ′-(oxydimethylene) diacrylate monomers are preferable.
Specifically, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-propyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2,2 ′-[ Oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (stearyl) -2,2 ′-[ Xybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) -2,2 ′-[oxybis (methylene) ] Bis-2-propenoate, di (1-methoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxyethyl) -2,2'-[oxybis (methylene) ] Bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2 '-[Oxybis (methylene)] bis-2-propenoate, di (t-butylcyclohexyl) -2,2'-[oxybis (me Tylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) -2,2 ′-[oxybis (Methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 ′-[oxybis (methylene)] bis-2- Examples include propenoate and di (2-methyl-2-adamantyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, and one or more of these can be used.

Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2 ′-[ Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. From the viewpoints of little coloring, dispersibility, industrial availability, and the like, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate is more preferable.

(Ii-3) α- (Unsaturated alkoxyalkyl) acrylate monomer As the α- (unsaturated alkoxyalkyl) acrylate monomer, for example, alkyl- (α-methallyloxymethyl) acrylate, α -(Allyloxymethyl) acrylate is preferred. Of these, α- (allyloxymethyl) acrylate is more preferable.

Examples of the α- (allyloxymethyl) acrylate include the following general formula (2):

A compound represented by the formula (wherein R ³ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms which may have a substituent) is preferable. In this specification, “α- (allyloxymethyl) acrylate” includes a compound in which R ³ is a hydrogen atom (that is, α-allyloxymethylacrylic acid).

R ³ may be appropriately selected according to the purpose and application, but the organic group having 1 to 30 carbon atoms that R ³ can represent may have a substituent, and 1 to 30 carbon atoms. The hydrocarbon group is preferably. Specifically, for example, a chain saturated hydrocarbon group exemplified in JP2013-061599A [0037]; an alkoxy-substituted chain in which a part of the hydrogen atoms of the chain saturated hydrocarbon group is replaced with an alkoxy group Linear saturated hydrocarbon group; hydroxy-substituted chain saturated hydrocarbon group in which part of chain saturated hydrocarbon group hydrogen atom is replaced with hydroxy group; part of chain saturated hydrocarbon group hydrogen atom is replaced with halogen Halogen-substituted chain saturated hydrocarbon group; chain unsaturated hydrocarbon group, and chain unsaturated hydrocarbon group in which part of the hydrogen atom is replaced with an alkoxy group, hydroxy group or halogen; alicyclic hydrocarbon group And an alicyclic hydrocarbon group in which a part of the hydrogen atom is replaced by an alkoxy group, a hydroxy group or a halogen; an aromatic hydrocarbon group and a part of the hydrogen atom are an alkoxy group, a hydroxy And aromatic hydrocarbon groups substituted with halogen; and the like. Moreover, arbitrary substituents may be further bonded to these organic groups.

Specific examples of the α- (allyloxymethyl) acrylate include, for example, α-allyloxymethyl acrylic acid, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid. n-propyl, α-allyloxymethyl acrylate i-propyl, α-allyloxymethyl acrylate n-butyl, α-allyloxymethyl acrylate s-butyl, α-allyloxymethyl acrylate t-butyl, α- N-amyl allyloxymethyl acrylate, s-amyl α-allyloxymethyl acrylate, t-amyl α-allyloxymethyl acrylate, neopentyl α-allyloxymethyl acrylate, n-hexyl α-allyloxymethyl acrylate , Α-allyloxymethyl acrylate s-hexyl, -N-heptyl allyloxymethyl acrylate, n-octyl α-allyloxymethyl acrylate, s-octyl α-allyloxymethyl acrylate, t-octyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid 2-ethylhexyl, α-allyloxymethyl acrylate capryl, α-allyloxymethyl acrylate nonyl, α-allyloxymethyl acrylate decyl, α-allyloxymethyl acrylate undecyl, α-allyloxymethyl acrylate, α -Tridecyl allyloxymethyl acrylate, myristyl α-allyloxymethyl acrylate, pentadecyl α-allyloxymethyl acrylate, cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, α-allyloxy Contains chain saturated hydrocarbon groups such as stearyl dimethyl acrylate, nonadecyl α-allyloxymethyl acrylate, eicosyl α-allyloxymethyl acrylate, seryl α-allyloxymethyl acrylate, melyl α-allyloxymethyl acrylate, etc. α- (allyloxymethyl) acrylate is preferred. In addition, compounds exemplified in JP2013-061599A [0037] (for example, alkoxyalkyl-α- (allyloxymethyl) acrylate) are also suitable. Among these, methyl α-allyloxymethyl acrylate (also referred to as α- (allyloxymethyl) methyl acrylate) is particularly preferable.

The α- (unsaturated alkoxyalkyl) acrylate monomer can be produced by, for example, a production method disclosed in International Publication No. 2010/114077.

The content ratio of the monomer capable of introducing a ring structure into the main chain skeleton of the polymer (total ratio when two or more are used) is, for example, 1 to 40 mass with respect to 100 mass% of the base polymer component. % Is preferred. When it is within this range, it becomes possible to obtain a cured film having further improved heat resistance, dispersibility, surface hardness, and the like. In particular, the content ratio of N-substituted maleimide monomer, acrylic ether dimer, and / or α- (unsaturated alkoxyalkyl) acrylate monomer (total ratio when two or more types are used) It is preferable that it is 1-40 mass% with respect to 100 mass% of the said base polymer component. When the content of the main chain ring structure derived from these monomer components increases, the adhesion tends to be improved. Further, when the addition amount of the N-substituted maleimide monomer is further increased, a cured product that is superior in terms of hardness can be obtained, and by using an acrylic ether dimer, a cured product that is superior in terms of heat resistance coloring property can be obtained. can get. If the content ratio of the N-substituted maleimide monomer is too large, the development speed may not be more appropriate.
The content ratio of the N-substituted maleimide monomer, acrylic ether dimer, and / or α- (unsaturated alkoxyalkyl) acrylate monomer is more preferably 2 to 40% by mass, and still more preferably 3 to 35. % By mass.

(Iii) Other monomer The above monomer component is also, if necessary, other (meth) acrylic acid ester monomers and aromatic vinyl monomers not corresponding to the above-mentioned monomers. 1 type, or 2 or more types can be used.

The other (meth) acrylic acid ester monomers are dialkyl-2,2 ′-(oxydimethylene) diacrylate monomers and (meta) other than α- (unsaturated alkoxyalkyl) acrylates. ) Acrylic acid ester monomer.
Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) S-butyl acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, t-amyl (meth) acrylate, n- (meth) acrylate Hexyl, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, octyl (meth) acrylate, (meth) Isooctyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, Phenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (Meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 3-hydroxybutyl, (meth) acrylic acid 4-hydroxybutyl, (meth) acrylic acid 2-methoxyethyl, (Meth) acrylic acid 2-ethoxyethyl, (meth) acrylic acid phenoxyethyl, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid glycidyl, (meth) acrylic acid β-methylglycidyl, (meth) acrylic acid β -Ethyl glycidyl, (meth) acrylic acid (3,4- Xylcyclohexyl) methyl, N, N-dimethylaminoethyl (meth) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, etc., 1,4-dioxaspiro [4,5] deca-2 -Ylmethacrylic acid, (meth) acryloylmorpholine, tetrahydrofurfuryl acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2 -Methyl-2-isobutyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2,2-dimethyl -1,3-dioxolane, alkoxylated phenylphenol (meta Acrylate, and the like.

Among these, in terms of excellent heat resistance, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, alkoxylated phenylphenol It is also preferable to use (meth) acrylate. More preferably, in terms of excellent heat resistance, adhesion, and developability, methyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, and / or alkoxylated phenylphenol (meth) acrylate Is to use.

Examples of the aromatic vinyl monomer include styrene, vinyl toluene, α-methyl styrene, methoxy styrene, and the like. Of these, styrene and vinyltoluene are preferable from the viewpoint of heat resistance coloring property and heat decomposition property of the resin.

The content ratio of the other (meth) acrylic acid ester monomer and / or aromatic vinyl monomer (total ratio when two or more are used) is, for example, 100% by mass of the base polymer component. On the other hand, it is suitable that it is 0-80 mass%. When it is in this range, a cured product that is more excellent in heat-resistant colorability and alkali solubility can be obtained. More preferably, it is 1-80 mass%, More preferably, it is 5-75 mass%, Most preferably, it is 10-70 mass%.

Examples of the other monomer include (meth) acrylamides exemplified in JP2013-227485A [0051]; a macromonomer having a (meth) acryloyl group at one end of a polymer molecular chain. Conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; unsaturated isocyanates; The content is preferably 20% by mass or less in 100% by mass of the base polymer component.

Here, from the viewpoint of further improving the electrical characteristics of the cured product, it is preferable that the base polymer does not have a hydrophilic group such as a hydroxyl group. Therefore, it is preferable that the monomer component copolymerized to obtain the base polymer contains as little a monomer having a hydrophilic group as possible (for example, a (meth) acrylic acid ester having a hydroxyl group). Specifically, the content ratio of the monomer having a hydrophilic group is preferably 20% by mass or less in 100% by mass of the base polymer component. More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less.

As a method for polymerizing the monomer component, a commonly used technique such as bulk polymerization, solution polymerization, emulsion polymerization or the like can be used, and it may be appropriately selected according to the purpose and application. Among these, solution polymerization is preferred because it is industrially advantageous and structural adjustments such as molecular weight are easy. The polymerization mechanism of the monomer component may be a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization, but the polymerization method based on the radical polymerization mechanism is industrial. Is also preferable.

A preferred form of the polymerization reaction is as described in JP 2013-227485 A [0053] to [0065]. The polymerization time is preferably 1 to 12 hours, and more preferably 1 to 8 hours, for example.

The alkali-soluble resin is preferably a polymer obtained by reacting the base polymer obtained as described above with a compound having a functional group capable of binding to an acid group and a polymerizable double bond. Thereby, the sclerosis | hardenability of the said photosensitive resin composition is improved more, and the hardened | cured material excellent in adhesiveness with a board | substrate etc. and surface hardness can be obtained. Thus, the form in which the alkali-soluble resin is a polymer having a double bond in the side chain is one of the preferred forms of the present invention.

In the compound having a functional group capable of binding to the acid group and a polymerizable double bond, examples of the polymerizable double bond include a (meth) acryloyl group, a vinyl group, an allyl group, a methallyl group, and the like. A compound having one or more of these compounds is suitable. Of these, a (meth) acryloyl group is preferable in terms of reactivity. In addition, examples of the functional group capable of binding to an acid group include a hydroxy group, an epoxy group, an oxetanyl group, an isocyanate group, and the like, and those having one or more of these as the compound are suitable. . Of these, epoxy groups (including glycidyl groups) are preferred from the viewpoint of the speed of the modification treatment reaction, heat resistance, and dispersibility.

Examples of the compound having a functional group capable of binding to the acid group and a polymerizable double bond include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, Examples thereof include vinyl benzyl glycidyl ether, allyl glycidyl ether, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, vinylcyclohexene oxide, and the like, and one or more of these can be used. Among these, it is preferable to use a compound (monomer) having an epoxy group and a (meth) acryloyl group.

The amount of the compound having a functional group capable of binding to the acid group and a polymerizable double bond is, for example, 1 to 100 parts by mass of the base polymer component (total amount of monomer components constituting the base polymer). The amount is preferably 50 parts by mass. More preferably, it is 5-45 mass parts.

The amount of the compound having a functional group capable of binding to the acid group and a polymerizable double bond (mixing ratio) is also determined by the monomer having an acid group and a polymerizable double bond constituting the base polymer (this is referred to as “ The compounding ratio (mass%) of a compound having a functional group capable of binding to an acid group and a polymerizable double bond (hereinafter referred to as “compound y”) added to the carboxylic acid of “monomer x” That is, it is obtained by “{molar amount of compound y (mol) / molar amount of monomer x (mol)} × {mixing ratio of monomer x (mass%)}”, and is 50 mass% or less. It is preferable to set to. Thereby, the hardened | cured material with more favorable electrical characteristics can be obtained. More preferably, it is less than 50% by mass, whereby a cured product having more excellent electrical characteristics and light resistance can be obtained. More preferably, it is 45 mass% or less, Most preferably, it is 40 mass% or less, Most preferably, it is 35 mass% or less. Moreover, it is suitable that it is 5 mass% or more.
The “mixing ratio of monomer x (mass%)” here means the mixing of monomer x when the total amount of the base polymer component (monomer component forming the base polymer) is 100 mass%. It means quantity (mass%).
In addition, for example, GMA (glycidyl methacrylate) is used as a compound having a functional group capable of bonding to an acid group and a polymerizable double bond (compound y), and a monomer (single monomer having an acid group and a polymerizable double bond). When MAA (methacrylic acid) is used as the monomer x), the above-mentioned “mixing ratio (mass%) of the compound having a functional group capable of binding to an acid group and a polymerizable double bond” (mass%) ”is added. This means mass% in terms of MAA mass in terms of GMA, and is determined by “{GMA molar amount (mol) / MAA molar amount (mol)} × MAA blending ratio (mass%)”. It is preferable that this numerical value is within the above preferable range.

The side chain double bond-containing polymer is preferably obtained, for example, by the method described in JP 2013-227485 A [0069] to [0076].

The side chain double bond-containing polymer also preferably has an ethylenically unsaturated group equivalent, that is, a double bond equivalent of 200 to 10,000. Thereby, curability and storage stability become better. Especially, it is more preferable that it is 400-5000. The lower limit is more preferably 450 or more, particularly preferably 500 or more, and the upper limit is more preferably 4000 or less, still more preferably 3000 or less, particularly preferably 2000 or less, and most preferably 1500 or less.

The double bond equivalent is the mass (g) of the solid content of the polymer solution per 1 mol of the double bond of the polymer. The mass of the solid content of the polymer solution referred to here is, for example, the mass of the base polymer component, the mass of the monomer having a functional group capable of bonding to the acid group to be added to the base polymer and a polymerizable double bond. And the mass of the chain transfer agent. It can be determined by dividing the mass of the solid content of the polymer solution by the double bond amount of the polymer. The double bond amount of the polymer can be determined from the amount of the charged acid group and the monomer having a functional group capable of bonding and a polymerizable double bond.

<Polyfunctional polymerizable compound>
The photosensitive resin composition of the present invention also contains a polyfunctional polymerizable compound.
The polyfunctional polymerizable compound is a compound having two or more polymerizable unsaturated bonds (also referred to as polymerizable unsaturated groups) in the molecule. The polymerizable unsaturated group is a free radical, electromagnetic wave (for example, infrared ray, UV, X-ray, etc.), a group that can be polymerized by irradiation with active energy rays such as electron beams. A compound having at least two radical polymerizable unsaturated groups in the molecule is preferred.

Content (solid content) of the said polyfunctional polymerizable compound is 30-50 mass parts with respect to 100 mass parts of solid content of alkali-soluble resin. When it is 30 parts by mass or more, the surface hardness of the cured product is improved, and when it is 50 parts by mass or less, the dielectric constant of the cured product is reduced. In a product, high surface hardness and low dielectric constant can be achieved in a balanced manner. Preferably it is 35 mass parts or more, Preferably it is 45 mass parts or less.

The content (solid content) of the polyfunctional polymerizable compound is also preferably 10 to 20% by mass with respect to 100% by mass of the total solid content of the photosensitive resin composition. Within this range, a high surface hardness and a low dielectric constant can be achieved in a balanced manner in the cured product. More preferably, it is 18 mass% or less, More preferably, it is 15 mass% or less.

Although the molecular weight of the polyfunctional polymerizable compound is not particularly limited, it is preferably, for example, 2000 or less from the viewpoint of handling. More preferably, it is 1000 or less. Moreover, 100 or more are suitable.

Examples of the polyfunctional polymerizable compound include polyfunctional (meth) acrylate compounds described below (bifunctional (meth) acrylate compounds, trifunctional or more polyfunctional (meth) acrylate compounds, etc.), and JP2013-227485A. No. [0097] to [0098], polyfunctional vinyl ether compounds; vinyl ether group-containing (meth) acrylate compounds; polyfunctional allyl ether compounds; allyl group-containing (meth) acrylic esters; polyfunctional (meth) Acryloyl group-containing isocyanurates; polyfunctional allyl group-containing isocyanurates; polyfunctional urethane (meth) acrylates; polyfunctional aromatic vinyls; the above-mentioned unsaturated polyvalent carboxylic acids and unsaturated acid anhydrides; Can be mentioned.

Examples of the bifunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and butylene glycol di (meth) acrylate. Hexanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate, and the like.

Examples of the trifunctional or higher polyfunctional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, ethylene oxide-added trimethylolpropane tri ( (Meth) acrylate, ethylene oxide-added ditrimethylolpropane tetra (meth) acrylate, ethylene oxide-added pentaeri Ritol tetra (meth) acrylate, ethylene oxide-added dipentaerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added ditrimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (meth) Acrylate, propylene oxide-added dipentaerythritol hexa (meth) acrylate, ε-caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) Acrylate, ε-caprolactone-added dipentaerythritol hexa (meth) acrylate Relates and the like.

The number of functional groups of the polyfunctional polymerizable compound may be 2 or more, but is preferably 3 or more. Thereby, photosensitivity and sclerosis | hardenability can be improved more, and the hardness and transparency of hardened | cured material can be improved more. More preferably, it is 4 or more, More preferably, it is 5 or more. Further, from the viewpoint of further suppressing curing shrinkage, the functional number is preferably 10 or less, more preferably 8 or less.
Here, even if it is a polyfunctional polymerizable compound with few functional numbers, if it is a compound which has a fluorene skeleton, since the hardness of hardened | cured material can be improved more, it is preferable.
In addition, when it has two or more functional groups, the same functional group may be sufficient, but a different functional group may be sufficient.

Among the polyfunctional polymerizable compounds described above, from the viewpoints of reactivity, economy, availability, etc., polyfunctional (meth) acrylate compounds, polyfunctional urethane (meth) acrylate compounds, (meth) acryloyl group-containing isocyanurate compounds, etc. It is preferable to use a compound having a (meth) acryloyl group. More preferably, it is a polyfunctional (meth) acrylate compound (that is, a compound having two or more (meth) acryloyl groups), whereby the resin composition becomes more excellent in photosensitivity and curability, and has higher hardness. A highly transparent cured product can be obtained. More preferably, a trifunctional or higher polyfunctional (meth) acrylate compound is used.

<Inorganic fine particles>
The photosensitive resin composition of the present invention also contains inorganic fine particles. The inorganic fine particles mean fine particles containing an inorganic component and are suitable as a filler (also referred to as a filler).
The content (solid content) of the inorganic fine particles is 90 to 110 parts by mass with respect to 100 parts by mass of the solid content of the alkali-soluble resin. When it is 90 parts by mass or more, the light-resistant adhesion of the cured product is improved, and when it is 110 parts by mass or less, the dielectric constant of the cured product is reduced, so that it is in the range of 90 to 110 parts by mass, In the cured product, high surface hardness and high light-resistant adhesion can be achieved in a balanced manner. Preferably it is 95 mass parts or more, Preferably it is 105 mass parts or less.

The content of the inorganic fine particles (solid content) is also preferably 20 to 30% by mass with respect to 100% by mass of the total solid content of the photosensitive resin composition. Within this range, in the cured product, both high surface hardness and high light-resistant adhesion can be achieved in a well-balanced manner in the cured product. More preferably, it is 23 mass% or more, More preferably, it is 25 mass% or more.

Examples of the inorganic fine particles include metalloids or metals, salts thereof (carbonates, sulfates, etc.), oxides thereof, and the like. Among these, a semimetal or a metal oxide is preferable. One molecule may have one or more metalloid atoms or metal atoms.

The metalloid or metal is not particularly limited. For example, the metal is preferably silicon, and the metal is preferably titanium, zirconium, calcium, barium, aluminum, or the like. More preferred is silicon, zirconium, titanium and / or aluminum. Among these, from the viewpoint of further increasing the surface hardness, it is preferable to contain at least silicon, whereby a cured product having an even higher surface hardness can be obtained. For example, silicon oxide (such as silica); a composite metal oxide containing other metal (or metalloid) atoms in addition to silicon is preferable. More preferred are silica fine particles.

The average particle diameter of the inorganic fine particles is preferably 1 to 500 nm, for example. By being in this range, the dispersibility and dispersion stability of the inorganic fine particles become more sufficient, and it becomes possible to give a cured product that is superior in dispersibility and further suppressed in change with time. More preferably, it is 1-300 nm, More preferably, it is 1-200 nm, Most preferably, it is 1-100 nm.
The average particle diameter can be measured, for example, using a laser diffraction particle size distribution measuring machine.

The inorganic fine particles may be in the form of a powder that has been dried, or in the form of a dispersion (eg, colloidal silica) dispersed in an organic solvent. From the viewpoint of dispersion stability, it is preferable to use a dispersion in which the dispersion is dispersed in an organic solvent. That is, the inorganic fine particles are preferably contained in the photosensitive resin composition as an organic solvent dispersion.

Examples of the organic solvent (dispersion medium) used for forming the dispersion include ketone solvents, ester solvents, ether solvents, alcohol solvents, amide solvents, xylene, toluene, and the like. These 1 type (s) or 2 or more types can be used. Among them, it is preferable to use a ketone solvent, an ester solvent and / or an ether solvent. More preferably, a ketone-based solvent and / or an ester-based solvent is used, whereby the dispersibility can be maintained with no change in appearance such as discoloration, coloring, cracking, etc., and the curing has high surface hardness and adhesion. You can get things.
Specific examples of each solvent include various solvents described in JP2013-227485A [0024].

When a dispersion formed by dispersing in an organic solvent is used as the inorganic fine particles, the amount of the organic solvent (dispersion medium) is preferably set to an amount capable of sufficiently dispersing the inorganic fine particles. That is, the amount of the organic solvent used can be adjusted so that the content of the inorganic fine particles in the photosensitive resin composition is within the above-described preferable range and the inorganic fine particles are sufficiently dispersed. preferable. For example, the total amount of the organic solvent as the dispersion medium is preferably 50 parts by mass or more with respect to 100 parts by mass of the inorganic fine particles. More preferably, it is 70 mass parts or more, More preferably, it is 100 mass parts or more. Moreover, since there exists a possibility that a hardening process cannot be performed simply when there is too much solvent amount more than necessary, it is suitable that it is 600 mass parts or less. More preferably, it is 550 mass parts or less, More preferably, it is 500 mass parts or less.

The organic solvent dispersion can be obtained by sufficiently dispersing the inorganic fine particles in the organic solvent described above, but commercially available products can also be used. For example, MEK-ST, MEK-ST-L, MEK-ST-ZL, MEK-ST-UP, MEK-AC-2101, MEK-AC-4101, MEK-EC-2104, MEK-AC-2202, MEK- Organosilica sol with methyl ethyl ketone as dispersion medium such as AC-5101; Organosilica sol with methyl isobutyl ketone as dispersion medium such as MIBK-ST, MIBK-SD, MIBK-SD-L; Dispersion medium with ethyl acetate as EAC-ST Organosilica sol with butyl acetate as a dispersion medium such as NBAC-ST; Organosilica sol with methanol as a dispersion medium such as methanol silica sol and MA-ST-M; IPA-ST, IPA-ST-L, etc. Organosilica sol with isopropanol as dispersion medium; EG-ST, etc. Organosilica sol using ethylene glycol as dispersion medium; Organosilica sol using xylene / n-butanol as dispersion medium such as XBA-ST; Organo using alkylene glycol monoalkyl ether such as NPC-ST-30 and PGM-ST as dispersion medium Examples include silica sol; organosilica sol using dimethylacetamide such as DMAC-ST as a dispersion medium; organosilica sol using toluene as a dispersion medium such as TOL-ST; and the like (all manufactured by Nissan Chemical Co., Ltd.).

Here, in the photosensitive resin composition of the present invention, the other constitutions of the present invention are satisfied even when other inorganic compounds such as organic-inorganic hybrid compounds are used instead of or together with the inorganic fine particles. If it is a thing, it can give the hardened | cured material which has sufficient surface hardness and is excellent in various physical properties, such as an electrical property and adhesiveness.
That is, a photosensitive resin composition containing an alkali-soluble resin, a polyfunctional polymerizable compound, an inorganic compound, and a photopolymerization initiator, wherein the alkali-soluble resin has a weight average molecular weight of 15,000 to 20,000 and an acid value of 50 to 80 mgKOH The solid content of the alkali-soluble resin is 20 to 30% by mass with respect to 100% by mass of the total solid content of the photosensitive resin composition, and is 100 parts by mass of the solid content of the alkali-soluble resin. , 30 to 50 parts by mass of the polyfunctional polymerizable compound, 90 to 110 parts by mass of the total amount of the inorganic compound, and 60 to 80 parts by mass of the photopolymerization initiator (all having a solid content) A thing is also one of the inventions by this inventor.
As the inorganic compound, inorganic fine particles and / or organic-inorganic hybrid compounds are preferable. The organic-inorganic hybrid compound is as described later.

<Photopolymerization initiator>
The photosensitive resin composition of the present invention also contains a photopolymerization initiator.
Content (solid content) of a photoinitiator is 60-80 mass parts with respect to 100 mass parts of solid content of alkali-soluble resin. By being 60 mass parts or more, the light-resistant adhesiveness and surface hardness of hardened | cured material are improved, and the storage stability of a resin composition will become favorable as it is 80 mass parts or less. Preferably it is 65 mass parts or more, More preferably, it is 70 mass parts or more, Preferably it is 75 mass parts or less.

The content (solid content) of the photopolymerization initiator is also preferably 10 to 25% by mass with respect to 100% by mass of the total solid content of the photosensitive resin composition. Within this range, the light-resistant adhesion and surface hardness of the cured product are further improved, and the storage stability of the resin composition is further improved. More preferably, it is 15 mass% or more, More preferably, it is 18 mass% or more, More preferably, it is 23 mass% or less.

The photopolymerization initiator is preferably a radical polymerizable photopolymerization initiator.
A radical polymerizable photopolymerization initiator is one that generates a polymerization initiating radical by irradiation with an active energy ray such as an electromagnetic wave or an electron beam, and one or more commonly used ones can be used. . Moreover, you may use together 1 type (s) or 2 or more types of photosensitizers, radical photopolymerization promoters, etc. as needed. Sensitivity and curability are further improved by using a photosensitizer and / or a radical photopolymerization accelerator in combination with the photopolymerization initiator.

Specific examples of the photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“IRGACURE907”, manufactured by BASF), 2-benzyl. 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (“IRGACURE369”, manufactured by BASF), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morphol Aminoketone compounds such as phospho-4-yl-phenyl) -butan-1-one (“IRGACURE379”, manufactured by BASF); 2,2-dimethoxy-1,2-diphenylethane-1-one (“IRGACURE651”, BASF), phenylglyoxylic acid methyl ester ("DAROCUR MBF", manufactured by BASF), etc. 1-hydroxy-cyclohexyl-phenyl-ketone (“IRGACURE184”, manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (“DAROCUR1173”, manufactured by BASF) ), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (“IRGACURE2959”, manufactured by BASF), 2-hydroxy-1- {4 -[4- (2-Hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (“IRGACURE127”, manufactured by BASF), [1-hydroxy-cyclohexyl-phenyl- Ketone + Benzophenone] ("IRGACURE500", manufactured by BASF) In addition to the above-mentioned hydroketone compounds, alkylphenone compounds, benzophenone compounds, benzoin compounds, thioxanthone compounds, halomethylated triazine compounds exemplified in JP2013-227485A [0084] to [0086] Halomethylated oxadiazole compounds; biimidazole compounds; oxime ester compounds; titanocene compounds; benzoate ester compounds; acridine compounds and the like; phosphine oxide compounds; oxime ester compounds;

Among the photopolymerization initiators, it is particularly preferable to use at least an aminoketone compound (also referred to as an aminoketone polymerization initiator). That is, the photopolymerization initiator preferably includes an aminoketone polymerization initiator. Thereby, hardness and developability become more excellent. It is also preferable to use a hydroketone compound (also referred to as a hydroketone polymerization initiator) or a benzyl ketal compound (also referred to as a benzyl ketal polymerization initiator).

In the present invention, as described above, it is preferable to use an aminoketone polymerization initiator as the polymerization initiator. In this case, the total amount of the polymerization initiator (that is, the aminoketone polymerization initiator and other polymerization initiators) The aminoketone polymerization initiator is preferably 20% by mass or more with respect to 100% by mass of the total amount). More preferably, it is 30 mass% or more, More preferably, it is 50 mass% or more, Most preferably, it is 55 mass% or more.

<Solvent>
It is preferable that the photosensitive resin composition also contains a solvent. A solvent is preferably used as a diluent or the like. That is, specifically, the viscosity is lowered and the handleability is improved; the coating film is formed by drying; the coloring material is used as a dispersion medium; and the like. It is a low-viscosity organic solvent that can dissolve or disperse each of the components.

As the solvent, one or more commonly used solvents can be used, and it may be appropriately selected depending on the purpose and application, and is not particularly limited. For example, monoalcohols; glycols; cyclic ethers; glycol monoethers; glycol ethers; esters of glycol monoethers (eg, propylene glycol monomethyl ether) exemplified in JP2013-227485A [0092] Acetates; alkyl esters; ketones; aromatic hydrocarbons; aliphatic hydrocarbons; amides;

The amount of the solvent used may be appropriately set according to the purpose and application, and is not particularly limited, but is 10 to 90% by mass in the total amount of 100% by mass of the photosensitive resin composition of the present invention. It is preferable. More preferably, it is 20-80 mass%, Most preferably, it is 40-80 mass%, Most preferably, it is 60-80 mass%.

<Other ingredients>
The photosensitive resin composition of the present invention may also contain one or more other components (also referred to as other components) as necessary (for example, depending on the required characteristics of each application to be applied). Good.
Examples of other components include coupling agents; polymerization inhibitors; fluorine additives; polymerizable compounds other than polyfunctional polymerizable compounds; fillers other than inorganic fine particles; photosensitizers; photoradical polymerization accelerators; (Also referred to as a colorant); dispersant; heat resistance improver; leveling agent; development aid; filler; thermosetting resin such as epoxy resin, phenol resin, and polyvinylphenol; curing aid such as polyfunctional thiol compound; plasticizer UV absorber, antioxidant, matting agent, antifoaming agent, antistatic agent, slip agent, surface modifier, thixotropic agent, thixotropic agent, quinonediazide compound, polyhydric phenol compound, cationic polymerizable compound Acid generator; leveling agent; and the like.

It is preferable that content (solid content) of the said other component (The total mass when 2 or more types of other components are included) is 0-100 mass parts with respect to 100 mass parts of solid content of alkali-soluble resin. More preferably, it is 1-80 mass parts, More preferably, it is 2-60 mass parts, Most preferably, it is 5-60 mass parts.

The content (solid content) of the other component (the total mass when two or more other components are included) is also 0 to 40% by mass with respect to 100% by mass of the total solid content of the photosensitive resin composition. Is preferred. More preferably, it is 1-40 mass%, More preferably, it is 5-30 mass%.

Among the other components described above, it is preferable to include a coupling agent and / or a fluorine additive. When the photosensitive resin composition further includes a coupling agent, the adhesion can be further improved, and by further including the fluorine additive, the curability can be further improved. Moreover, when using the said photosensitive resin composition for a color filter use, it is preferable that a coloring material is included. Furthermore, it is preferable to contain a polymerization inhibitor from the viewpoint of improving storage stability.
Below, coupling agents, fluorine additives, polymerizable compounds other than polyfunctional polymerizable compounds (also referred to as other polymerizable compounds), fillers other than inorganic fine particles (also referred to as other fillers), photosensitizers Further, the radical photopolymerization accelerator will be further described.

-Coupling agent-
The coupling agent has a property of bonding with an oxidized surface of an inorganic substance by a hydrolysis reaction or a condensation reaction. By using this property, for example, adhesion to a substrate or the like on which ITO or the like is deposited is performed. It becomes possible to fully exhibit the property. Thus, the form in which the photosensitive resin composition further contains a coupling agent is also one of the preferred forms of the present invention.

When the said coupling agent is included, it is preferable that the content (solid content) is 10-90 mass parts with respect to 100 mass parts of solid content of alkali-soluble resin. More preferably, it is 20-80 mass parts, More preferably, it is 20-60 mass parts.

The content (solid content) of the coupling agent is also preferably 0 to 35% by mass with respect to 100% by mass of the total solids of the photosensitive resin composition. More preferably, it is 5-30 mass%.

Specific examples of the coupling agent include, for example, vinyl group, (meth) acryl group, epoxy group, amino group, mercapto group, -N = C = O group, -N (R) -C (= O)-. A coupling agent having a group (R represents a hydrogen atom (H) or an arbitrary group) or the like is preferable. Among these, those having a vinyl group, a (meth) acryloyl group and / or an epoxy group are preferable. More preferred is a (meth) acryloyl group. Further, as the central metal, those containing so-called semimetals such as silicon atoms, titanium, zirconium, calcium, barium, aluminum and the like are preferable, but among these, silicon, zirconium, titanium and / or aluminum are more preferable. . Among these, from the viewpoint of further increasing the adhesion and surface hardness of the cured product, silicon is more preferable, and the form in which the coupling agent is a silane coupling agent is one of the preferred forms of the present invention.
One molecule may have one or more metalloid atoms or metal atoms.

As the silane coupling agent, group and one or more of the above-described alkoxysilane groups _{^{(-Si (OR 4) 3-}} n (R 5) n; OR 4 represents a hydrolyzable group, R ⁴ is preferably a hydrocarbon group, R ⁵ is a hydrocarbon group, and n is 0, 1 or 2. Among them, it is preferable to use a silane coupling agent having a vinyl group, a (meth) acryloyl group and / or an epoxy group, so that there is no change over time in appearance such as discoloration, coloring, cracks, etc. even after exposure to high temperatures, A cured product having more sufficient surface hardness and adhesion can be obtained.

Examples of the silane coupling agent having a vinyl group include vinyltrimethoxysilane and vinyltriethoxysilane.

Examples of the silane coupling agent having the (meth) acryloyl group include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, and 3- (meth) acryloxypropyltri Examples include methoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, and 3- (meth) acryloxypropyltriethoxysilane.

Specific examples of the silane coupling agent having an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Examples thereof include glycidoxypropylmethyldimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

Examples of the silane coupling agent having an amino group include N-phenyl-3-aminopropyltrimethoxysilane.
Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.

Examples of the silane coupling agent having a —N═C═O group include 3-isocyanatopropyltriethoxysilane and the like, and a silane coupling agent having a —N (R) —C (═O) — group. Examples include tris- (trimethoxysilylpropyl) isocyanurate.

Among the silane coupling agents, a silane coupling agent having a (meth) acryloyl group is particularly preferable, and thereby the storage stability of the resin composition becomes better. In addition, the adhesion is further improved.
In addition, as a coupling agent which has metals other than silicon as a central metal, a zirco aluminate coupling agent, a titanate coupling agent, etc. are mentioned, for example.

-Fluorine-based additive-
A fluorine-based additive (also referred to as a fluorine additive) is a compound having a fluorine atom in the structure, and by including this, the curability of the photosensitive resin composition can be further improved.
Note that the fluorine-based additive also has a function as a leveling agent.

When the said fluorine-type additive is included, it is preferable that the content (solid content) is 0.05-10 mass parts with respect to 100 mass parts of solid content of alkali-soluble resin. More preferably, it is 0.1-5 mass parts.

The content (solid content) of the fluorine-based additive is preferably 0.05 to 5% by mass with respect to 100% by mass of the total solid content of the photosensitive resin composition. More preferably, it is 0.1-3 mass%, More preferably, it is 0.1-2 mass%.

As the fluorine-based additive, compounds usually used as a fluorine-based surfactant or a fluorine-based surface modifier can be used.

The fluorine-based additive is also soluble in various organic solvents (for example, ether solvents, ester solvents, ketone solvents, alcohol solvents, etc.) from the viewpoint that it is preferable not to separate components in the photosensitive resin composition. Those having high properties are more preferably used. Specifically, for example, those having an HLB value (hydrophilic / lipophilic balance) in the range of 0 to 16 are suitable. The HLB value is more preferably 1-13.
The HLB value is obtained by, for example, the Griffin method or the Davis method.

The fluorine-containing additive preferably further contains 0.01 to 80% by mass of fluorine in a total amount of 100% by mass of the fluorine-based additive. The fluorine content can be quantified by, for example, ion chromatography.

The fluorine-based additive also includes nonionic and anionic ones, and nonionic ones are preferable from the viewpoint of dispersibility with the resin and the like.

Specific examples of the fluorine-based additive include perfluorobutane sulfonate (Megafac F-114), perfluoroalkyl group-containing carboxylates (Megafac F-410), perfluoroalkylethylene oxide adducts ( Mega-Fuck F-444, EXP.TF-2066), perfluoroalkyl group-containing phosphate ester (Mega-Fact EXP.TF-2148), perfluoroalkyl group-containing phosphate ester-type neutralized amine (MegaFack EXP.TF) -2149), fluorine-containing group / hydrophilic group-containing oligomer (Megafac F-430, EXP • TF-1540), fluorine-containing group / lipophilic group-containing oligomer (Megafac F-552, F-554, F-558) F-561, R-41), fluorine-containing group / hydrophilic group / lipophilic group-containing o Gomer (Megafuck F-477, F-553, F-555, F-556, F-557, F-559, F-562, R-40, EXP / TF-1760), fluorine-containing group / hydrophilic group -Oligophilic group / UV-reactive group-containing oligomer (Megafac RS-72-K, RS-75, RS-76-E, RS-76-NS, RS-77), etc. ). Among them, compounds containing lipophilic groups (fluorinated group / lipophilic group-containing oligomers, fluorine-containing groups / hydrophilic groups / lipophilic group-containing oligomers, fluorine-containing groups / hydrophilic groups / lipophilic groups / UV-reactive groups) Oligomer) is preferred.

-Other polymerizable compounds-
As the other polymerizable compound, a monofunctional compound having one polymerizable unsaturated group in the molecule (referred to as a monofunctional polymerizable compound) is preferable.
Specific examples of the monofunctional polymerizable compound include, for example, N-substituted maleimide monomers and (meth) acrylic among the compounds exemplified above as monomers preferably contained in the monomer component of the alkali-soluble resin. Acid esters; (meth) acrylamides; unsaturated monocarboxylic acids; unsaturated polycarboxylic acids; unsaturated monocarboxylic acids in which the chain between the unsaturated group and the carboxyl group is extended; unsaturated acid anhydrides; Aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; unsaturated isocyanates; Among these, (meth) acrylic acid ester monomers are preferable. That is, in other words, a monofunctional (meth) acrylate compound is preferable.

Examples of the monofunctional (meth) acrylate compound include monofunctional (meth) acrylate compounds having an aliphatic hydrocarbon group and monofunctional (meth) acrylate compounds having an aromatic ring (aromatic hydrocarbon group). Among them, the former is preferable, and a compound having one (meth) acryloyl group and an aliphatic hydrocarbon group having 1 to 24 carbon atoms in one molecule is particularly preferable. Specific examples of the aliphatic hydrocarbon group include an aliphatic saturated hydrocarbon group (alkyl group) and an aliphatic unsaturated hydrocarbon group (for example, alkenyl group). Among these, an aliphatic saturated hydrocarbon group is preferable because the effects of the present invention can be more fully exhibited. Specifically, a group represented by C _n H _{2n + 1} (n = 1 to 24) is preferable.

The aliphatic hydrocarbon group preferably has 1 to 24 carbon atoms. As a result, the surface hardness of the cured product becomes more sufficient, and the compatibility with other components is also improved. Preferably it is 22 or less as carbon number, More preferably, it is 20 or less. Specifically, for example, a monofunctional (meth) acrylate compound having an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or a fat having 5 to 24 carbon atoms (preferably 8 to 22, more preferably 10 to 20 carbon atoms). It is preferable to use a monofunctional (meth) acrylate compound having a group hydrocarbon group.

The monofunctional (meth) acrylate compound having an aliphatic hydrocarbon group is preferably, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n -Butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, t-amyl (meth) acrylate, n-hexyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate Both ), Tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, cetyl (meth) acrylate, 2-decyltetradecyl (Meth) acrylate, 2-decyltetradecanyl (meth) acrylate, eicosyl (meth) acrylate, compounds having a linear or branched aliphatic hydrocarbon group such as behenyl (meth) acrylate; isobornyl (meth) acrylate And compounds having an aliphatic hydrocarbon group having a cyclic structure such as adamantyl (meth) acrylate; Among these, compounds having an aliphatic saturated hydrocarbon group having a preferable carbon number described above are more preferable.

When the photosensitive resin composition contains the monofunctional (meth) acrylate compound having an aliphatic hydrocarbon group, which is an optional component described above, the content is 100% by mass of the total solid content of the photosensitive resin composition. It is suitable that it is 3-20 mass% with respect to. Thereby, transparency of hardened | cured material is improved more. More preferably, it is 4 mass% or more, More preferably, it is 15 mass% or less, More preferably, it is 12 mass% or less.

-Other fillers-
As the other filler, for example, an organic-inorganic hybrid compound such as a semimetal or an organic compound containing a metal is suitable. The metalloid or metal is the same as that described for the inorganic fine particles, and those containing silicon are particularly suitable.
The organic-inorganic hybrid compound does not include the above-described coupling agent. For example, the organic-inorganic hybrid compound preferably has a molecular weight exceeding 2000.

The organic-inorganic hybrid compound is an organic compound containing a metalloid atom or metal atom, that is, a compound containing a metalloid atom or metal atom and an organic group. Such an organic-inorganic hybrid compound is preferably a silsesquioxane compound; a compound having a semimetal atom or metal atom, an alkoxy group, and a structural unit derived from a polymerizable monomer (also referred to as an alkoxy group-containing compound) ; These preferred forms are as described later. Among these, from the viewpoint of further improving the surface hardness, the latter alkoxy group-containing compound is preferable.
The structural unit derived from the polymerizable monomer means a structure in which the polymerizable double bond (C═C) of the polymerizable monomer is opened to form a single bond (—C—C—). .

The organic-inorganic hybrid compound preferably contains a siloxane bond (Si—O—Si bond). In this case, examples of the structure of the siloxane skeleton that essentially requires a siloxane bond include a chain shape (straight or branched), a ladder shape, a net shape, a ring shape, a cage shape, a cubic shape, and the like. Especially, since the effect is easily exhibited even if the addition amount of the organic-inorganic hybrid compound is small, a ladder shape, a net shape, or a cage shape is preferable. The proportion of the siloxane skeleton is preferably 10 to 80% by mass when one molecule of the organic-inorganic hybrid compound is 100% by mass.

Although the molecular weight of the organic-inorganic hybrid compound is not particularly limited, the weight average molecular weight is preferably 200,000 or less from the viewpoint of developability. The lower limit of the weight average molecular weight is preferably more than 2000.

(I-1) Silsesquioxane Compound As the silsesquioxane compound, for example, a compound having a basic skeleton represented by a general formula: R ⁶ SiO _1.5 (R ⁶ represents an organic group) is used. Preferably, an organic group having, for example, a methyl group, a phenyl group, a methyl group and a phenyl group, or a thiol group and a methyl group is suitable.

Specific examples of the silsesquioxane compound include TM-100 (silsesquioxane derivative, manufactured by Toagosei Co., Ltd.); SR-13, SR-23, SR-20, SR-3321 (polysilsesquioxane, All of them are commercially available products (all trade names).

(I-2) Alkoxy group-containing compound In a compound (alkoxy group-containing compound) having a semi-metal atom or metal atom, an alkoxy group, and a structural unit derived from a polymerizable monomer, a configuration derived from a polymerizable monomer Although it does not specifically limit as a polymerizable monomer which forms a unit, For example, an unsaturated monocarboxylic acid type monomer, an unsaturated dicarboxylic acid type monomer, a (meth) acrylic acid ester type monomer, an aromatic A vinyl-type monomer, a urethane-type monomer, etc. are mentioned, These 1 type (s) or 2 or more types are suitable. Among them, (meth) acrylic skeleton monomers (C) such as (meth) acrylic acid ester monomers and (meth) acrylic acid (salt) monomers that are a kind of unsaturated monocarboxylic acid monomers ^{= C (R a) -COO-;} . R a is a monomer having a representative) a hydrogen atom or a methyl group ((meth) referred to as acrylic monomer) is preferred.

The (meth) acrylic acid (salt) monomer is acrylic acid, methacrylic acid or a salt thereof. Examples of the salt herein include metal salts, ammonium salts, and organic amine salts. Specifically, for example, monovalent metal salts such as sodium salts, lithium salts, and potassium salts; two salts such as magnesium salts and calcium salts; Metal salt; transition metal salt such as iron salt; alkanolamine salt such as monoethanolamine salt, diethanolamine salt and triethanolamine salt; alkylamine salt such as monoethylamine salt, diethylamine salt and triethylamine salt; Examples thereof include salts of organic amines such as polyamines such as ethylenediamine salts. The salt is preferably a sodium salt or a potassium salt.

As said (meth) acrylic acid ester-type monomer, the compound which has a C1-C30 hydrocarbon group is preferable, for example, (meth) acrylic acid methyl, (meth) acrylic acid ethyl, N-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylic acid n-amyl, s-amyl (meth) acrylate, t-amyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, (meth) Tridecyl acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic acid Sooctyl, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, trimethyl (meth) acrylate And cyclodecanyl. Among these, (meth) acrylic acid ester-based singles having a hydrocarbon group having 1 to 10 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and cyclohexyl (meth) acrylate. A monomer is preferred. The hydrocarbon group is preferably an alkyl group.

The alkoxy group is preferably bonded to a metalloid atom or a metal atom. That is, the alkoxy group-containing compound is a compound having an alkoxy group bonded to a metalloid atom or a metal atom and a structural unit derived from a polymerizable monomer (preferably a (meth) acrylic monomer). Is preferred. As an alkoxy group bonded to a metalloid atom or a metal atom, the following formula (3);
_{^{-X (OR 7) a-n}} (R 8) n (3)
(In the formula, X represents a metalloid atom or a metal atom. R ⁷ represents an alkyl group. R ⁸ represents a hydrocarbon group. A represents the number of bonds of the atom represented by X − .n representing the 1, 0 or more, (a-1) there may be mentioned groups represented by the following represents a number.), R ⁷ in formula (3), represents an alkyl group or an aryl group Is preferred. Of these, an alkyl group is preferred. n is preferably 0.

More preferably, as the group represented by the above formula (3), the following formula (4);
—Si (OR ⁷ ) _{3-n ′} (R ⁸ ) _{n ′} (4)
(Wherein R ⁷ and R ⁸ are as described above. N ′ represents a number of 0 or more and 2 or less), that is, an alkoxysilyl group-containing group. Thereby, the adhesiveness with respect to substrates, such as ITO, improves more, and the heat-resistant coloring property of a cured film is also improved. Also in formula (4), n ′ is most preferably 0.

Specific examples of the alkoxy group-containing compound include Composelane AC (alkoxy group-containing silane-modified acrylic resin: for example, AC601, AC611), Composelan E (alkoxy group-containing silane-modified bisphenol A type epoxy resin, alkoxy group-containing silane-modified novolak type). Epoxy resin), Composelan P (alkoxy group-containing silane-modified phenol resin), Composelan H800 (alkoxy group-containing silane-modified polyamic acid resin), Composelan H700 (alkoxy group-containing silane-modified soluble polyimide resin), Composelan H900 (alkoxy group-containing silane-modified) Polyamideimide resin, Juliano U (alkoxy group-containing silane-modified polyurethane resin: for example, U201, U301, U303), Composelan HBSQ105-7 ( Z-12-2226, KR-513, X-41-1810 (all manufactured by Shin-Etsu Chemical Co., Ltd.), etc. (all trade names). A compound having a silyl group-containing group is preferred.

-Photosensitizer, radical photopolymerization accelerator-
As described above, by using a photosensitizer and / or a radical photopolymerization accelerator together with a photopolymerization initiator, sensitivity and curability are further improved. Examples of photosensitizers and photoradical polymerization accelerators include dye-based compounds; dialkylaminobenzene-based compounds; mercaptan-based hydrogen donors and the like exemplified in JP2013-227485A [0088]. .

The content (total amount) of the photosensitizer and / or photoradical polymerization accelerator may be appropriately set depending on the purpose and application, and is not particularly limited. From the viewpoint of balance, it is preferably 0.001 to 20% by mass with respect to 100% by mass of the total solid content of the photosensitive resin composition. More preferably, it is 0.01-15 mass%, More preferably, it is 0.05-10 mass%.

<Method for producing photosensitive resin composition>
It does not specifically limit as a manufacturing method of the photosensitive resin composition of this invention, For example, it can prepare by mixing and disperse | distributing the component mentioned above using various mixers and a disperser. A dispersion process and a mixing process are not specifically limited, What is necessary is just to perform by a normal method. Further, it may further include other steps that are normally performed. In the case where the photosensitive resin composition contains a color material, it is preferable to produce the color material through a color material dispersion treatment step.

[Curing film]
Next, the cured film formed using the photosensitive resin composition of the present invention will be described.
The photosensitive resin composition of the present invention can form a cured film by irradiation (exposure) with active energy rays. Specifically, for example, the photosensitive resin composition is applied onto a substrate (also referred to as a base material) and dried, and a cured film is formed by irradiating (exposing) an active energy beam to the coated surface. It is preferable. Thus, the cured film formed with the said photosensitive resin composition is also one of this invention. In addition, since the photosensitive resin composition is suitably used as a resist material, the form in which the cured film formed from the photosensitive resin composition is a resist cured film is also a preferred form of the present invention. One.

The substrate (also referred to as a base material) on which the photosensitive resin composition is applied is not particularly limited. For example, a transparent glass substrate such as white plate glass, blue plate glass, silica coated blue plate glass; polyethylene terephthalate (PET), polyester Sheet or film made of thermoplastic resin such as ring-opening polymer of polycarbonate, polyolefin, polysulfone, cyclic olefin or hydrogenated product thereof; Sheet or film made of thermosetting resin such as epoxy resin or unsaturated polyester resin; Aluminum Metal substrates such as plates, copper plates, nickel plates, and stainless steel plates; ceramic substrates; semiconductor substrates having photoelectric conversion elements; members composed of various materials such as glass substrates (color filters for LCD) having a color material layer on the surface; Etc. Especially, the sheet | seat or film which consists of heat resistant resin among a glass substrate and a plastic substrate from a heat resistant point is preferable. The substrate is preferably a transparent substrate.

If necessary, the substrate may be subjected to corona discharge treatment, ozone treatment, chemical treatment with a silane coupling agent, etc., and an inorganic component such as a gas barrier layer or a protective film on both sides or one side of the substrate. Or you may form the coating film of an organic component. Moreover, when using a cured film for the member for display apparatuses, it is suitable to form electrodes, such as ITO, on the said board | substrate. In addition, the cured film of this invention is excellent also in adhesiveness with not only a board | substrate but electrodes, such as an ITO film | membrane.

The method for applying the photosensitive resin composition to the substrate is not particularly limited, and examples thereof include spin coating, slit coating, roll coating, and cast coating, and any method can be preferably used.

The coating film after being applied to the substrate can be dried using, for example, a hot plate, an IR oven, a convection oven, or the like. The drying conditions are appropriately selected according to the boiling point of the solvent component contained, the type of the curing component, the film thickness, the performance of the dryer, etc., but are usually performed at a temperature of 50 to 150 ° C. for 10 seconds to 300 seconds. Is preferred.

As the light source of the active energy ray and the method of the exposure device, for example, the light source and the method of the exposure device exemplified in JP 2013-227485 A [0161] can be used.
In the irradiation process of the active energy beam, the active energy beam may be irradiated through a predetermined mask pattern depending on the application. In this case, the exposed portion is cured, and the cured portion is insolubilized or hardly soluble in the developer.

Further, if necessary, after the step of irradiating with the active energy beam, a step of developing with a developer to remove an unexposed portion and forming a pattern (also referred to as a developing step) may be performed. Thereby, a patterned cured film can be obtained.
The development process in the development step can be usually performed at a development temperature of 10 to 50 ° C. by a method such as immersion development, spray development, brush development, or ultrasonic development. In addition, when using alkaline aqueous solution as a developing solution, it is preferable to wash | clean with water after image development.

The developer is not particularly limited as long as it dissolves the photosensitive resin composition of the present invention. Usually, an organic solvent or an alkaline aqueous solution is used, and a mixture thereof may be used.
Examples of the organic solvent suitable as the developer include ether solvents and alcohol solvents, and specific examples thereof include those described in JP2013-227485A [0163].

In addition to the alkaline agent, the alkaline aqueous solution may contain a surfactant, an organic solvent, a buffering agent, a dye, a pigment, and the like as necessary. Examples of the organic solvent in this case include organic solvents suitable as the developer described above. As the alkali agent, for example, one or two or more of inorganic alkali agents, amines, and the like exemplified in JP2013-227485A [0164] can be used. For example, 1 type, or 2 or more types, such as a nonionic surfactant; anionic surfactant; amphoteric surfactant, etc. which were illustrated by Unexamined-Japanese-Patent No. 2013-227485 [0165] can be used.

Further, if necessary, a post-curing step (also referred to as post-baking or post-treatment step) may be performed. The post-curing step includes, for example, a post-heating step (also referred to as a heat treatment step) in addition to a step of exposing with a light amount of, for example, 0.5 to 5 J / cm ² using a light source such as a high-pressure mercury lamp. . By performing such post-treatment, it becomes possible to further strengthen the hardness and adhesion of the patterned cured film.

Among the post-treatment steps described above, the latter heat treatment step is preferred, and the temperature at that time is preferably 60 ° C. or higher. By performing the heat treatment step in this temperature range, the reactive compound is decomposed, and the effects of the present invention can be more fully exhibited. A form in which the cured film is heat-treated at a temperature of 60 ° C. or higher is also a preferred form of the present invention. The heat treatment temperature is more preferably 80 ° C. or higher, and preferably 300 ° C. or lower. Moreover, although heat processing time is not specifically limited, For example, it is preferable that it is 10 seconds-300 minutes.

[Use of photosensitive resin composition, etc.]
The photosensitive resin composition of the present invention provides a cured product (cured film) having a high surface hardness and excellent in various physical properties such as electrical characteristics and adhesion. Therefore, the cured product (cured film) formed from such a photosensitive resin composition is, for example, a component member of various display devices such as a liquid crystal display device, a solid-state imaging device, a touch panel display device, ink, printing, and the like. It is preferably used for various applications such as various optical members such as plates, printed wiring boards, semiconductor elements, and photoresists, electric machines and electronic devices. Among them, it is preferable to use for color filters used for liquid crystal display devices, solid-state imaging devices, etc., and touch panel type display devices. In particular, protective films (colors) in these various display devices using the above-mentioned photosensitive resin composition. It is preferable to form a protective film for a filter, a protective film for a touch panel display device, or an insulating film (such as an insulating film for a touch panel display device). As a result, the reliability of display quality and imaging quality of various display devices can be sufficiently increased to the extent that it can sufficiently meet the recent demand for higher performance. As described above, the photosensitive resin composition is a photosensitive resin composition for forming a protective film or an insulating film, the cured film is a protective film or an insulating film, and the cured film is a cured film for a touch panel. These forms are also included in the preferred forms of the present invention. Moreover, the cured film formed with the said photosensitive resin composition; The protective film for touch panels formed with the said photosensitive resin composition; The member for display apparatuses which has this cured film or the protective film for touch panels; This cured film or a touch panel A display device having a protective film is included in the present invention.

The member for a display device and the display device of the present invention have the cured film and / or the protective film for a touch panel, but may further have one or more other constituent members. The cured film and the touch panel protective film formed from the photosensitive resin composition are stable and excellent in adhesion to a substrate and the like, have high hardness, and have high transparency and coating performance. Therefore, it is very useful as a protective film or an insulating film in various display devices. Although it does not specifically limit as a display apparatus, For example, a liquid crystal display device, a solid-state image sensor, a touchscreen display apparatus etc. are suitable. As the touch panel display device, a capacitance type device is particularly preferable.

The display device member may be a film-like single layer or multilayer member composed of the cured film or the protective film for the touch panel, and other layers may be added to the single layer or multilayer member. It may be a combined member, or may be a member (for example, a color filter) that includes the above-described cured film or touch panel protective film in its configuration.

Since the photosensitive resin composition of this invention is the above structures, it can give the hardened | cured material (cured film) which has high surface hardness and excellent in various physical properties, such as an electrical property and adhesiveness. Therefore, a display device member and a display device having a cured film or a touch panel protective film formed of such a photosensitive resin composition are very useful in the optical field, the electric field, and the electronic field.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.
In the following synthesis examples and preparation examples, various physical properties and the like were measured as follows.

1. Physical Properties of Resin Solution (Alkali-Soluble Resin) (1) GPC (weight average molecular weight polystyrene) using HLC-8220GPC (manufactured by Tosoh Corp.) and column TSKgel SuperHZM-M (manufactured by Tosoh Corp.) using tetrahydrofuran as an eluent. The weight average molecular weight was measured by a gel permeation chromatography) method.

(2) About 0.3 g of solid content polymer solution (resin solution) was weighed into an aluminum cup, dissolved by adding about 1 g of acetone, and then naturally dried at room temperature. Then, using a hot air dryer (trade name “PHH-101”, manufactured by Espec Corp.), after drying at 140 ° C. for 3 hours, it was allowed to cool in a desiccator and the mass was measured. From the mass reduction amount, the solid content concentration (% by mass) of the polymer solution was calculated.

(3) 1.5 g of acid value resin solution is precisely weighed and dissolved in a mixed solvent of 90 g of acetone / 10 g of water, and a 0.1N KOH aqueous solution is used as a titrant, and an automatic titrator (product of Hiranuma Sangyo Co. The acid value of the resin solution was measured by the name “COM-555”), and the acid value per 1 g of the solid content was determined from the acid value of the solution and the solid content of the solution.

2. Physical properties of coated film (cured film) (1) A resin composition was applied to an ITO (Indium Tin Oxide) vapor-deposited glass substrate having a dielectric constant of 5 cm square by spin coating so that the thickness after drying was 1.5 μm. After heat treatment (90 ° C. for 3 minutes), exposure dose of 60 mJ / cm ² (365 nm illuminance conversion) by a UV aligner (trade name “TME-150RNS” manufactured by TOPCON) equipped with a 2.0 kW super high pressure mercury lamp. Then, exposure was performed and heat treatment (230 ° C. for 30 minutes) was performed. Furthermore, gold (Au) was vapor-deposited on the surface so as to form a square pattern having a thickness of 40 nm and a side of 0.5 cm to form an electrode to obtain a sample for evaluation (a cured film having a thickness of 1.5 μm). The dielectric constant of the capacitance of this sample was determined by calculation from the film thickness value using an impedance analyzer 4294A (manufactured by Agilent Technologies).

(2) Surface hardness (pencil hardness)
An ITO substrate was prepared by depositing ITO with a thickness of 30 nm on glass. The resin composition obtained on this ITO substrate was applied by spin coating, heat-treated (90 ° C. for 3 minutes), and then UV aligner equipped with a 2.0 kW ultra-high pressure mercury lamp (trade name “Topcon”, product name “ TME-150RNS ”) was exposed at an exposure amount of 60 mJ / cm ² (in terms of 365 nm illuminance), followed by heat treatment (230 ° C. for 30 minutes). Using the obtained coating film, a pencil hardness test was performed according to JIS-K5600-5-4 (1999). All loads were performed with 500 g of the old JIS version JIS-K5400 (1990), and the hardness (surface hardness) of the hardest pencil that did not cause scars.
The hardness decreases in the order of 4H>3H>2H>H>F>HB>B>2B>3B> 4B.

(3) Light-resistant adhesion About the coating film (cured film having a thickness of 1.5 μm) obtained in the dielectric constant evaluation test of (1) above, UV is emitted from the glass surface using a xenon weather meter (X75SC, manufactured by Suga Test Instruments). Cross-cut test according to JIS-K5600-5-6 (1999), set on the machine in the direction of contact, and irradiated for 30 h at 60 W / m ² (300 to 400 nm integrated light intensity), BPT 63 ° C., 50% RH And evaluated. Specifically, the grids remaining after the test were visually confirmed. The evaluation was performed with a maximum score of 10 points, with 10 points when all of the grids remained and 0 points when all the grids were peeled off.

(Synthesis of resin solution)
First, resin solutions A to C were synthesized as alkali-soluble resins contained in the resin composition.

Synthesis example 1 (resin solution A)
A separable flask with a cooling tube as a reaction vessel was charged with 178.8 parts of propylene glycol monomethyl ether acetate (PGMEA), heated to 90 ° C. in a nitrogen atmosphere, and benzyl maleimide (BzMI) 25 as dropping system 1. 0.0 part, 20.5 parts of methacrylic acid (MAA), 102.2 parts of cyclohexyl acrylate (CHA), 25 parts of PGMEA, 3.0 parts of perbutyl O (trade name, manufactured by NOF Corporation), n-dodecyl as dropping system 2 Mercaptan (n-DM) 1.3 parts and PGMEA 58.7 parts were each continuously fed over 3 hours. Then, after maintaining at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C. and polymerization was continued for 1.5 hours. Next, 14.1 parts of glycidyl methacrylate (GMA), 0.5 parts of triethylamine (TEA) as a catalyst, and 0.2 parts of Antage W-400 (trade name, manufactured by Kawaguchi Chemical Co., Ltd.) as a polymerization inhibitor were added to this reaction solution. The resin solution A was obtained by continuing the reaction at 110 ° C. for 2 hours and 115 ° C. for 7 hours while bubbling nitrogen and oxygen mixed gas (oxygen concentration: 7%).
Various physical properties of the obtained resin solution A were measured. The results are shown in Table 1.

Synthesis Examples 2-3 (synthesis of BC)
Resin solutions B to C were obtained in the same manner as in Synthesis Example 1 except that the types and blending amounts of the monomer components were changed as shown in Table 1. About each obtained resin solution, various physical properties were measured similarly to the synthesis example 1. The results are shown in Table 1.

Details of the resin solutions A to C are shown in the upper part of Table 1.
In addition, the numerical value of each monomer which comprises the base polymer in Table 1 described the mixture ratio (mass%) of each monomer when the total amount of this monomer was 100 mass%. The numerical value of GMA added to the base polymer is the GMA added to the carboxylic acid content of the monomer having an acid group and a polymerizable double bond (MAA corresponds in Synthesis Examples 1 to 4). Is expressed as mass% in terms of MAA mass, and “the blending ratio (mass%) of GMA in terms of MAA mass = {molar amount of GMA (mol) / molar amount of MAA (mol)} × MAA blending ratio ( Mass%) ”. For example, in Synthesis Example 1, MAA was 13.88% by mass in the base polymer (100% by mass), and 99.31 mmol of GMA was added to 13.88% by mass (238.09 mmol) of MAA. Therefore, the blending ratio of the GMA was defined as “5.79”.

[Preparation of resin composition and evaluation test of coating film]
Example 1
In terms of solid content, 26.9 parts of resin solution A, 10.7 parts of dipentaerythritol hexaacrylate (DPHA), 28 parts of NBAC-ST (trade name, manufactured by Nissan Chemical Industries), Shin-Etsu Silicone KBM-503 (Trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 13.7 parts, Mega-Face F-554 (manufactured by DIC) 0.9 parts, Antage W-400 (trade name, manufactured by Kawaguchi Chemical Industry Co., Ltd.) 0.3 19.6 parts of IRGACURE907 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) and further adding a diluting solvent (propylene glycol monomethyl ether acetate; PGMEA) to a solid content concentration of 25% and stirring. A resin composition was obtained. About the obtained resin composition, the coating-film physical property was evaluated in accordance with the evaluation method mentioned above. The results are shown in Table 1.

Examples 2-3 and Comparative Examples 1-6
Each resin composition was obtained in the same manner as in Example 1 using the raw materials shown in the table at the mixing ratio shown in Table 1. About each of the obtained resin composition, the coating-film physical property was evaluated in accordance with the evaluation method mentioned above. The results are shown in Table 1.

In Table 1, the amount of each raw material is a solid content.
Table 1 omits the use of a diluting solvent (PGMEA: propylene glycol monomethyl ether acetate) for the preparation of each resin composition.

Abbreviations in Table 1 are as follows.
BzMI: benzyl maleimide MD: dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate AMA: α- (allyloxymethyl) methyl acrylate CHA: cyclohexyl acrylate MAA: methacrylic acid GMA: glycidyl methacrylate Mw: Weight average molecular weight DPHA of finally obtained polymer: dipentaerythritol hexaacrylate (trade name, manufactured by Kyoeisha Chemical Co., Ltd.)
NBAC-ST: butyl acetate dispersed silica sol (trade name, manufactured by Nissan Chemical Industries, Ltd.)
KBM-503: 3-methacryloxypropyltrimethoxysilane (trade name “Shin-Etsu Silicone KBM-503”, manufactured by Shin-Etsu Chemical Co., Ltd.)
F-554: Fluorine-containing / lipophilic group-containing oligomer (nonionic, trade name “Megafac F-554”, manufactured by DIC Corporation)
W-400: Phenolic antioxidant (trade name “ANTAGE W-400”, manufactured by Kawaguchi Chemical Co., Ltd.)
Irg907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name “IRGACURE907”, manufactured by Ciba Specialty Chemicals)

* 1: The numerical value in the “ratio to the whole” column is the content ratio (mass%) of each component when the total solid content of the photosensitive resin composition is 100 mass%.
* 2: The numerical value in the “ratio to resin” column is the content ratio (parts by mass) of each component when the solid content of the resin (A to C) is 100 parts by mass.

From Table 1, it was found that the critical significance of the numerical range of the present invention can be said as follows. That is, a resin composition having a configuration in which an alkali-soluble resin having a predetermined molecular weight and an acid value, a polyfunctional polymerizable compound, inorganic fine particles, and a photopolymerization initiator are set, and the solid content thereof is set within a predetermined range. As a result, it was found that the cured product had an advantageous effect that excellent adhesion (particularly light-resistant adhesion), low dielectric constant and high surface hardness could be exhibited in a well-balanced manner. .

Specifically, the following was found by comparing Example 1 with Comparative Examples 1-6.
That is, by comparing Example 1 with Comparative Example 1, the content of the alkali-soluble resin is larger than the range defined in the present invention, and the content of the polyfunctional polymerizable compound, the inorganic fine particles, and the photopolymerization initiator is the present. When the amount is less than the range specified in the invention, the surface hardness cannot be sufficiently improved; by comparing Example 1 with Comparative Example 2, the content of the polyfunctional polymerizable compound is more than the range specified in the present invention. If the content is too large, the dielectric constant cannot be reduced sufficiently; if the content of the inorganic fine particles is larger than the range defined in the present invention, the dielectric constant cannot be reduced sufficiently by comparison between Example 1 and Comparative Example 3. According to the comparison between Example 1 and Comparative Example 4, if the content of the photopolymerization initiator is less than the range defined in the present invention, neither the surface hardness nor the light adhesion can be improved sufficiently. Example 1 and Comparative Example 5 By comparison, if the weight average molecular weight of the alkali-soluble resin is smaller than the range specified in the present invention, the surface hardness and the light-resistant adhesion cannot be sufficiently improved; by comparing Example 1 and Comparative Example 6, It was found that when the acid value of the alkali-soluble resin is higher than the range specified in the present invention, the dielectric constant cannot be reduced more sufficiently and the light-resistant adhesion cannot be improved more sufficiently.

In the above-described examples, specific compounds are used as the respective components, but an alkali-soluble resin having a predetermined molecular weight and acid value, a polyfunctional polymerizable compound, inorganic fine particles, and a photopolymerization initiator are included. In addition, as long as the solid content is a resin composition having a structure set in a predetermined range, a cured product having sufficient surface hardness and excellent in various physical properties such as electric characteristics and adhesion can be provided. The effect of this invention can be produced. That is, the resin composition has the essential features of the present invention in such a configuration. If the resin composition satisfies this configuration, the effect is exhibited.
Although not shown above, the coating films obtained in Examples 1 to 3 were excellent in transparency and low colorability.

Claims (6)

A photosensitive resin composition comprising an alkali-soluble resin, a polyfunctional polymerizable compound, inorganic fine particles and a photopolymerization initiator,
The alkali-soluble resin has a weight average molecular weight of 15,000 to 20,000, an acid value of 50 to 80 mgKOH / g,
The solid content of the alkali-soluble resin is 20 to 30% by mass with respect to 100% by mass of the total solid content of the photosensitive resin composition,
The polyfunctional polymerizable compound is 30 to 50 parts by mass, the inorganic fine particles are 90 to 110 parts by mass, and the photopolymerization initiator is 60 to 80 parts by mass with respect to 100 parts by mass of the solid content of the alkali-soluble resin. A photosensitive resin composition characterized by being included. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin is a polymer having a ring structure in a main chain. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin is a polymer having a double bond in a side chain. A cured film formed of the photosensitive resin composition according to claim 1. A display device member comprising the cured film according to claim 4. A display device comprising the cured film according to claim 4.