JP2017058627A - Photosensitive resin composition and cured film of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that gives a cured film excellent in solvent resistance and a surface smoothness of high level, and to provide a cured film formed by curing the photosensitive resin composition, and a display device member and a display device achieving high color purity, high brightness and reduction in thickness by incorporating the cured film.SOLUTION: The photosensitive resin composition comprises an alkali-soluble resin, a polymerizable compound and a coloring material. The alkali-soluble resin is a resin having a heterocyclic structure in the main chain. The photosensitive resin composition is in at least one form selected from the group consisting of a form where the photosensitive resin contains at least a dye as the coloring material and a form where the photosensitive resin contains the coloring material with a content of 42 mass% or more relative to total 100 mass% of the solid content of the photosensitive resin composition.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive resin composition and a cured film formed thereby, as well as a display device member and a display device having a cured film.

The photosensitive resin composition is a composition whose physical properties are changed by irradiating the coating film with light or an electron beam, that is, for example, the exposed portion is cured and the other portion is soluble. It is a composition. Utilizing such characteristics, it is used in various fields such as electronic information materials and optical materials. One of the main uses is a color filter. The color filter is a main member constituting the liquid crystal display device and the imaging tube element.

Photosensitive resin compositions are usually composed of a composition containing a colorant such as a pigment or a dye in addition to an alkali-soluble resin or a polymerizable monomer, but in recent years, display quality in liquid crystal display devices, image pickup tube elements, etc. In order to improve image quality and image quality, there is a growing demand for higher color purity and higher brightness, and there is also a demand for a thinner film, which tends to increase the colorant concentration in the photosensitive resin composition. . As conventional photosensitive resin compositions, for example, compositions described in Patent Documents 1 and 2 have been developed.

Japanese Patent Laid-Open No. 2015-22175 International Publication No. 2010/74289 Pamphlet

As described above, in recent years, there is a tendency to increase the color material concentration in the photosensitive resin composition, but there are various problems such as insufficient dispersion stability and curability of the color material. Furthermore, the present inventors have found that when a cured film is formed using a photosensitive resin composition having a high color material concentration, the solvent resistance is not sufficient, and the color material is not contained in the solvent when the cured film is washed with a solvent. It has been newly found that there are problems such as elution in the surface and insufficient surface smoothness of the cured film. In addition, dyes and pigments are listed as representative examples of the color material, and it has been newly found out that the same problem occurs when dyes are used. Dyes tend to ooze out compared to pigments and have poor durability, so that the use of dyes has heretofore tended to be avoided.

The resin compositions described in Patent Documents 1 and 2 are excellent in various physical properties such as heat resistance and sensitivity, and are extremely useful for various applications such as color filters. However, Patent Documents 1 and 2 do not discuss the case where a dye is used as the color material or the case where the color material concentration exceeds 40% by mass.

This invention is made | formed in view of the said present condition, and it aims at providing the photosensitive resin composition which is excellent in solvent resistance and gives the cured film which has a high level surface smoothness. Further, there are provided a cured film obtained by curing such a photosensitive resin composition, and a display device member and a display device that can achieve high color purity, high brightness, and thin film by having the cured film. It is also intended to provide.

The present inventor has variously studied the photosensitive resin composition, and includes an alkali-soluble resin having a predetermined structure, a polymerizable compound, and a coloring material, and further includes at least a dye as a coloring material, and / or a coloring material concentration. Is a form having a higher concentration than in the prior art, it can provide a cured film that exhibits excellent solvent resistance and sufficiently suppresses the seepage of the coloring material, and is extremely excellent in surface smoothness. We have found that it can fully meet the demands for purifying, increasing the brightness, and reducing the film thickness. It was also found that this cured film is excellent in developability (development speed). In view of the conventional tendency to avoid the use of dyes as coloring materials and the fact that the content of pigments is at most about 40% by mass or less, such a configuration of the present invention is easy for those skilled in the art. In addition, with the configuration of the present invention, a cured film excellent in solvent resistance, surface smoothness, and developability can be solved by solving the problems when using dyes or increasing the colorant concentration. It is not predictable by those skilled in the art. The present inventor also said that such a photosensitive resin composition is particularly suitable as a resist for a color filter. A cured film obtained by curing the resist, a member for a display device, and a display device are electronic information materials and optical materials. The present invention has been found to be extremely useful in various fields such as.

That is, the present invention is a photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound and a coloring material, wherein the alkali-soluble resin is a resin having a heterocyclic structure in the main chain, and the photosensitive resin composition Is at least one form selected from the group consisting of a form containing at least a dye as a color material and a form containing a color material in an amount of 42% by mass or more in a total solid content of 100% by mass of the photosensitive resin composition. It is a certain photosensitive resin composition.

The alkali-soluble resin has, in the main chain, the following general formula (1) or (2):

(In the formula, R ¹ and R ³ are the same or different and each represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. R ² represents a hydrogen atom or a methyl group. X, Y and Z are the same. Or differently, a methylene group, a methylene group in which a hydrogen atom is substituted with a methyl group, an oxygen atom, a sulfur atom, or an imino group, provided that at least one of X, Y, and Z is an oxygen atom, sulfur It preferably has a heterocyclic-containing structural unit represented by: an atom or an imino group.

The color material preferably contains 10% by mass or more of a dye in a total amount of 100% by mass of the color material.

The present invention is also a cured film obtained by curing 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.

Since the photosensitive resin composition of the present invention is configured as described above, it can provide a cured film having excellent solvent resistance and developability, and having a high level of surface smoothness. It can fully meet the demands for higher brightness and thinner film. Such a photosensitive resin composition is particularly suitable as a resist for a color filter, and a cured film, a display device member and a display device obtained by curing the resist are used in various fields such as electronic information materials and optical materials. Very useful.

Although the preferable form of this invention is demonstrated concretely below, this invention is not limited only to the following description, In the range which does not change the summary of this invention, it can change suitably and can apply. In addition, the form which combined each preferable form of this invention described below 2 or 3 or more also corresponds to the preferable form of this invention.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention (also simply referred to as a resin composition) comprises (A) an alkali-soluble resin, (B) a polymerizable compound (also referred to as a polymerizable monomer), and (C) a coloring material. It contains at least components (A) to (C). If necessary, one or more other components may be further contained, and one or two or more of each component may be used.

In the present specification, the “total amount of solid content” means the total amount of components that form a cured product, that is, the total amount of components (solid content and non-volatile content) excluding the solvent that volatilizes when the cured product is formed. Specifically, when an alkali-soluble resin, a polymerizable monomer, a colorant, and other cured product-forming components (for example, a photopolymerization initiator, a dispersant, etc.) are included, the total of the components The solid content mass of

(A) Alkali-soluble resin An alkali-soluble resin is a resin (polymer) that exhibits alkali solubility, and preferably has an acid group in the molecule. Examples of the acid group include a functional group that neutralizes with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, and a sulfonic acid group, and has only one of these. You may have, and you may have 2 or more types. Among these, a carboxyl group and a carboxylic anhydride group are preferable, and a carboxyl group is more preferable.
The alkali-soluble resin can act as a binder resin in the resin composition.

The acid value (AV) of the alkali-soluble resin is preferably 20 mgKOH / g or more, for example. Thereby, sufficient alkali solubility is expressed, and it becomes possible to give a cured product having better developability (development speed). More preferably, it is 50 mgKOH / g or more, More preferably, it is 70 mgKOH / g or more, The action effect of this invention that it is excellent in solvent resistance and surface smoothness so that an acid value is large in this way is exhibited notably. More preferably, it is 90 mgKOH / g or more, and the development speed is remarkably excellent. Especially preferably, it is 95 mgKOH / g or more, Most preferably, it is 99 mgKOH / g or more. Moreover, although the upper limit of an acid value is not specifically limited, For example, from a viewpoint of sclerosis | hardenability and the water resistance improvement of hardened | cured material, it is preferable that it is 300 mgKOH / g or less. More preferably, it is 250 mgKOH / g or less, More preferably, it is 200 mgKOH / g or less, Most preferably, it is 150 mgKOH / g or less.
In the present specification, the acid value of the polymer can be determined by the method described in Examples described later.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5000 or more, for example. Thereby, the hardened | cured material which is more excellent in heat resistance or mechanical strength can be given. More preferably, it is 6000 or more, More preferably, it is 7000 or more, Most preferably, it is 8000 or more. For example, the upper limit of Mw is preferably 50,000 or less. Thereby, since the viscosity of a resin composition becomes more suitable and it becomes easy to form a coating film, developability is improved more. More preferably, it is 30,000 or less, More preferably, it is 20,000 or less.
In this specification, a weight average molecular weight can be measured by the method as described in the Example mentioned later.

The alkali-soluble resin has a heterocyclic structure in the main chain. By having a heterocyclic structure in the main chain, for example, basic performance (adhesiveness, curability, dry resolubility, etc.) that contributes to platemaking when producing color filters, etc., reliability and spectral characteristics of cured products The photosensitive resin composition is extremely excellent in basic performance (heat resistance, transparency, etc.) that contributes to In particular, it is possible to give a cured product having extremely excellent solvent resistance, developability and surface smoothness.

The heterocyclic structure is also called a heterocyclic structure, and is preferably a 4- to 6-membered cyclic structure from the viewpoint of stable polymerization activity. More preferably, it is a 5-6 membered ring structure. Moreover, the hetero atom which comprises a heterocyclic structure has an oxygen atom, a sulfur atom, or a nitrogen atom preferable, and an oxygen atom or a sulfur atom is more preferable from a viewpoint of transparency improvement. Among these, oxygen atoms are more preferable from the viewpoint of coloring suppression and the like.

The form in which the alkali-soluble resin has a heterocyclic structure in the main chain is preferably a form having a heterocyclic-containing structural unit represented by the general formula (1) or (2). Especially, the form which has a heterocyclic containing structural unit represented by the said General formula (1) from a viewpoint which sclerosis | hardenability and solvent resistance increase further is more preferable.

In the above formulas (1) and (2), X and Z preferably represent a methylene group from the viewpoint of improving flexibility. In this case, Y preferably represents an oxygen atom, a sulfur atom or an imino group, more preferably an oxygen atom or a sulfur atom, and still more preferably an oxygen atom. Thus, it is particularly preferred that X and Z in the above formula represent a methylene group and Y represents an oxygen atom, that is, the alkali-soluble resin has a tetrahydrofuran ring and / or a tetrahydropyran ring in the main chain. Most preferably, it has a tetrahydrofuran ring in the main chain.

In the general formulas (1) and (2), R ¹ and R ³ are the same or different and each represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. If having the general formula (1) or more in the hetero ring-containing structural unit represented by (2) molecules, R ¹ and R ³ in each occurrence, R ¹ and R ³ in other structural units And may be the same or different. The same is true for R ^2.

Although the said C1-C30 organic group should just be suitably set according to the objective and use and is not specifically limited, For example, it is a C1-C30 hydrocarbon group which may have a substituent. preferable. Carbon number becomes like this. Preferably it is 1-25, More preferably, it is 1-12, More preferably, it is 1-8.

Specific examples of the organic group having 1 to 30 carbon atoms include, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-amyl, s-amyl, t -Amyl, n-hexyl, s-hexyl, n-heptyl, n-octyl, s-octyl, t-octyl, 2-ethylhexyl, capryl, nonyl, decyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl , Stearyl, nonadecyl, eicosyl, ceryl, melyl, and the like chain saturated hydrocarbon groups; methoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, ethoxyethyl, ethoxyethoxyethyl, phenoxyethyl, phenoxyethoxyethyl, etc. Of the hydrogen atom of the chain saturated hydrocarbon group An alkoxy-substituted chain saturated hydrocarbon group in which a part is replaced with an alkoxy group; a hydroxy-substituted chain saturated hydrocarbon in which a part of hydrogen atoms of a chain saturated hydrocarbon group such as hydroxyethyl, hydroxypropyl, hydroxybutyl, etc. is replaced with a hydroxyl group Hydrogen group; halogen-substituted chain saturated hydrocarbon group in which part of the hydrogen atoms of the chain saturated hydrocarbon group is replaced by halogen, such as fluoroethyl, difluoroethyl, chloroethyl, dichloroethyl, bromoethyl, dibromoethyl; vinyl, allyl Chain unsaturated hydrocarbon groups such as methallyl, crotyl, propargyl, etc., and chain unsaturated hydrocarbon groups in which part of the hydrogen atoms are replaced by alkoxy groups, hydroxyl groups or halogens; cyclopentyl, cyclohexyl, 4-methylcyclohexyl 4-t-butylcyclohexyl, tricyclodecanyl Cycloaliphatic hydrocarbon groups such as isobornyl, adamantyl, dicyclopentadienyl, and alicyclic hydrocarbon groups in which part of the hydrogen atoms are replaced by alkoxy groups, hydroxyl groups or halogens; phenyl, methylphenyl, dimethylphenyl , Trimethylphenyl, 4-t-butylphenyl, benzyl, diphenylmethyl, diphenylethyl, triphenylmethyl, cinnamyl, naphthyl, anthranyl and the like, and some of the hydrogen atoms are alkoxy groups, hydroxyl groups, An aromatic hydrocarbon group substituted by halogen; and the like, and further a substituent may be bonded. Among these, from the viewpoint of improving heat resistance, a group having a primary or secondary carbon which is difficult to be removed by acid or heat, such as methyl, ethyl, cyclohexyl, benzyl and the like is preferable.

R ¹ and R ³ are particularly preferably the same or different and each represents a hydrogen atom or a methyl group. R ² is particularly preferably a hydrogen atom.

What is necessary is just to set suitably the content rate of the heterocyclic containing structural unit which exists in a principal chain according to the objective and use of the photosensitive resin composition, and the molecular weight of alkali-soluble resin in the said alkali-soluble resin. For example, it is preferable that it is 1-99 mol% with respect to 100 mol% of all repeating units, More preferably, it is 2-98 mol%, More preferably, it is 5-95 mol%. In addition, when the alkali-soluble resin has a high molecular weight, the performance tends to be exhibited even if the molar ratio of the heterocyclic-containing structural unit is small, and when the molecular weight is low, the performance is better when the molar ratio is increased. It tends to be easy. From this viewpoint, the number of heterocyclic-containing structural units contained per main chain (also referred to as the average number of functional groups) is preferably 0.5 or more, more preferably 1.0 or more, and still more preferably 2. 0 or more.

The alkali-soluble resin can be produced, for example, by polymerizing a monomer component containing a monomer having an acid group and a monomer capable of introducing a heterocyclic structure into the main chain skeleton of the polymer. However, it is also preferable to produce by introducing a polymerizable double bond into a side chain of a polymer (also referred to as a base polymer) obtained by the polymerization. The side chain double bond-containing polymer obtained by the latter production method is also included in the alkali-soluble resin of the present invention. Among these, the alkali-soluble resin is preferably a side chain double bond-containing polymer from the viewpoints of photosensitivity, curability, thermal decomposition resistance, and the like. The raw material monomers can be used alone or in combination of two or more, and the monomer component forming the base polymer (also referred to as monomer composition) is also referred to as “base polymer component”.
Below, the raw material component and polymerization method of alkali-soluble resin are further demonstrated.

-Raw material components (monomers, etc.)-
(I) Monomer having an acid group A monomer having an acid group is a compound having an acid group and a polymerizable double bond in the molecule. For example, unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid and vinylbenzoic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid; Unsaturated monocarboxylic acids in which the chain between an unsaturated group and a carboxyl group, such as acid mono (2-acryloyloxyethyl) and succinic acid mono (2-methacryloyloxyethyl); maleic anhydride, itaconic anhydride Unsaturated acid anhydrides such as phosphoric acid group-containing unsaturated compounds such as light ester P-1M (manufactured by Kyoeisha Chemical); 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 preferred are unsaturated monocarboxylic acids in terms of reactivity, alkali solubility, etc., more preferred is (meth) acrylic acid (ie acrylic acid and / or methacrylic acid), and particularly preferred is methacrylic acid. .

The blending ratio of the monomer having an acid group is preferably, for example, 5% by mass or more with respect to 100% by mass of the total amount of the base polymer component. Thereby, the solubility with respect to an alkali becomes more sufficient, and it becomes a more useful resin composition for the use where developability is required. Moreover, it is preferable that it is 70 mass% or less at the point which can maintain the outstanding external appearance, adhesiveness, etc. of the hardened | cured material after high temperature exposure. More preferably, it is 10-60 mass%, More preferably, it is 15-50 mass%.

(Ii) A monomer capable of introducing a heterocyclic structure into the main chain skeleton of the polymer As a monomer capable of introducing a heterocyclic structure into the main chain skeleton of the polymer, for example, a double bond-containing heterocyclic ring in the molecule Examples thereof include a monomer having a structure and a monomer that gives a heterocyclic structure to the main chain skeleton by cyclopolymerization. Especially, the monomer represented by the following general formula (3) or (4) is preferable. Thereby, the obtained alkali-soluble resin has a heterocyclic-containing structural unit represented by the general formula (1) or (2) described above. More preferably, it is a monomer represented by the following general formula (3).

The symbols in the general formulas (3) and (4) are the same as the symbols in the general formulas (1) and (2) described above. Especially, it is especially preferable that X and Z represent a methylene group and Y represents an oxygen atom.

Preferred examples of the monomer represented by the general formula (3) include the following compounds.
α-allyloxymethyl acrylic acid, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, n-propyl α-allyloxymethyl acrylate, i-propyl α-allyloxymethyl acrylate, α- N-butyl allyloxymethyl acrylate, s-butyl α-allyloxymethyl acrylate, t-butyl α-allyloxymethyl acrylate, n-amyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate s -Amyl, α-allyloxymethyl acrylate t-amyl, α-allyloxymethyl acrylate n-hexyl, α-allyloxymethyl acrylate s-hexyl, α-allyloxymethyl acrylate n-heptyl, α-allyl N-octyl oxymethyl acrylate, α-allyloxymethyl S-octyl crylate, t-octyl α-allyloxymethyl acrylate, 2-ethylhexyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate capryl, α-allyloxymethyl acrylate nonyl, α-allyloxy Decyl methyl acrylate, undecyl α-allyloxymethyl acrylate, lauryl α-allyloxymethyl acrylate, tridecyl α-allyloxymethyl acrylate, myristyl α-allyloxymethyl acrylate, pentadecyl α-allyloxymethyl acrylate, Cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, stearyl α-allyloxymethyl acrylate, nonadecyl α-allyloxymethyl acrylate, eicosi α-allyloxymethyl acrylate , Ceryl α-allyloxymethyl acrylate, melyl α-allyloxymethyl acrylate,

methoxyethyl α-allyloxymethyl acrylate, methoxyethoxyethyl α-allyloxymethyl acrylate, methoxyethoxyethoxyethyl α-allyloxymethyl acrylate, 3-methoxybutyl α-allyloxymethyl acrylate, α-allyloxymethyl Ethoxyethyl acrylate, ethoxyethoxyethyl α-allyloxymethyl acrylate, phenoxyethyl α-allyloxymethyl acrylate, phenoxyethoxyethyl α-allyloxymethyl acrylate, hydroxyethyl α-allyloxymethyl acrylate, α-allyl Hydroxypropyl oxymethyl acrylate, hydroxybutyl α-allyloxymethyl acrylate, fluoroethyl α-allyloxymethyl acrylate, difluoro α-allyloxymethyl acrylate Chill, chloroethyl α-allyloxymethyl acrylate, dichloroethyl α-allyloxymethyl acrylate, bromoethyl α-allyloxymethyl acrylate, dibromoethyl α-allyloxymethyl acrylate, vinyl α-allyloxymethyl acrylate, α -Allyloxymethyl acrylate, α-allyloxymethyl methacrylic acid, crotyl α-allyloxymethyl acrylate, propargyl α-allyloxymethyl acrylate, cyclopentyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic Acid cyclohexyl, α-allyloxymethyl acrylate 4-methylcyclohexyl, α-allyloxymethyl acrylate 4-t-butylcyclohexyl, α-allyloxymethyl acrylate tricyclodecanyl, α-a Isobornyl ryloxymethyl acrylate, adamantyl α-allyloxymethyl acrylate, dicyclopentadienyl α-allyloxymethyl acrylate, phenyl α-allyloxymethyl acrylate, methyl phenyl α-allyloxymethyl acrylate, α- Dimethylphenyl allyloxymethyl acrylate, trimethylphenyl α-allyloxymethyl acrylate, 4-t-butylphenyl α-allyloxymethyl acrylate, benzyl α-allyloxymethyl acrylate, diphenylmethyl α-allyloxymethyl acrylate , Α-allyloxymethyl acrylate diphenylethyl, α-allyloxymethyl acrylate triphenylmethyl, α-allyloxymethyl acrylate cinnamyl, α-allyloxymethyl naphthyl, α-a Anthranyl ryloxymethyl acrylate and the like.

Preferred examples of the monomer represented by the general formula (4) include the following compounds.
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 ′-[oxybis (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 (methylene)] 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-propenoate, di (2-methyl) -2-adamantyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate and the like.

The blending ratio of the monomer capable of introducing a heterocyclic structure into the main chain skeleton of the polymer is preferably 2% by mass or more with respect to 100% by mass of the total amount of the base polymer components. Thereby, transparency, heat resistance, etc. can be improved further. Moreover, it is preferable that it is 60 mass% or less from a viewpoint of the gelatinization at the time of superposition | polymerization and an efficient viewpoint. More preferably, it is 3-50 mass%, More preferably, it is 5-40 mass%.

(Iii) Monomer having a cyclic structure The base polymer component preferably also contains a monomer having a cyclic structure (excluding a compound corresponding to the monomer (ii) above). Preferred examples of the monomer having a cyclic structure include cyclic structure-containing (meth) acrylic acid ester monomers; N-substituted maleimide monomers; aromatic vinyl compounds.

Examples of the cyclic structure-containing (meth) acrylic acid ester monomer include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, ( (Meth) acrylic acid dicyclopentenyl, (meth) acrylic acid dicyclopentenyloxyethyl, (meth) acrylic acid dicyclopentanyl, biphenyl (meth) acrylate, o-biphenyloxyethyl (meth) acrylate, o-biphenyloxyethoxy Ethyl (meth) acrylate, m-biphenyloxyethyl acrylate, p-biphenyloxyethyl (meth) acrylate, o-biphenyloxy-2-hydroxypropyl (meth) acrylate, p-biphenyloxy-2-hydroxypropyl (meth) Acrylate, m-biphenyloxy-2-hydroxypropyl (meth) acrylate, N- (meth) acryloyloxyethyl-o-biphenyl = carbamate, N- (meth) acryloyloxyethyl-p-biphenyl = carbamate, N- (meth) ) Biphenyl group-containing monomers such as acryloyloxyethyl-m-biphenyl = carbamate, o-phenylphenol glycidyl ether acrylate, naphthalene ring-containing monomers such as vinylnaphthalene, terphenyl (meth) acrylate, o-terphenyloxyethyl (meth) An acrylate etc. are mentioned.

Examples of the N-substituted maleimide monomer include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, Nt-butylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide, p-methylbenzylmaleimide, p-butylbenzylmaleimide, p-hydroxybenzylmaleimide, o-chlorobenzylmaleimide, o-dichlorobenzylmaleimide, p-dichlorobenzylmaleimide, etc. Among these, N-phenylmaleimide and N-benzylmaleimide are preferable from the viewpoint of transparency, and N-benzylmaleimide is particularly preferable. Examples of 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; and the like.

Examples of the aromatic vinyl compound include styrene, vinyl toluene, α-methylstyrene, and the like.

Among the above-described monomers having a cyclic structure, a cyclic structure-containing (meth) acrylic acid ester monomer or an aromatic vinyl compound is preferable in terms of good transparency and resistance to heat resistance. More preferred are cyclic structure-containing (meth) acrylic acid ester monomers. More preferred are cyclohexyl (meth) acrylate, benzyl (meth) acrylate, o-biphenyloxyethyl (meth) acrylate, and o-biphenyloxyethoxyethyl (meth) acrylate.

The blending ratio of the monomer having a cyclic structure is not particularly limited. For example, it is preferably 0 to 80% by mass with respect to 100% by mass of the total amount of the base polymer component. Among these, from the viewpoints of heat resistance, hardness, colorant dispersibility, development speed, transparency and the like, it is more preferably 2 to 80% by mass, further preferably 10 to 75% by mass, and particularly preferably 20 to 70% by mass. %.

(Iv) Other monomer The above base polymer component may also contain other monomers copolymerizable with at least one of the above-described monomers, if necessary (also referred to as other monomers). 1 type or 2 types or more may be included.

The other monomer is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid (Meth) acrylates such as n-butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate (however, , Except those corresponding to the monomers (ii) and (iii) above); (meth) acryloylmorpholine, (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- Butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, Nt-butyl (meth) acrylic N-octyl (meth) acrylamide, diacetone (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-phenyl (meth) ) Acrylamide, N-benzyl (meth) acrylamide, N-triphenylmethyl (meth) acrylamide, (meth) acrylamides such as N, N-dimethyl (meth) acrylamide (provided that (ii) and (iii) above) Butadiene or isoprene and other butadiene or substituted butadiene compounds; ethylene, propylene, vinyl chloride, acrylonitrile and other ethylene or substituted ethylene compounds; vinyl acetate and other vinyl esters; and the like. Among these, (meth) acrylic acid esters are preferable, and methyl (meth) acrylate is more preferable in terms of good transparency and resistance to heat resistance.

The blending ratio of the other monomer is not particularly limited. For example, it is preferably 0 to 80% by mass with respect to 100% by mass of the total amount of the base polymer component. Especially, it is more preferable that it is 0.1-80 mass% from viewpoints, such as heat-resistant coloring property and color material dispersibility, More preferably, it is 1-50 mass%, Especially preferably, it is 1-20 mass%.

-Polymerization method-
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 preferable because it is industrially advantageous and structural adjustment such as molecular weight is 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 cyclized. The rate (for example, the ratio in which the structural unit represented by the general formula (1) or (2) is generated from the monomer represented by the general formula (3) or (4)) is high, and industrially It is preferable because it is advantageous. The polymerization concentration and polymerization temperature vary depending on the type and ratio of the monomers used and the molecular weight of the target polymer. Preferably, the polymerization temperature is 40 to 150 ° C., and the polymerization concentration is 20 to 50% by mass. More preferably, the polymerization temperature is set to 60 to 130 ° C., and the polymerization concentration is set to 30 to 45%.

In the case of using a solvent for the polymerization, the solvent is not particularly limited as long as it is a solvent used in a normal radical polymerization reaction, but it is efficient to use a solvent that is used later to form a photosensitive resin composition. Is preferable. In addition, 1 type (s) or 2 or more types can be used for a solvent.

Specific examples of the solvent include the following compounds.
Monoalcohols such as methanol, ethanol, isopropanol, n-butanol, s-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol monoethers such as glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 3-methoxybutanol; ethylene glycol dimethyl ether, ethylene glycol Jie Ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, glycol ethers such as propylene glycol diethyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Esters of glycol monoethers such as monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate Methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Alkyl esters such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate, ethyl acetoacetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; benzene, toluene, xylene, ethylbenzene, etc. Aromatic hydrocarbons; Aliphatic hydrocarbons such as hexane, cyclohexane and octane; Amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone;

Among these, from the viewpoint of polymerization efficiency, it is preferable to use glycol monoether esters, monoalcohols and / or glycol monoethers. More preferably, glycol monoether esters are used at least, and it is also suitable to use glycol monoether esters in combination with glycol monoethers.

In the above polymerization, one or more polymerization initiators may be used as necessary.
Although it does not specifically limit as a polymerization initiator, For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amyl Organic peroxides such as peroxy-2-ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexane Carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), azo compounds such as dimethyl 2,2′-azobis (2-methylpropionate); hydrogen peroxide, persulfate; Can be mentioned. A reducing agent such as a transition metal salt or an amine may be used in combination with the polymerization initiator.

The amount of the polymerization initiator used may be set as appropriate according to the type and amount of the monomer used, the polymerization reaction conditions such as the polymerization temperature and concentration, the molecular weight of the target polymer, etc., but is not particularly limited. For example, it is preferable to set it as 0.1-20 mass parts with respect to 100 mass parts of total amounts of a base polymer component. This makes it possible to easily obtain a polymer having a weight average molecular weight in a preferred range without gelation. More preferably, it is 0.5-15 mass parts.

In the polymerization, a chain transfer agent may be used as necessary for adjusting the molecular weight.
Examples of the chain transfer agent include mercaptan chain transfer agents such as n-dodecyl mercaptan, mercaptopropionic acid, mercaptoacetic acid and methyl mercaptoacetate, α-methylstyrene dimer, and the like, as well as JP2015-22175A [0047]. And the compounds described in. Among these, n-dodecyl mercaptan and / or mercaptopropionic acid is preferably used because they have a high chain transfer effect, can reduce residual monomers, and are easily available.

When using a chain transfer agent, the amount used may be appropriately set according to the type and amount of monomers used, polymerization reaction conditions such as polymerization temperature and concentration, the molecular weight of the target polymer, etc. Although it does not specifically limit, For example, it is preferable to set it as 0.1-15 mass parts with respect to 100 mass parts of total amounts of a base polymer component. This makes it possible to easily obtain a polymer having a weight average molecular weight in a preferred range without gelation. More preferably, it is 0.5-10 mass parts, More preferably, it is 1-8 mass parts.

-Method of introducing polymerizable double bond into side chain-
The alkali-soluble resin also preferably contains a polymerizable double bond in the side chain. By giving a polymerizable double bond to the side chain, it can be cured by heat or light. Therefore, the thermal decomposition resistance is further improved, the sensitivity to light is improved, the resin is cured with less light, and the mechanical strength after curing is also increased. Examples of the method for introducing a polymerizable double bond into the side chain include a method in which a compound containing a functional group capable of bonding to an acid group and a polymerizable double bond is added to the base polymer.

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. What has these 1 type, or 2 or more types as a compound is suitable. Among these, a (meth) acryloyl group is preferable from the viewpoint of the reactivity of the obtained polymer. In addition, examples of the functional group that can be bonded to the acid group include an epoxy group, an oxazoline group, a hydroxyl group, an oxetanyl group, an isocyanate group, and the like, and those having one or more of these as the above compound are suitable. is there. Among these, an epoxy group, an oxazoline group, or a hydroxyl group is preferable, and an epoxy group (including a glycidyl group) is more preferable 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 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, allyl alcohol, and the like. A compound having a heavy bond; glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, vinylbenzyl glycidyl ether, allyl glycidyl ether, 3, (meth) acrylic acid 3, Compounds having an epoxy group and a double bond such as 4-epoxycyclohexylmethyl, allyl glycidyl ether and vinylcyclohexene oxide; compounds having an oxazoline group and a double bond such as vinyl oxazoline and isopropenyl oxazoline; One or more of these It is possible to use. Among these, it is preferable to use a compound (monomer) having an epoxy group and a (meth) acryloyl group. In particular, glycidyl (meth) acrylate and / or (from the viewpoint of high reactivity and easy control of the reaction, easy availability, and the ability to introduce not only radically polymerizable double bonds but also hydroxyl groups at the same time. More preferred is (meth) acrylic acid 3,4-epoxycyclohexylmethyl.

The addition amount of the compound containing the functional group capable of binding to the acid group and the polymerizable double bond is preferably 2 to 95 mass with respect to 100 mass parts of the total amount of the monomer component (base polymer component) giving the base polymer. Part. When the added amount of the compound is within this range, the curability of the photosensitive resin composition is further increased, and the strength after curing is further improved. The storage stability of the composite is further improved, and coloring is sufficiently suppressed in the cured product. More preferably, it is 10 mass parts or more, More preferably, it is 20 mass parts or more, Most preferably, it is 30 mass parts or more. Thus, when there is much addition amount, the effect of this invention will be exhibited more, and it will become possible to give the hardened | cured material which is more excellent with solvent resistance, surface smoothness, and developability. The upper limit is more preferably 85 parts by mass or less, still more preferably 80 parts by mass or less, and particularly preferably 75 parts by mass or less.

A method for adding a compound containing a functional group capable of bonding to an acid group and a polymerizable double bond to a part of the acid group in the base polymer may be a known method and is not particularly limited. The reaction temperature is preferably, for example, 60 ° C to 140 ° C. It is also preferable to use a known catalyst such as an amine compound such as triethylamine or dimethylbenzylamine; an ammonium salt such as tetraethylammonium chloride; a phosphonium salt such as tetraphenylphosphonium bromide; an amide compound such as dimethylformamide;

As a result of the introduction of the double bond, the double bond equivalent (meaning the molecular weight (g) per mol of double bond) of the alkali-soluble resin (polymer containing side chain double bond) obtained is preferably 250 to 4000 g / mol. When the double bond equivalent is in this range, the sensitivity to light is increased and the developability is further improved, coloring during curing is further suppressed, and storage stability and solubility in a solvent are further improved. The More preferably, it is 270-3000 g / mol, More preferably, it is 300-2000 g / mol, Most preferably, it is 320-2000 g / mol.

The double bond equivalent is a measure of the amount of double bonds contained in the molecule. If the compounds have the same molecular weight, the amount of double bonds introduced decreases as the value of the double bond equivalent increases. The double bond equivalent can be calculated from the charged amount of a polymer or a compound introducing a double bond. It can also be measured using various analyzes such as titration and elemental analysis, NMR and IR, and differential scanning calorimetry.
In the present specification, the double bond equivalent is determined by the following formula.
Double bond equivalent = (weight of base polymer + weight of compound containing functional group capable of binding to acid group and polymerizable double bond) / (compound containing functional group capable of binding to acid group and polymerizable double bond) Number of moles)

In the photosensitive resin composition of the present invention, the content (solid content ratio) of the alkali-soluble resin is, for example, 5 to 50% by mass with respect to 100% by mass of the total solid content of the photosensitive resin composition. preferable. Thereby, the effect by the said alkali-soluble resin is more fully exhibited. More preferably, it is 10-45 mass%, More preferably, it is 15-40 mass%.

(B) Polymerizable compound The polymerizable compound means a compound having a polymerizable group. A compound having a polymerizable double bond is preferable. Among these, from the viewpoint of photosensitivity and curability, a compound having two or more polymer double bonds in the molecule, that is, a bifunctional or higher polyfunctional compound is preferable, and a trifunctional or higher polyfunctional compound is more preferable. More preferably, it is a polyfunctional compound having 4 or more functional groups.

As the polymerizable compound, a compound having a (meth) acryloyl group is particularly preferable. Thereby, it becomes more excellent in photosensitivity and curability, and it becomes possible to give a hardened film with higher hardness. The (meth) acryloyl group means a methacryloyl group and / or an acryloyl group. In the present invention, those containing at least an acryloyl group are preferred from the viewpoint of better reactivity.

The molecular weight of the polymerizable compound (meaning an atomic weight equivalent (meaning the mass number of carbon atoms is 12.01)) is preferably 700 or less, more preferably 650 or less, and even more preferably 600 or less. Moreover, it is preferable that a double bond equivalent is 150 or less, More preferably, it is 140 or less, More preferably, it is 110 or less. The lower limit of the molecular weight and the double bond equivalent is not particularly limited as long as it can be cured. From the viewpoint of improving sensitivity, the molecular weight is preferably more than 250. Among them, a compound having a relatively small molecular weight and a small double bond equivalent is preferable from the viewpoint that an excellent pixel can be formed.

Preferable specific examples of the polymerizable compound include, for example, the following compounds.
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol Bifunctional (meta) such as di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene ) Acrylate compounds;

Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol 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 Addition pentaerythritol tetra (meth) acrylate, ethylene oxide addition dipe Taerythritol 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 Trifunctional or more polyfunctional (meth) acrylate compounds such as hexa (meth) acrylate;

Among these, from the viewpoint of improving the balance of various physical properties, a trifunctional or higher polyfunctional (meth) acrylate compound is preferable, such as pentaerythritol tetraacrylate, pentaerythritol triacrylate, dipentaerythritol tetra (meth) acrylate. It is particularly preferred to use dipentaerythritol penta (meth) acrylate and / or dipentaerythritol hexa (meth) acrylate.

The content ratio of the polymerizable compound is not particularly limited, and is preferably set appropriately in consideration of the ratio of other components such as a coloring material, for example, for 100 parts by mass of the total solid content of the photosensitive resin composition, It is preferable that it is 5-40 mass parts. Thereby, sclerosis | hardenability and transparency become higher. More preferably, it is 7-35 mass parts, More preferably, it is 10-30 mass parts.

(C) As the color material, a pigment (organic pigment, inorganic pigment), dye, or the like can be used.

The pigment is not particularly limited, and examples thereof include azo pigments, phthalocyanine pigments, polycyclic pigments (quinacridone, perylene, perinone, isoindolinone, isoindoline, dioxazine, thioindigo, and anthraquinone. , Quinophthalone, metal complex, diketopyrrolopyrrole, etc.), organic pigments such as dye lake pigments; white and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.) , Chromatic pigments (yellow lead, cadmium, chrome vermilion, nickel titanium, chrome titanium, yellow iron oxide, bengara, zinc chromate, red lead, ultramarine blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc. ), Black pigment (carbon black, bone black, graphite) Iron black, titanium black, etc.), the luminous material pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments (zinc sulfide, strontium sulfide, inorganic pigments strontium aluminate, etc.) and the like; and the like. Of these, organic pigments are preferred.

Although it does not specifically limit as said dye, For example, the organic dye described in Unexamined-Japanese-Patent No. 2010-9033, Unexamined-Japanese-Patent No. 2010-211198, Unexamined-Japanese-Patent No. 2009-51896, and Unexamined-Japanese-Patent No. 2008-50599 is used. Can be used. Of these, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like are preferable.

Among these, in the present invention, it is preferable to use at least a dye as a coloring material in order to meet the recent demand for higher color purity and higher brightness, and even if a dye is used, excellent cured material properties can be exhibited. Because it is very useful. When using at least a dye, the content of the dye is preferably 10% by mass or more with respect to 100% by mass of the total amount of the coloring material. More preferably, it is 20 mass% or more, More preferably, it is 40 mass% or more, Especially preferably, it is 60 mass% or more, Most preferably, it is 80 mass% or more. An upper limit is 100% by mass, that is, a mode in which only a dye is used as a colorant is also suitable, and a mode in which less than 100% by mass, that is, a dye and another colorant (for example, a pigment) are used in combination is also suitable. When the dye and the pigment are used in combination, the mass ratio (dye / pigment) is preferably 10 to 99/90 to 1, more preferably 20 to 99/80 to 1, still more preferably 40 to 99/60 to 1, Especially preferably, it is 60-99 / 40-1, Most preferably, it is 80-99 / 20-1.

The total amount of the color material (total content of the color material) is preferably 10% by mass or more with respect to 100% by mass of the total solid content of the photosensitive resin composition. More preferably, it is 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more. This makes it possible to sufficiently meet recent demands for higher color purity and higher brightness. . Especially preferably, it is 42 mass% or more, Most preferably, it is 44 mass% or more. Although an upper limit is not specifically limited, From a viewpoint of fully exhibiting image formability, such as photosensitivity, solubility, and sclerosis | hardenability resulting from other containing components (for example, alkali-soluble resin and a polymerizable monomer), 60 It is preferable that it is below mass%. More preferably, it is 55 mass% or less, More preferably, it is 50 mass% or less.

As described above, the resin composition of the present invention is (i) a form containing at least a dye as a color material, and (ii) 42% by mass of the color material in 100% by mass of the total solid content of the photosensitive resin composition. One or more of the above-described forms are satisfied. The preferable range of the dye content and the total color material content is as described above, and particularly preferably satisfies the above-mentioned form (i), and at least a dye is included as the color material, and the color material is a photosensitive resin. It is a form containing 40% by mass or more in 100% by mass of the total solid content of the composition, and particularly preferably when satisfying the above form (ii), the total content of the coloring material is the solid content of the photosensitive resin composition. It is the form which is 44 mass% or more with respect to 100 mass% of total amounts. Thereby, the effect of this invention will be exhibited more notably.

(D) Photopolymerization initiator The resin composition of the present invention preferably also contains a photopolymerization initiator.
Although it does not specifically limit as a photoinitiator, For example, the following compounds etc. are mentioned.
2-dimethylamino-2-methyl-1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino-1-phenylpropane-1-one ON, 2-dimethylamino-2-methyl-1- (4-methylphenyl) propan-1-one, 2-dimethylamino-1- (4-ethylphenyl) -2-methylpropan-1-one, 2- Dimethylamino-1- (4-isopropylphenyl) -2-methylpropan-1-one, 1- (4-butylphenyl) -2-dimethylamino-2-methylpropan-1-one, 2-dimethylamino-1 -(4-Methoxyphenyl) -2-methylpropan-1-one, 2-dimethylamino-2-methyl-1- (4-methylthiophenyl) propan-1-one 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- Benzyl-2-dimethylamino-1- (4-dimethylaminophenyl) -butan-1-one, 2-dimethylamino-2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) Α-aminoketone compounds such as phenyl] -1-butanone; 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenylketone, 2-hydroxy-2-methyl-1-phenyl Propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propyl Lopan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1- (4 -Methylthiophenyl) -2-morpholinopropan 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4- Alkylphenone compounds such as methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone;

2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 -Ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarboquinylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine, and other halomethylated triazine compounds 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4 Halomethylated oxadiazole compounds such as oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; , 2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′ , 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 Biimidazole compounds such as' -biimidazole; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- ( Oxime ester compounds such as 2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); bis (η5-2,4-cyclopentadien-1-yl) -bis (2 , 6-Difluoro-3- ( Titanocene compounds such as H-pyrrol-1-yl) -phenyl) titanium; benzoate compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; acridine compounds such as 9-phenylacridine; Hydroxycyclohexyl phenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2 Α-hydroxy ketone compounds such as -hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one;

Among the above photopolymerization initiators, it is particularly preferable to use at least an α-aminoketone compound from the viewpoint of excellent adhesion and a cured film shape. Among the α-amino ketone compounds, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butan-1-one and 2-dimethylamino-2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone are preferred, and 2-methyl-1 is more preferred. -(4-Methylthiophenyl) -2-morpholinopropan-1-one. As a commercially available product, for example, IRGACURE (registered trademark) 907, 369, 379 (all manufactured by BASF Japan Ltd.) and the like are preferable.

The content ratio of the photopolymerization initiator is not particularly limited, and is preferably set as appropriate in consideration of the ratio of other components such as a coloring material. For example, the total content of the photosensitive resin composition is 100% by mass. It is preferable that it is 0.5-30 mass%. Thereby, sclerosis | hardenability and transparency are improved further. More preferably, it is 1-25 mass%, More preferably, it is 1.5-20 mass%.

(E) Solvent It is preferable that the resin composition of the present invention also contains a solvent.
It does not specifically limit as a solvent, The various compounds mentioned above are mentioned as a specific example of the polymerization solvent at the time of obtaining alkali-soluble resin. Among these, it is preferable to use glycol monoether esters, monoalcohols, and / or glycol monoethers. More preferably, glycol monoether esters are used at least, and it is also preferable to use glycol monoether esters in combination with glycol monoethers.

The content rate of the said solvent is not specifically limited, It is preferable to set suitably according to the usage form (for example, application | coating etc.) of the photosensitive resin composition. For example, it is preferable to set the content ratio of the solvent so that the total solid content (solid content concentration) in 100% by mass of the photosensitive resin composition is 1 to 90% by mass. The total solid content in 100% by mass of the photosensitive resin composition is more preferably 5 to 70% by mass, and still more preferably 10 to 50% by mass.

(F) Dispersant The resin composition of the present invention preferably contains a dispersant. The dispersant is not particularly limited. For example, it has an interaction site to the color material and an interaction site to the dispersion medium (alkali-soluble resin, solvent, etc.), and stabilizes the dispersion of the color material in the dispersion medium. What has the function to do is preferable. In general, a dispersant that is classified into a resin-type dispersant (polymer dispersant), a surfactant (low molecular dispersant), and a pigment derivative, and that is usually used may be used.

Examples of the resin-type dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, and polysiloxanes. , Long-chain polyaminoamide phosphate, hydrogen group-containing polycarboxylic acid ester, amide formed by reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group, or a salt thereof, (meth) acrylic acid-styrene Copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, polyester, modified polyacrylate, ethylene oxide / polypropylene oxide adduct, etc. All It is. Among them, from the structural aspect, a resin having a graft structure in which the main chain is an anchor chain having an interaction site with a coloring material and the graft chain is a compatible chain having an interaction property with a dispersion medium, A resin having a block structure with a compatible chain is particularly preferably used.

Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, Anionic surfactants such as sodium stearate and sodium lauryl sulfate; nonions such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate Surfactants; cationic boundaries such as alkyl quaternary ammonium salts and their ethylene oxide adducts Alkyl betaines such as alkyl dimethylamino acetic acid betaine, and amphoteric surfactants such as alkyl imidazolines; active agents.

The dye derivative is a compound having a structure in which a functional group is introduced into the dye. Examples of the functional group include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a dialkylamino group, a hydroxyl group, a carboxyl group, an amide group, and a phthalimide group. Examples thereof include azo, anthraquinone, quinophthalone, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrene, perylene, and diketopyrrolopyrrole.

The content of the dispersant is not particularly limited, and may be set as appropriate depending on the purpose and application. For example, the balance of dispersion stability, durability (heat resistance, light resistance, weather resistance, etc.), transparency, and the like. In consideration of the above, it is preferable that the solid content of the dispersant is 0.01 to 60 parts by mass with respect to 100 parts by mass of the total solid content of the coloring material. More preferably, it is 0.1-50 mass parts, More preferably, it is 0.5-40 mass parts.

(G) Other components The photosensitive resin composition of the present invention may also contain one or more other components as long as the effects of the present invention are not impaired. For example, binder resins other than alkali-soluble resins; heat resistance improvers; leveling agents; coupling agents; development aids; fillers such as aluminum hydroxide, talc, clay and barium sulfate; antifoaming agents; sensitizers; Agents; lubricants; plasticizers; antioxidants; ultraviolet absorbers; flame retardants; polymerization inhibitors; thickeners;

Although the usage-amount of said other component should just be suitably set according to the objective and a use, it is preferable that it is 0-70 mass% in 100 mass% of solid content total amount of the photosensitive resin composition, for example. More preferably, it is 0.01-70 mass%, More preferably, it is 0.1-60 mass%, Most preferably, it is 0.3-50 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 and may further include the other process normally performed. Specifically, for example, after preparing a color material dispersion (mill base) containing a color material, a dispersant, a binder resin (alkali-soluble resin, etc.) and a solvent, a polymerizable monomer, a photopolymerization initiator is further prepared. It is preferable to prepare by adding a transparent resist solution (also referred to as a clear resist solution) containing a binder resin (alkali-soluble resin or the like) and a solvent. The obtained resin composition is preferably filtered with a filter or the like to remove fine dust.

In preparing the color material dispersion, it is preferable to finely disperse the color material using a disperser such as a paint conditioner, a bead mill, a roll mill, a ball mill, a jet mill, a homogenizer, a kneader, or a blender. More preferably, after kneading and dispersing with a roll mill, kneader, blender or the like, fine dispersion with a media mill such as a bead mill filled with 0.01 to 1 mm beads.

[Use of photosensitive resin composition]
The photosensitive resin composition of the present invention is excellent in various physical properties such as transparency and heat resistance, and can provide a cured product having excellent solvent resistance and high level of surface smoothness. It can be used for various applications such as materials, various coating agents, and paints. Preferable uses include various optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, and photoresists used in liquid crystal display devices and solid-state imaging devices, and electrical / electronic devices. Among these, the photosensitive resin composition is useful as a material for producing a color filter, an optical waveguide, and the like (for example, an alkali developing negative resist material). The display quality of various display devices and the reliability of imaging quality can be sufficiently enhanced to the extent that they can be sufficiently handled. In particular, the photosensitive resin composition is extremely useful for color filter applications.

As described above, the photosensitive resin composition is preferably used as a raw material for a color filter or a raw material for an optical waveguide. In addition to these, a protective film (a protective film for a color filter, a touch panel display) It is also suitable to use as a protective film for devices, etc.) or an insulating film (insulating film for touch panel display devices, etc.).

<Curing film>
The cured film of the present invention is obtained by curing the above-described photosensitive resin composition of the present invention, and can be obtained by irradiating (exposing) an active energy beam to the resin composition. Specifically, for example, the resin composition is preferably applied on a substrate (also referred to as a base material), dried, and irradiated (exposed) with an active energy ray on the coated surface. Since the photosensitive resin composition of the present invention is suitably used as a resist material, the form in which the cured film obtained by curing the photosensitive resin composition is a resist cured film is one of the preferred forms of the present invention. is there.

An example of an embodiment having the cured film is a color filter having the cured film on a substrate. This production method will be described in detail below.
The members constituting the color filter specifically include three primary color (RGB) pixels, a resin black matrix, a protective film, a columnar spacer, etc. At least one of these members constituting the color filter is a book. It is preferable to have a cured film formed by the photosensitive resin composition of the invention. Here, when forming RGB pixels, the resin composition of the present invention contains three primary colors of red, green, and blue, and when forming a resin black matrix, it contains a black color.

The color filter can be produced as follows, for example.
1) A photosensitive resin composition is coated (coated) on a substrate by a known coating method and dried to prepare a coating film. A transparent substrate is preferable as the substrate, and specific examples include glass (preferably non-alkali glass) and transparent plastic. Known coating methods include spin coating and spraying, with spin coating being preferred. Regarding the drying conditions, the drying temperature is preferably room temperature to 120 ° C, more preferably 60 to 100 ° C. The drying time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 10 minutes. Moreover, it is preferable to heat-dry under a normal pressure or a vacuum.

2) Then, a photomask (patterning film) provided with an opening corresponding to the desired pattern shape is placed on the coating obtained in 1) in a contact state or in a non-contact state and irradiated with light. , Cure. Light means not only visible light but also radiation such as ultraviolet rays, X-rays, and electron beams, but ultraviolet rays are most preferred. In general, a high-pressure mercury lamp is preferably used as the ultraviolet ray source.

3) After the light irradiation of 2), development is performed with a solvent, water, an alkaline aqueous solution or the like. Among these, an aqueous alkali solution is preferable because it has a low environmental load and can be developed with high sensitivity. Although it does not specifically limit as an alkali component in alkaline aqueous solution, A potassium hydroxide, sodium hydroxide, and / or sodium carbonate etc. are preferable. The concentration of the alkali component is preferably 0.01 to 5% by mass in 100% by mass of the alkaline aqueous solution. When the concentration of the alkali component is within this range, the solubility of the alkali-soluble resin is further improved, and the developability (development speed) can be further increased. More preferably, it is 0.05-3 mass%, More preferably, it is 0.1-1 mass%. A surfactant may be added to the alkaline aqueous solution.

4) The above steps 1) to 3) are performed using a photosensitive resin composition containing a black color material to form a resin black matrix on the substrate.

5) Next, the colorants of the photosensitive resin composition are sequentially changed to red (R), green (G), and blue (B), and the above steps 1) to 3) are repeated, and R, G, B These pixels are formed to produce RGB pixels.

6) Next, a protective film is formed as necessary for the purpose of protecting the RGB pixels formed on the substrate and improving the surface smoothness.

7) When the color filter is a color filter for a liquid crystal display device, it is preferable to further form a column spacer. The columnar spacer can be produced by applying the photosensitive resin composition to a thickness that is the height of the desired spacer on the surface on which the spacer is to be formed, and performing the steps 1) to 3).

Here, when producing a color filter, when each member is produced, post-development heating (post-bake) is performed to further cure, and if the solvent remains, it can be completely removed. preferable. The temperature during post-baking is preferably 120 to 300 ° C. When this temperature is set, the smoothness of the coating film due to coloring and thermal decomposition of the pixels can be more sufficiently suppressed, and the curing further proceeds and the coating film strength is further increased. More preferably, it is 150-250 degreeC, More preferably, it is 180-230 degreeC. The post-baking may be performed after development in the formation of each member (after the above-mentioned 3 at the time of creating each member) or after all the members are formed.

<Display device member and display device>
The member for a display device and the display device of the present invention have the cured film, but may further include one or more other constituent members. In recent years, with the advancement of technology of display devices and the like, there is a strong demand for higher performance for each member used. However, if the photosensitive resin composition of the present invention is used, such needs are increased. Therefore, the display quality and imaging quality of various display devices can be sufficiently improved. 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 a member in which another layer is combined with the single layer or multilayer member. Moreover, the member (for example, color filter etc.) which contains the said cured film in a structure may be sufficient.

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 weight”, “%” means “% by weight (mass%, wt%)”, and “v” means “volume”.

1. Physical property evaluation of copolymer solution (alkali-soluble resin) (1) Weight average molecular weight: Mw
Tetrahydrofuran (THF) was used as an eluent with GPC (trade name: HLC-8220 GPC, manufactured by Tosoh Corporation), TSKgel SuperHZM-N (manufactured by Tosoh Corporation) was used as a column, and calculation was performed in terms of standard polystyrene.

(2) Concentration of solid content (nonvolatile content) About 0.3 g of the copolymer solution prepared in each production example was weighed into an aluminum cup, dissolved by adding about 1 g of acetone, and then naturally dried at room temperature. Thereafter, using a hot air dryer (trade name: PHH-101, manufactured by ESPEC Corp.), the mixture was dried at 140 ° C. for 3 hours, then allowed to cool in a desiccator, and the weight was measured. From the weight reduction amount, the weight (solid content concentration) of the solid content (resin) of the copolymer solution was calculated.

(3) Acid value 1.5 g of the copolymer solution prepared in each production example was precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated with a 0.1 N aqueous KOH solution. Titration was performed using an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of polymer was determined from the solid content concentration (mgKOH / g).

(4) Double bond equivalent Determined according to the above formula.

2. Evaluation of physical properties of coating film (cured film) (1) Absorbance of photosensitive resin composition G (Green resist) A photosensitive resin composition G is spin-coated on a 5 cm square glass substrate and dried at 90 ° C. for 3 minutes. Thereafter, exposure was performed at 100 mJ with a high-pressure mercury lamp, and heat treatment was performed at 230 ° C. for 30 minutes to obtain a thin film having a thickness of 5 μm. Then, it was immersed in 20 g of 1-methyl-2-pyrrolidone (NMP) at 80 ° C. for 15 minutes, and the hue of NMP eluted from the coating film was measured with a spectrophotometer UV3100 (manufactured by Shimadzu Corporation) to determine the absorbance at 445 nm. (In other words, the amount of the color material exuded from the glass substrate was evaluated by measuring the absorbance of the NMP immersion liquid after the test). Table 3 shows the evaluation results of the photosensitive resin compositions G1 to 9 as Examples 1 to 9, and the evaluation result of the photosensitive resin composition G10 as Comparative Example 1.

(2) Absorption curable resin composition B of photosensitive resin composition B (Blue resist) is spin-coated on a 5 cm square glass substrate, dried at 90 ° C. for 3 minutes, and then exposed to 100 mJ with a high-pressure mercury lamp. A heat treatment was performed at 230 ° C. for 30 minutes to obtain a thin film having a thickness of 5 μm. Thereafter, the film was immersed in 20 g of NMP at 55 ° C. for 5 minutes, and the hue of NMP eluted from the coating film was measured with a spectrophotometer UV3100 (manufactured by Shimadzu Corporation) to determine the absorbance at 670 nm (that is, the NMP immersion liquid after the test) The amount of the color material exuded from the glass substrate was evaluated by measuring the absorbance of the glass substrate). Table 4 shows the evaluation results of the photosensitive resin compositions B1 to 9 as Examples 11 to 19 and the evaluation result of the photosensitive resin composition B10 as Comparative Example 2.

(3) Development speed and in-plane uniformity (Ra)
The photosensitive resin composition was applied onto a 10 cm square glass substrate with a spin coater and dried in an oven at 90 ° C. for 3 minutes. After drying, by a UV aligner (trade name: TME-150RNS, manufactured by TOPCON Co., Ltd.) equipped with a 2.0 kW ultra high pressure mercury lamp, with a photomask having a 100 μm line and space at a distance of 100 μm from the coating film , And irradiated with ultraviolet rays at an intensity of 100 mJ / cm ² (in terms of 365 nm illuminance). After UV irradiation, 0.05% aqueous potassium hydroxide solution is sprinkled on the coating film with a spin developer to dissolve and remove the unexposed area, and the remaining exposed area is developed by washing with pure water for 10 seconds. Thus, a line and space pattern was formed. About the obtained pattern, it used for evaluation of the development speed and in-plane uniformity as follows. The results are shown in Tables 3 and 4.
(3-1) Development speed The shortest time (seconds) during which a pattern can be formed during development was defined as the development speed.
(3-2) In-plane uniformity (Ra)
The width and height of the pattern were measured using a laser microscope (trade name: VK-9700, manufactured by Keyence Corporation). A range of 280 μm × 90 μm of a pattern formed with a 100 μm line and space photomask was measured.

3. Preparation 1 of alkali-soluble resin
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, in the monomer dropping tank, 15 g of (α-allyloxymethyl) methyl acrylate (AMA-M), 36.5 g of methacrylic acid (MAA), 47 g of cyclohexyl methacrylate (CHMA), methyl methacrylate ( MMA) 1.5 g and t-butyl peroxy-2-ethylhexanoate (trade name: Perbutyl (registered trademark) O, manufactured by NOF Corporation, hereinafter also referred to as PBO) were added and mixed with stirring. Moreover, as a chain transfer agent solution, 3.2 g of β-mercaptopropionic acid (β-MPA) and 18 g of propylene glycol methyl ether acetate (PGMEA) were added to the chain transfer agent dropping tank and mixed with stirring.
The reaction vessel was charged with 112 g of PGMEA and 56 g of propylene glycol monomethyl ether (PGME), purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition was added dropwise over 180 minutes and the chain transfer agent solution was added dropwise over 210 minutes. After completion of the dropwise addition of the chain transfer agent solution, 0.5 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1 hour, a gas introduction tube was attached to the separable flask and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 33 g of glycidyl methacrylate (GMA), 0.04 g of 6-tert-butyl-2,4-xylenol (trade name: Topanol, manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor, and dimethylbenzylamine as a catalyst (DMBA) 0.4 g was charged and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-1) containing 42.0 weight% of resin.
The double bond equivalent, the weight average molecular weight (Mw) and the acid value of the copolymer solution (A-1) are shown in Table 1 together with the copolymer solutions (A-2) to (A-10).

Production Example 2
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, AMA-M 15 g, MAA 42.5 g, CHMA 41 g, MMA 1.5 g, and PBO 2 g were added as a monomer composition to the monomer dropping tank and mixed with stirring. Moreover, as a chain transfer agent solution, 3.2 g of β-MPA and 18 g of PGMEA were added to the chain transfer agent dropping tank and mixed with stirring.
After charging 112 g of PGMEA and 56 g of PGME into the reaction tank and replacing with nitrogen, the reaction tank was heated to 90 ° C. by heating in an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition was added dropwise over 180 minutes and the chain transfer agent solution was added dropwise over 210 minutes. After completion of the dropwise addition of the chain transfer agent solution, 0.5 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1 hour, a gas introduction tube was attached to the separable flask and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 41 g of GMA, 0.04 g of topanol as a polymerization inhibitor, and 0.4 g of DMBA as a catalyst were charged in a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-2) containing 43.4 weight% of resin.

Production Example 3
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 15 g of AMA-M, 36.5 g of MAA, 47 g of benzyl methacrylate (BzMA), 1.5 g of MMA, and 2 g of PBO were added as a monomer composition to the monomer dropping tank and mixed with stirring. Moreover, as a chain transfer agent solution, 3.2 g of β-MPA and 18 g of PGMEA were added to the chain transfer agent dropping tank and mixed with stirring.
After charging 112 g of PGMEA and 56 g of PGME into the reaction tank and replacing with nitrogen, the reaction tank was heated to 90 ° C. by heating in an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition was added dropwise over 180 minutes and the chain transfer agent solution was added dropwise over 210 minutes. After completion of the dropwise addition of the chain transfer agent solution, 0.5 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1 hour, a gas introduction tube was attached to the separable flask and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 33 g of GMA, 0.04 g of topanol as a polymerization inhibitor, and 0.4 g of DMBA as a catalyst were charged in a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-3) containing 41.7 weight% of resin.

Production Example 4
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, AMA-M 15 g, MAA 31.5 g, CHMA 47 g, MMA 6.5 g, and PBO 2 g were added as a monomer composition into the monomer dropping tank and mixed with stirring. Moreover, as a chain transfer agent solution, 3.2 g of β-MPA and 18 g of PGMEA were added to the chain transfer agent dropping tank and mixed with stirring.
After charging 112 g of PGMEA and 56 g of PGME into the reaction tank and replacing with nitrogen, the reaction tank was heated to 90 ° C. by heating in an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition was added dropwise over 180 minutes and the chain transfer agent solution was added dropwise over 210 minutes. After completion of the dropwise addition of the chain transfer agent solution, 0.5 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1 hour, a gas introduction tube was attached to the separable flask and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 33 g of GMA, 0.04 g of topanol as a polymerization inhibitor, and 0.4 g of DMBA as a catalyst were charged in a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-4) containing 41.8 weight% of resin.

Production Example 5
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, AMA-M 15 g, MAA 41.5 g, CHMA 42 g, MMA 1.5 g, and PBO 2 g were added as a monomer composition into the monomer dropping tank and mixed with stirring. Moreover, as a chain transfer agent solution, 3.2 g of β-MPA and 18 g of PGMEA were added to the chain transfer agent dropping tank and mixed with stirring.
After charging 112 g of PGMEA and 56 g of PGME into the reaction tank and replacing with nitrogen, the reaction tank was heated to 90 ° C. by heating in an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition was added dropwise over 180 minutes and the chain transfer agent solution was added dropwise over 210 minutes. After completion of the dropwise addition of the chain transfer agent solution, 0.5 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1 hour, a gas introduction tube was attached to the separable flask and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 33 g of GMA, 0.04 g of topanol as a polymerization inhibitor, and 0.4 g of DMBA as a catalyst were charged in a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-5) containing 42.1 weight% of resin.

Production Example 6
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, AMA-M15g, MAA35.5g, CHMA47g, MMA2.5g, and PBO2g were put into the monomer dropping tank as a monomer composition and mixed with stirring. Further, 4.0 g of β-MPA and 18 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
After charging 112 g of PGMEA and 56 g of PGME into the reaction tank and replacing with nitrogen, the reaction tank was heated to 90 ° C. by heating in an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition was added dropwise over 180 minutes and the chain transfer agent solution was added dropwise over 210 minutes. After completion of the dropwise addition of the chain transfer agent solution, 0.5 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1 hour, a gas introduction tube was attached to the separable flask and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 33 g of GMA, 0.04 g of topanol as a polymerization inhibitor, and 0.4 g of DMBA as a catalyst were charged in a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-6) containing 41.8 weight% of resin.

Production Example 7
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, AMA-M15g, MAA37g, CHMA47g, MMA1g, and PBO2g were put into the monomer dropping tank as a monomer composition and mixed with stirring. Further, 2.3 g of β-MPA and 18 g of PGMEA were added to the chain transfer agent dropping tank as a chain transfer agent solution, and mixed with stirring.
After charging 112 g of PGMEA and 56 g of PGME into the reaction tank and replacing with nitrogen, the reaction tank was heated to 90 ° C. by heating in an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition was added dropwise over 180 minutes and the chain transfer agent solution was added dropwise over 210 minutes. After completion of the dropwise addition of the chain transfer agent solution, 0.5 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1 hour, a gas introduction tube was attached to the separable flask and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 33 g of GMA, 0.04 g of topanol as a polymerization inhibitor, and 0.4 g of DMBA as a catalyst were charged in a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-7) containing resin 43.3% by weight.

Production Example 8
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 15 g of AMA-M, 34 g of acrylic acid (AA), 47 g of CHMA, 4 g of MMA, and 2 g of PBO were added as a monomer composition into the monomer dropping tank and mixed with stirring. Moreover, as a chain transfer agent solution, 3.2 g of β-MPA and 18 g of PGMEA were added to the chain transfer agent dropping tank and mixed with stirring.
After charging 112 g of PGMEA and 56 g of PGME into the reaction tank and replacing with nitrogen, the reaction tank was heated to 90 ° C. by heating in an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition was added dropwise over 180 minutes and the chain transfer agent solution was added dropwise over 210 minutes. After completion of the dropwise addition of the chain transfer agent solution, 0.5 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1 hour, a gas introduction tube was attached to the separable flask and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 33 g of GMA, 0.04 g of topanol as a polymerization inhibitor, and 0.4 g of DMBA as a catalyst were charged in a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-8) containing 42.0 weight% of resin.

Production Example 9
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, AMA-M 30 g, MAA 36.5 g, CHMA 32 g, MMA 1.5 g, and PBO 2 g were added as a monomer composition into the monomer dropping tank and mixed with stirring. Moreover, as a chain transfer agent solution, 3.2 g of β-MPA and 18 g of PGMEA were added to the chain transfer agent dropping tank and mixed with stirring.
After charging 112 g of PGMEA and 56 g of PGME into the reaction tank and replacing with nitrogen, the reaction tank was heated to 90 ° C. by heating in an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition was added dropwise over 180 minutes and the chain transfer agent solution was added dropwise over 210 minutes. After completion of the dropwise addition of the chain transfer agent solution, 0.5 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1 hour, a gas introduction tube was attached to the separable flask and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 33 g of GMA, 0.04 g of topanol as a polymerization inhibitor, and 0.4 g of DMBA as a catalyst were charged in a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-9) containing 42.1 weight% of resin.

Production Example 10
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 36.5 g of MAA, 62 g of CHMA, 1.5 g of MMA, and 2 g of PBO were added as a monomer composition into the monomer dropping tank and mixed with stirring. Moreover, as a chain transfer agent solution, 3.2 g of β-MPA and 18 g of PGMEA were added to the chain transfer agent dropping tank and mixed with stirring.
After charging 112 g of PGMEA and 56 g of PGME into the reaction tank and replacing with nitrogen, the reaction tank was heated to 90 ° C. by heating in an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition was added dropwise over 180 minutes and the chain transfer agent solution was added dropwise over 210 minutes. After completion of the dropwise addition of the chain transfer agent solution, 0.5 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1 hour, a gas introduction tube was attached to the separable flask and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 33 g of GMA, 0.04 g of topanol as a polymerization inhibitor, and 0.4 g of DMBA as a catalyst were charged in a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-10) containing 41.8 weight% of resin.

4. Preparation and evaluation of photosensitive resin composition G (Green resist) Preparation Example G1
7.38 g of copolymer solution (A-1) as a binder resin (that is, resin 3.1 g), 1.04 g of SOLPERSE24000GR (manufactured by Nippon Lubrizol, hereinafter referred to as SP24000) and SOLPERSE12000 (manufactured by Nippon Lubrizol, hereinafter SP12000) as a dispersant. 0.26 g, C.I. I. Pigment Green 36 (Heubach, hereinafter referred to as PG36) 5.4 g and C.I. I. 3.6 g of Pigment Yellow 150 (manufactured by Lanxess, hereinafter referred to as PY150) was weighed into a 225 ml mayonnaise bottle and diluted with PGMEA to a non-volatile content concentration of 20% by weight. To this, 67 g of zirconia beads having a diameter of 1.0 mm was added and capped. This was shaken with a paint shaker for 3 hours for dispersion treatment.
In this dispersion, 3.1 g of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., hereinafter referred to as DPHA) as a polymerizable monomer and 3.81 g of a copolymer solution (A-1) as a binder resin (that is, resin 1) .6 g), and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE (registered trademark) 369, manufactured by BASF Japan Ltd., as a photopolymerization initiator, 1.9 g) (represented as Irg369) was added, and diluted with PGMEA so that the non-volatile content concentration was 20% by weight. After removing the zirconia beads, the mixture was filtered with a filter having a pore size of 1.0 μm to prepare a photosensitive resin composition G1. The composition is shown in Table 2.

Preparation Examples G2 to G10
Photosensitive resin compositions G2 to G10 were respectively prepared in the same manner as in Preparation Example G1, except that the copolymer solutions (A-2 to A-10) were used as the binder resins, respectively. The composition is shown in Table 2.

Examples 1-9, Comparative Example 1
For each of the photosensitive resin compositions G1 to G10, the absorbance is evaluated according to the above-described evaluation method “2 (1) Absorbance of the photosensitive resin composition G (Green resist)”, and the development speed and surface are evaluated according to the evaluation method. Inner uniformity (Ra) was also evaluated. The results are shown in Table 3.

5. Preparation of Photosensitive Resin Composition B (Blue Resist) and Evaluation Preparation Example B1
8.33 g of copolymer solution (A-1) as binder resin (that is, 3.5 g of resin) and DISPERBYK-2001 (non-volatile content: 1.3 g, manufactured by BYK Japan, Inc., hereinafter referred to as “byk2001”) as a dispersant 2.86 g C. of a pigment as a coloring material. I. Pigment Violet 23 (manufactured by Clariant, hereinafter referred to as PV23) 1.6 g and C.I. I. 6.4 g of Solvent Blue 35 (manufactured by MP Biomedicals, hereinafter referred to as SB35) was weighed into a 225 ml mayonnaise bottle and diluted with PGMEA so that the nonvolatile content concentration was 20% by weight. To this, 64 g of zirconia beads having a diameter of 1.0 mm was added and capped. This was shaken with a paint shaker for 3 hours for dispersion treatment.
In this dispersion, 3.5 g of DPHA as a polymerizable monomer, 4.29 g of a copolymer solution (A-1) (that is, 1.8 g of resin) as a binder resin, and 1. Irg369 as a photopolymerization initiator. 9 g was added and diluted with PGMEA so that the nonvolatile content concentration was 20% by weight. After removing the zirconia beads, the mixture was filtered through a filter having a pore diameter of 1.0 μm to prepare a photosensitive resin composition B1. The composition is shown in Table 2.

Preparation Examples B2 to B10
Photosensitive resin compositions B2 to B10 were prepared in the same manner as in Preparation Example B1, except that the copolymer solutions (A-2 to A-10) were used as binder resins, respectively. The composition is shown in Table 2.

Examples 11-19, Comparative Example 2
For each of the photosensitive resin compositions B1 to B10, the absorbance is evaluated according to the above-described evaluation method “2 (2) Absorbance of photosensitive resin composition B (Blue resist)”, and the development speed and surface are evaluated according to the evaluation method. Inner uniformity (Ra) was also evaluated. The results are shown in Table 4.

From the above examples and comparative examples, the following was confirmed.
Examples 1 to 9 and Comparative Example 1 are mainly different in that the alkali-soluble resin used has a heterocyclic structure in the main chain. Under this difference, comparing the results of evaluating the absorbance, development speed and in-plane uniformity at a wavelength close to the maximum absorption wavelength of the color material used, the results were obtained using an alkali-soluble resin having a heterocyclic structure in the main chain. In Examples 1 to 9, all the measurement results of absorbance, development speed, and in-plane uniformity are remarkably low as compared with Comparative Example 1 using an alkali-soluble resin having no heterocyclic structure. That is, in Examples 1 to 9, as compared with Comparative Example 1, the bleeding of the coloring material into the solvent was remarkably suppressed, the developability was very high, and a cured product having excellent surface smoothness was obtained. I understand. The same is confirmed from the comparison between Examples 11 to 19 and Comparative Example 2.

Moreover, although the cured | curing material obtained in Examples 1-19 contains a dye as a coloring material at least or contains a coloring material at a very high density | concentration, as above-mentioned, in solvent resistance, developability, and surface smoothness. Since it is extremely excellent, it is very useful as a material / component for improving the display quality and imaging quality of liquid crystal display devices, imaging tube elements, etc., and can fully meet the demands for thinning the components. .
Although not specified above, the cured film of the photosensitive resin composition obtained in the examples was excellent in transparency and heat resistance.

In addition, when the influence on the solvent resistance due to the difference in the amount of GMA used to obtain the alkali-soluble resin was examined separately, it was found that the solvent resistance was improved when the amount of GMA added was large. This is considered to result from the fact that the coloring material is more difficult to ooze out because the crosslinking density increases when the amount of the compound containing a functional group capable of binding to an acid group such as GMA and a polymerizable double bond is large. On the other hand, the heterocyclic structure that the alkali-soluble resin has in the main chain itself has a function of reducing the inhibition of curing by oxygen by being combined with oxygen, and as a result, curing proceeds further, and solvent resistance and surface smoothness are improved. It is thought to improve. Therefore, when the alkali-soluble resin is a side chain double bond-containing polymer (in particular, as described above, the base polymer component has a functional group capable of binding to an acid group such as GMA and a polymerizable double bond. In the case where the amount of the compound to be added is 30 parts by mass or more), the action and effect of the present invention are more remarkably exhibited by the synergistic effect of both of them.

Claims (6)

A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound and a coloring material,
The alkali-soluble resin is a resin having a heterocyclic structure in the main chain,
The photosensitive resin composition is selected from the group consisting of a form containing at least a dye as a coloring material and a form containing a coloring material in an amount of 42% by mass or more in 100% by mass of the total solid content of the photosensitive resin composition. A photosensitive resin composition characterized by being in at least one form. The alkali-soluble resin has, in the main chain, the following general formula (1) or (2):

(In the formula, R ¹ and R ³ are the same or different and each represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. R ² represents a hydrogen atom or a methyl group. X, Y and Z are the same. Or differently, a methylene group, a methylene group in which a hydrogen atom is substituted with a methyl group, an oxygen atom, a sulfur atom, or an imino group, provided that at least one of X, Y, and Z is an oxygen atom, sulfur The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition has a heterocyclic-containing structural unit represented by: an atom or an imino group. 3. The photosensitive resin composition according to claim 1, wherein the coloring material contains 10% by mass or more of a dye in a total amount of 100% by mass of the coloring material. A cured film obtained by curing 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.