JP6782077B2 - Photosensitive resin composition for color filters - Google Patents

Description

The present invention relates to a photosensitive resin composition for a color filter.

A color filter used in an image display device such as a liquid crystal display device is usually manufactured by a photolithography method or the like after applying a photosensitive resin composition containing a color material such as a pigment and a photocurable resin to a transparent substrate. Has been done. In recent years, with the demand for higher performance of image display devices, color filters that can contribute to improvement of brightness, contrast, etc. are required.

Examples of the method of forming the color filter that can contribute to the improvement of the brightness and the contrast include a method of refining the pigment as the coloring material in the photosensitive resin composition, a method of using a dye as the coloring material, and the like. However, there is a problem that the finer the pigment, the worse the dispersibility and stability. Further, the photosensitive resin composition containing the finely divided pigment or dye has a problem that the developing speed becomes slow. Further, by extending the developing time, it is necessary to further improve the adhesion of the color filter formed of the photosensitive resin composition to the substrate.

Japanese Unexamined Patent Publication No. 2010-168580

The present invention has been made to solve the above problems, and an object of the present invention is a photosensitive for a color filter capable of forming a color filter having excellent development speed, surface smoothness and adhesion to a substrate. The purpose is to provide a sex resin composition.

式（４）〜（７）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６はそれぞれ独立して、水素原子または炭素数が１〜３０の直鎖状もしくは分岐状のアルキル基である。
１つの実施形態においては、上記側鎖に芳香環を有する構成単位が、側鎖にビフェニル基を有する構成単位である。
１つの実施形態においては、上記側鎖にビフェニル基を有する構成単位が、一般式（１０）または（１１）で表されるモノマー由来の構成単位である。

式（１１）中、ｎ１は１〜１０である。
１つの実施形態においては、上記アルカリ可溶性樹脂が、側鎖に酸基を有する構成単位を含む。
１つの実施形態においては、上記アルカリ可溶性樹脂が、側鎖に炭素二重結合を有する構成単位を含む。
１つの実施形態においては、上記色材が、顔料および／または染料である。 The photosensitive resin composition for a color filter of the present invention contains an alkali-soluble resin, a coloring material, and a polyfunctional monomer, and the alkali-soluble resin has a structural unit having a ring structure in the main chain and an aroma in the side chain. Includes a structural unit having a ring group.
In one embodiment, the alkali-soluble resin is a (meth) acrylic resin.
In one embodiment, the structural unit having a ring structure in the main chain is at least one selected from the structural units represented by the general formulas (1) to (7).

In formulas (4) to (7), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently linear or branched with hydrogen atoms or 1 to 30 carbon atoms. It is an alkyl group.
In one embodiment, the structural unit having an aromatic ring in the side chain is a structural unit having a biphenyl group in the side chain.
In one embodiment, the structural unit having a biphenyl group in the side chain is a monomer-derived structural unit represented by the general formula (10) or (11).

In formula (11), n1 is 1-10.
In one embodiment, the alkali-soluble resin comprises a structural unit having an acid group in the side chain.
In one embodiment, the alkali-soluble resin comprises a building block having a carbon double bond in the side chain.
In one embodiment, the colorant is a pigment and / or dye.

According to the present invention, a photosensitive resin composition for a color filter having an excellent development speed can be obtained by containing an alkali-soluble resin having a ring structure in the main chain and an aromatic ring group in the side chain. .. Further, by using the photosensitive resin composition for a color filter, it is possible to form a color filter having excellent smoothness and adhesion to a substrate. Further, when a pigment is used as the coloring material, a photosensitive resin composition for a color filter having excellent dispersion stability of the pigment can be obtained. Further, in the present invention, the pigment can be miniaturized while having excellent dispersion stability.

A. Outline of Photosensitive Resin Composition for Color Filter The photosensitive resin composition for color filter of the present invention (hereinafter, also simply referred to as a photosensitive resin composition) contains an alkali-soluble resin, a coloring material, and a polyfunctional monomer. .. The alkali-soluble resin contains a structural unit having a ring structure in the main chain and a structural unit having an aromatic ring group in the side chain. Practically, the photosensitive resin composition may further comprise any suitable solvent and / or any suitable additive such as a dispersant, a photopolymerization initiator. The photosensitive resin composition for a color filter of the present invention is preferably a negative photosensitive resin composition.

B. Alkali-soluble resin As described above, the alkali-soluble resin contains a structural unit (A) having a ring structure in the main chain and a structural unit (B) having an aromatic ring group in the side chain. In one embodiment, the alkali-soluble resin further comprises a building block (C) and / or other building blocks (D) having an acid group in the side chain. The alkali-soluble resin is typically a (meth) acrylic resin. The (meth) acrylic resin is not particularly limited as long as it is a resin obtained by polymerizing a monomer composition containing at least 10% by weight or more of a (meth) acrylic monomer such as a (meth) acrylic acid ester. The composition may contain other monomers copolymerizable with the (meth) acrylic monomer.

The alkali-soluble resin has a monomer composition containing a monomer (a) having a ring structure in the main chain and / or a monomer (a') capable of forming a ring structure, and a monomer (b) having an aromatic ring group in the side chain. It can be obtained by polymerizing a product. The monomer composition may further include a monomer (c) having an acid group, a monomer (c') into which an acid group can be introduced, and / or other monomers (d) constituting another structural unit (D). In one embodiment, the monomer (b), monomer (c), monomer (c') and / or monomer (d) are (meth) acrylic monomers, preferably acrylic monomers.

B-1. Structural unit (A) having a ring structure in the main chain
When the alkali-soluble resin has a structural unit (A) having a ring structure in the main chain, a photosensitive resin composition having high solubility in a developing solution can be obtained. By using such a photosensitive resin composition, a color filter can be quickly formed without causing a development residue. Further, by using an alkali-soluble resin having a structural unit (A) having a ring structure in the main chain, a color filter having excellent transparency and substrate adhesion can be obtained.

Examples of the structural unit (A) having a ring structure in the main chain include a structural unit having a maleimide structure, an N-substituted maleimide structure, a lactone ring structure, a glutaric anhydride structure, a maleic anhydride structure, and the like. Of these, a maleimide structure or an N-substituted maleimide structure is preferable. By using an alkali-soluble resin having a structural unit having a maleimide structure or an N-substituted maleimide structure in the main chain, a photosensitive resin composition having higher solubility in a developing solution can be obtained. Specifically, the structural unit (A) having a ring structure in the main chain is preferably at least one selected from the structural units represented by the general formulas (1) to (3), and the general formula (1). ) Is more preferable. By using an alkali-soluble resin (preferably (meth) acrylic resin) having a structural unit represented by the general formula (1), a photosensitive resin composition capable of forming a high-strength color filter can be obtained. ..

式（４）〜（７）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６はそれぞれ独立して、水素原子または炭素数が１〜３０の直鎖状もしくは分岐状のアルキル基であり、好ましくは水素原子または炭素数が１〜１０の直鎖状もしくは分岐状のアルキル基であり、より好ましくは水素原子または炭素数が１〜５の直鎖状もしくは分岐状のアルキル基であり、さらに好ましくはメチル基である。 The structural unit (A) having a ring structure in the main chain may be at least one selected from the structural units represented by the general formulas (4) to (7). Of these, it is a structural unit represented by the general formula (4) or (7).

In formulas (4) to (7), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently linear or branched with hydrogen atoms or 1 to 30 carbon atoms. It is an alkyl group, preferably a linear or branched alkyl group having 1 to 10 hydrogen atoms or carbon atoms, and more preferably a linear or branched alkyl group having 1 to 5 hydrogen atoms or carbon atoms. It is a group, more preferably a methyl group.

The structural unit (A) having a ring structure in the main chain may be composed of the monomer (a) having a ring structure in the main chain. Examples of the monomer (a) having a ring structure in the main chain include maleimide, benzylmaleimide, phenylmaleimide, naphthylmaleimide, NO-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, and Np-hydroxyphenylmaleimide. , NO-Chlorophenylmaleimide, Nm-chlorophenylmaleimide, Np-chlorophenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, NO- Aromatic substituted maleimides such as methoxyphenyl maleimide, Nm-methoxyphenyl maleimide, Np-methoxyphenyl maleimide; alkyl substituted maleimides such as cyclohexyl maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, isopropyl maleimide and the like. Be done. Of these, maleimide, benzylmaleimide, phenylmaleimide, and cyclohexylmaleimide are preferable, benzylmaleimide, phenylmaleimide, and cyclohexylmaleimide are more preferable, and benzylmaleimide is more preferable. The above-mentioned monomers may be used alone or in combination of two or more.

式（８）および（９）中、Ｒ^１、Ｒ^２およびＲ^３は上記で説明したとおりである。 As the monomer constituting the structural unit (A) having a ring structure in the main chain, a monomer (a') capable of forming a ring structure by an intramolecular cyclization step may be used. According to the monomer (a'). The structural units represented by the general formulas (4) to (7) are formed. Examples of the monomer (a') include 1,6-dienes represented by the general formula (8) or (9).

In formulas (8) and (9), R ¹ , R ² and R ³ are as described above.

The content ratio of the structural unit (A) having a ring structure in the main chain is preferably 5 parts by weight to 50 parts by weight, more preferably 8 parts by weight or more, based on 100 parts by weight (mass part) of the alkali-soluble resin. It is 30 parts by weight, more preferably 10 parts by weight to 25 parts by weight.

In the above-mentioned monomer composition I for forming an alkali-soluble resin, the content ratio of the monomer (a) having a ring structure in the main chain is preferably 5 parts by weight to 50 parts by weight with respect to 100 parts by weight of all the monomers in the monomer composition I. It is a part by weight, more preferably 8 parts by weight to 30 parts by weight, and further preferably 10 parts by weight to 25 parts by weight. Further, in the above-mentioned monomer composition I for forming an alkali-soluble resin, the content ratio of the monomer (a') capable of forming a ring structure is preferably 5 parts by weight with respect to 100 parts by weight of all the monomers in the monomer composition I. It is ~ 50 parts by weight, more preferably 8 parts by weight to 30 parts by weight, and further preferably 10 parts by weight to 25 parts by weight.

B-2. Structural unit (B) having an aromatic ring group in the side chain
When the alkali-soluble resin has a structural unit (B) having an aromatic ring group in the side chain, a photosensitive resin composition having excellent dispersion stability of the pigment can be obtained. Further, if an alkali-soluble resin having a structural unit (B) having an aromatic ring group in the side chain is used, a photosensitive resin composition having an excellent developing speed can be obtained. Further, a color filter produced by using a photosensitive resin composition containing an alkali-soluble resin having a structural unit (B) having an aromatic ring group in a side chain has excellent adhesion to a substrate and is smooth. Is also excellent.

式（１１）中、ｎ１は１〜１０であり、好ましくは１または２である。 Preferably, the structural unit (B) having an aromatic ring group in the side chain is the structural unit (B1) having a biphenyl group in the side chain. Further, preferably, the structural unit (B) having an aromatic ring group in the side chain is a structural unit derived from a (meth) acrylic monomer. Examples of such a structural unit (B1) include biphenyl (meth) acrylate, o-biphenyloxyethyl (meth) acrylate (ethoxylated o-phenylphenol (meth) acrylate), and o-biphenyloxyethoxyethyl (meth). Acrylate, m-biphenyloxyethyl acrylate, p-biphenyloxyethyl (meth) acrylate, o-biphenyloxy-2-hydroxypropyl (meth) acrylate, p-biphenyloxy-2-hydroxypropyl (meth) acrylate, m-biphenyl Oxy-2-hydroxypropyl (meth) acrylate, N- (meth) acryloyloxyethyl-o-biphenyl = carbamate, N- (meth) acryloyloxyethyl-p-biphenyl = carbamate, N- (meth) acryloyloxyethyl- Examples thereof include structural units derived from a monomer (b1) having a biphenyl group on the side chain such as m-biphenyl = carbamate, o-phenylphenol glycidyl ether acrylate, and o-biphenyloxypropyl (meth) acrylate. Of these, it is a constituent unit derived from an acrylic monomer. If an acrylic monomer having no methyl group in the double bond portion is used, a photosensitive resin composition having a high developing speed can be obtained. In one embodiment, the structural unit (B1) having a biphenyl group in the side chain is a structural unit derived from the monomer (b1) represented by the general formula (10) or (11). More preferably, the structural unit (B1) having a biphenyl group in the side chain is a structural unit derived from the monomer (b1) represented by the general formula (11). The above-mentioned monomers may be used alone or in combination of two or more.

In formula (11), n1 is 1 to 10, preferably 1 or 2.

The content ratio of the structural unit (B) having an aromatic ring group in the side chain is preferably 10 parts by weight to 80 parts by weight, and more preferably 15 parts by weight to 70 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. It is more preferably 20 parts by weight to 65 parts by weight. Within such a range, the effect of the present invention becomes more remarkable.

In the above-mentioned monomer composition I for forming an alkali-soluble resin, the content ratio of the monomer (b) having a biphenyl group in the side chain is preferably 20 parts by weight to 80 parts by weight with respect to 100 parts by weight of all the monomers in the monomer composition I. It is a part by weight, more preferably 30 parts by weight to 70 parts by weight, and further preferably 40 parts by weight to 65 parts by weight. Within such a range, the effect of the present invention becomes more remarkable.

B-3. Constituent unit (C) having an acid group in the side chain
Preferably, the alkali-soluble resin has a structural unit (C) having an acid group in the side chain. If the alkali-soluble resin has a structural unit (C) having an acid group in the side chain, a photosensitive resin composition having excellent alkali developability can be obtained. Examples of the monomer (monomer (c) having an acid group) constituting the structural unit (C) having an acid group in the side chain include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, and itaconic acid. Monomers having a carboxyl group such as acid and ω-carboxy-polycaprolactone monoacrylate; monomers having a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride can be mentioned. Of these, (meth) acrylic acid is preferable. These monomers may be used alone or in combination of two or more.

As the monomer constituting the structural unit (C) having an acid group in the side chain, a monomer (c') into which an acid group can be introduced may be used. The monomer (c') is a monomer capable of imparting an acid group after polymerization. Examples of the monomer (c') include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and an isocyanate such as 2-isocyanatoethyl (meth) acrylate. Examples include monomers having a group. These monomers may be used alone or in combination of two or more. The post-treatment for imparting an acid group differs depending on the type of monomer (c') used, but when a monomer (c') having a hydroxyl group is used, for example, succinic anhydride and tetrahydrophthalic anhydride , An acid anhydride such as maleic anhydride may be added. When a monomer (c') having an epoxy group is used, for example, a compound having an amino group and an acid group such as N-methylaminobenzoic acid and N-methylaminophenol is added, or (meth). An acid anhydride (for example, succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride) may be added to the hydroxyl group generated after the addition of an acid such as acrylic acid. When a monomer (c') having an isocyanate group is used, for example, a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be added.

The content ratio of the structural unit (C) having an acid group in the side chain is preferably 10 parts by weight to 60 parts by weight, more preferably 15 parts by weight to 50 parts by weight, based on 100 parts by weight of the alkali-soluble resin. Yes, more preferably 15 to 45 parts by weight.

The content ratio of the monomer (c) having an acid group in the above-mentioned monomer composition I for forming the alkali-soluble resin is preferably 15 parts by weight to 60 parts by weight, more preferably 20 parts by weight to 50 parts by weight. More preferably, it is 20 parts by weight to 45 parts by weight. Further, in the above-mentioned monomer composition I for forming an alkali-soluble resin, the content ratio of the monomer (c') into which an acid group can be introduced is preferably 15 parts by weight to 60 parts by weight, and more preferably 20 parts by weight to 50 parts by weight. It is a part by weight, more preferably 20 parts by weight to 45 parts by weight.

B-4. Other structural units (D)
The alkali-soluble resin may further have another structural unit (D). Other structural units include a structural unit (D1) having two or more oxyalkylene groups in the side chain, the above-mentioned monomer (a), monomer (a'), monomer (b), monomer (c) and / or monomer ( Examples thereof include a structural unit (D2) derived from another monomer (d2) that can be polymerized with c').

(Constituent unit (D1) having two or more oxyalkylene groups in the side chain)
When the alkali-soluble resin has a structural unit (D1) having two or more oxyalkylene groups in the side chain, a photosensitive resin composition capable of forming a color filter having high crosslink density and high breaking strength can be obtained. Can be done. In addition, a photosensitive resin composition having particularly excellent color material dispersibility can be obtained. When an alkali-soluble resin having a structural unit (D1) and a polyfunctional monomer described later (preferably a polyfunctional monomer having no oxyalkylene group) are combined to form a photosensitive resin composition, the above effect is obtained. This is especially noticeable.

式（１２）中、Ｒ^７、Ｒ^８およびＲ^９はそれぞれ独立して、水素原子またはメチル基であり、好ましくは水素原子である。Ｒ^１０は、炭素数が１〜２０の直鎖状もしくは分岐状のアルキル基、炭素数が２〜２０の直鎖状もしくは分岐状のアルケニル基または炭素数が６〜２０の芳香族炭化水素基であり、好ましくは水素原子、炭素数が１〜２０の直鎖状のアルキル基、炭素数が２〜２０の直鎖状のアルケニル基または炭素数が６〜２０の芳香族炭化水素基であり、より好ましくは炭素数が１〜１０の直鎖状のアルキル基または炭素数が６〜１２の芳香族炭化水素基であり、さらに好ましくは炭素数が１〜５の直鎖状のアルキル基、フェニル基またはビフェニル基であり、特に好ましくはメチル基、フェニル基またはビフェニル基である。なお、アルキル基、アルケニル基および芳香族炭化水素基は、置換基を有していてもよい。ＡＯは、オキシアルキレン基を表す。ＡＯで表されるオキシアルキレン基の炭素数は２〜２０であり、好ましくは２〜１０であり、より好ましくは２〜５であり、さらに好ましくは２である。構成単位（Ｄ１）は１種または２種以上のオキシアルキレン基を含み得る。ｘは０〜２の整数を表す。ｙは０または１を表す。ｎ２は、オキシアルキレン基の平均付加モル数を表し、２以上であり、好ましくは２〜１００であり、より好ましくは２〜５０であり、さらに好ましくは２〜１５である。ｎ２がこのような範囲であれば、基材との密着性に優れるカラーフィルターを形成し得る感光性樹脂組成物を得ることができる。 Examples of the structural unit (D1) having two or more oxyalkylene groups in the side chain include the structural unit represented by the general formula (12).

In formula (12), R ⁷ , R ⁸ and R ⁹ are independently hydrogen atoms or methyl groups, preferably hydrogen atoms. R ¹⁰ is a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. It is preferably a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. , More preferably a linear alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and even more preferably a linear alkyl group having 1 to 5 carbon atoms. It is a phenyl group or a biphenyl group, and particularly preferably a methyl group, a phenyl group or a biphenyl group. The alkyl group, alkenyl group and aromatic hydrocarbon group may have a substituent. AO represents an oxyalkylene group. The oxyalkylene group represented by AO has 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and even more preferably 2. The structural unit (D1) may contain one or more oxyalkylene groups. x represents an integer from 0 to 2. y represents 0 or 1. n2 represents the average number of moles of the oxyalkylene group added, and is 2 or more, preferably 2 to 100, more preferably 2 to 50, and even more preferably 2 to 15. When n2 is in such a range, a photosensitive resin composition capable of forming a color filter having excellent adhesion to a substrate can be obtained.

The structural unit (D1) having two or more oxyalkylene groups in the side chain is composed of the monomer (d1) having two or more oxyalkylene groups in the side chain. Examples of the monomer (d1) include ethoxylated o-phenylphenol (meth) acrylate (EO2 mol), phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate (EO4 mol), and methoxypolyethylene glycol (meth) acrylate. (EO 9 mol), methoxypolyethylene glycol (meth) acrylate (EO 13 mol), methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate, 2-ethylhexyldiethylene glycol (meth) acrylate, methoxy Dipropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate (EO4-17 mol), nonylphenoxypolyethylene glycol (meth) acrylate (PO5 mol), EO-modified cresol (meth) Examples thereof include acrylate (2 mol of EO). These monomers may be used alone or in combination of two or more. In the present specification, for example, notations such as "EO 2 mol" and "PO 5 mol" represent the average number of moles of oxyalkylene groups added.

The content ratio of the structural unit (D1) having two or more oxyalkylene groups in the side chain is preferably 0.1 part by weight to 10 parts by weight, more preferably 0 parts by weight, based on 100 parts by weight of the alkali-soluble resin. It is 5 parts by weight to 5 parts by weight.

In the above-mentioned monomer composition I for forming the alkali-soluble resin, the content ratio of the monomer (d1) having two or more oxyalkylene groups in the side chain is preferably 1 part by weight to 10 parts by weight, more preferably 2 parts by weight. ~ 5 parts by weight.

(Constituent unit (D2) derived from other monomer (d2))
The structural unit (D2) derived from the other monomer (d2) is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth). Acrylamide, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, biphenyl ( Meta) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethylene glycol (meth) acrylate, 2-ethylhexyl ethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, phenoxyethyl (meth) Acrylamide, biphenoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tricyclodecyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclodecyloxyethyl (meth) acrylate, nonylphenoxy (Meta) acrylic acid esters such as ethylene glycol (meth) acrylate, nonylphenoxypropylene glycol, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acryloylmorpholin (morpholino (meth) acrylate), ( Meta) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, N-t-butyl (meth) acrylamide, N-t- Octyl (meth) acrylamide, diacetone (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (Meta) Acrylamides such as (meth) acrylamide, N-triphenylmethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, etc. Acrylamide or substituted butadiene compounds such as butadiene, isoprene, ethylene, propylene, vinyl chloride , Ethylene or substituted ethylene compound such as acrylonitrile; constituent units derived from monomer (d2) such as vinyl esters such as vinyl acetate. These monomers may be used alone or in combination of two or more.

The content ratio of the structural unit (D2) is preferably 0 parts by weight to 55 parts by weight, more preferably 5 parts by weight to 50 parts by weight, and further preferably 10 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. It is a part by weight to 45 parts by weight.

B-5. Polymerization of Alkali-Soluble Resin The alkali-soluble resin can be obtained by polymerizing a monomer composition containing the above-mentioned monomer by any suitable method. Examples of the polymerization method include a solution polymerization method.

The monomer composition may contain any suitable solvent. Examples of the solvent include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and propylene glycol monomethyl ether; ketones such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and 3-methoxybutyl. Examples include esters such as acetate; alcohols such as methanol and ethanol; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; chloroform; dimethylsulfoxide and the like. These solvents may be used alone or in combination of two or more. The polymerization concentration when polymerizing the above-mentioned monomer composition is preferably 5% by weight (mass%) to 90% by weight, more preferably 5% by weight to 50% by weight, and further preferably 10% by weight to 50% by weight. Weight%.

The monomer composition may contain any suitable polymerization initiator. Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-amylperoxy-2. Organic peroxides such as -ethylhexanoate, t-butylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexanecarbonitrile), Examples thereof include azo compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile) and dimethyl 2,2'-azobis (2-methylpropionate). The content ratio of the polymerization initiator is preferably 0.1 parts by weight to 15 parts by weight, more preferably 0.2 parts by weight to 10 parts by weight, based on 100 parts by weight of all the monomers in the monomer composition.

The monomer composition may include any suitable chain transfer agent. Examples of the chain transfer agent include monofunctional thiol compounds such as n-dodecyl mercaptoethanol and β-mercaptopropionic acid; bifunctional thiol compounds such as both-terminal mercapto-modified polysiloxane; Examples include modified polysiloxane. The content ratio of the chain transfer agent is preferably 0.1 parts by weight to 15 parts by weight, more preferably 0.5 parts by weight to 10 parts by weight, based on 100 parts by weight of all the monomers in the monomer composition.

The polymerization temperature when the alkali-soluble resin is polymerized by the solution polymerization method is preferably 40 ° C. to 150 ° C., more preferably 60 ° C. to 130 ° C.

The alkali-soluble resin may be a random copolymer or a block copolymer.

The weight average molecular weight of the alkali-soluble resin is preferably a value measured by gel permeation chromatography (GPC) in a tetrahydrofuran (THF) solvent, preferably 3,000 to 200,000, more preferably. It is 4,000 to 100,000, more preferably 5,000 to 50,000. Within such a range, it is possible to obtain a photosensitive resin composition having heat resistance and an appropriate viscosity for forming a coating film.

The acid value of the alkali-soluble resin is preferably 20 mgKOH / g to 300 mgKOH / g, more preferably 25 mgKOH / g to 200 mgKOH / g, and even more preferably 30 mgKOH / g to 150 mgKOH / g. Within such a range, it is possible to obtain a photosensitive resin composition capable of forming a color filter having excellent alkali developability, less generation of development residue, and excellent adhesion.

The content of the alkali-soluble resin in the photosensitive resin composition of the present invention is preferably 1% by weight to 50% by weight, more preferably 5% by weight to 40% by weight, based on the total solid content of the composition. Is.

B-6. Alkali-soluble resin having a structural unit (E) having a carbon double bond in the side chain In one embodiment, the alkali-soluble resin has a structural unit (E) having a carbon double bond in the side chain. If the alkali-soluble resin has a structural unit (E) having a carbon double bond in the side chain, it is possible to form a color filter having excellent strength and obtain a photosensitive resin composition having high exposure sensitivity. it can. The structural unit (E) having a carbon double bond in the side chain is composed of a part or all (preferably a part) of the acid group of the structural unit (C) having an acid group in the side chain as a reaction point. It can be obtained by adding a compound having a double bond.

When the acid group of the structural unit (C) having an acid group in the side chain is a carboxyl group, the compound having a carbon double bond includes a compound having an epoxy group and a double bond, and an isocyanate group and a double bond. Compounds and the like can be used. Examples of the compound having an epoxy group and a double bond include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinyl. Benzyl glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether and the like can be mentioned. Examples of the compound having an isocyanate group and a double bond include 2-isocyanatoethyl (meth) acrylate. When the acid group of the structural unit (C) having an acid group in the side chain is a carboxylic acid anhydride group, a compound having a hydroxyl group and a double bond can be used as the compound having a carbon double bond. Examples of the compound having a hydroxyl group and a double bond include 2-hydroxyethyl (meth) acrylate.

When an alkali-soluble resin having a structural unit (E) having a carbon double bond in the side chain is obtained, the above-mentioned monomer composition is polymerized, and then the compound having the above-mentioned carbon double bond is added to the obtained resin. As the carbon double bond, an ethylenically unsaturated double bond is preferable. Any suitable method can be adopted as the method for adding the compound having a carbon double bond. For example, in the presence of a polymerization inhibitor and a catalyst, a compound having a carbon double bond is reacted with a part or all (preferably a part) of the acid group of the structural unit (C) having an acid group in the side chain. By adding the mixture, a structural unit (E) having a carbon double bond in the side chain can be formed.

The addition amount of the compound having a carbon double bond is preferably 5 parts by weight with respect to 100 parts by weight of the alkali-soluble resin after the polymerization (that is, the alkali-soluble resin before adding the compound having a carbon double bond). It is 10 parts by weight or more, more preferably 15 parts by weight or more, and particularly preferably 20 parts by weight or more. Within such a range, a photosensitive resin composition having excellent exposure sensitivity can be obtained. By using such a photosensitive resin composition, it is possible to form a dense cured coating film and to form a color filter having excellent substrate adhesion and high strength. Further, when the addition amount of the compound having a carbon double bond is within the above range, a photosensitive resin composition in which hydroxyl groups are sufficiently generated by the addition of the compound having a carbon double bond and has excellent solubility in an alkaline developer can be obtained. Obtainable. The upper limit of the addition amount of the compound having a carbon double bond is preferably with respect to 100 parts by weight of the alkali-soluble resin after the polymerization (that is, the alkali-soluble resin before the compound having a carbon double bond is added). It is 150 parts by weight or less, more preferably 100 parts by weight or less, and further preferably 80 parts by weight or less.

Examples of the polymerization inhibitor include alkylphenol compounds such as 6-tert-butyl-2,4-xylenol. Examples of the catalyst include tertiary amines such as dimethylbenzylamine and triethylamine.

C. Polyfunctional Monomer The photosensitive resin composition for a color filter of the present invention may contain a polyfunctional monomer. Examples of the polyfunctional monomer include polyfunctional aromatic vinyl-based monomers such as divinylbenzene, diallythritolate, and diallythritol phosphonate; (di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and trimethyl propanedi. (Meta) acrylate, trimethritol propanthritol (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol Tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol di (meth) acrylate, tripentaerythritol tri (meth) acrylate , Tryentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tris (hydroxyethyl) ) Polyfunctional (meth) acrylates such as tri (meth) acrylate of isocyanurate; polyfunctional monomers obtained by modifying these monomers with caprolactone or alkylene oxide. Of these, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, Tri (meth) acrylate of tris (hydroxyethyl) isocyanurate is preferable. By using these polyfunctional monomers, a color filter having a high crosslink density can be obtained because the number of functional groups is large. In the present invention, the binder polymer having an oxyalkylene group is used as described above, while the polyfunctional monomer may or may not have an oxyalkylene group. Preferably, a polyfunctional monomer having no oxyalkylene group is used.

The content ratio of the polyfunctional monomer is preferably 5 parts by weight to 200 parts by weight, and more preferably 10 parts by weight to 150 parts by weight with respect to 100 parts by weight of the alkali-soluble resin in the photosensitive resin composition. It is more preferably 30 parts by weight to 120 parts by weight, and particularly preferably 35 parts by weight to 100 parts by weight.

D. Coloring material In one embodiment, a pigment is used as the coloring material. As the pigment, any suitable pigment can be used. The pigment may be an organic pigment or an inorganic pigment. Examples of organic pigments include azo pigments, phthalocyanine pigments, and polycyclic pigments (quinacridone, perylene, perinone, isoindolinone, isoindoline, dioxazine, thioindigo, anthraquinone, quinophthalone, etc. Metal complex type, diketopyrrolopyrrole type, etc.), dye lake type pigment and the like. Examples of inorganic pigments include white / extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.) and chromatic pigments (yellow lead, cadmium, chromium vermillion, nickel titanium, etc.). Chromium titanium, yellow iron oxide, red iron oxide, zinc chromate, lead tan, ultramarine, dark blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), black pigments (carbon black, bone black, graphite, iron black, titanium black, etc.) Etc.), bright material pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments (zinc oxide, strontium sulfide, strontium aluminate, etc.) and the like. The pigment may be subjected to surface treatment such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc., depending on the purpose and application.

The number average primary particle size of the pigment may be any suitable particle size depending on the type of pigment. The number average primary particle size of the pigment is preferably 100 nm or less, more preferably 50 nm or less. The lower limit of the number average primary particle size of the pigment is, for example, 10 nm. In the present invention, by containing the alkali-soluble resin, the dispersibility of the pigment is improved, and it becomes possible to use a pigment having a small particle size.

The number average secondary particle size (initial particle size) of the pigment immediately after preparing the photosensitive resin composition is preferably 200 nm or less, more preferably 150 nm or less, still more preferably 120 nm or less, and particularly preferably. Is 100 nm or less. The particle size can be measured using a dynamic light scattering type particle size distribution measuring device.

The rate of change (particle size after 7 days / initial particle size) of the number average secondary particle size of the pigments after 7 days in an environment of 40 ° C. after preparing the photosensitive resin composition is It is preferably 150% or less, more preferably 130% or less, further preferably 110% or less, particularly preferably 105% or less, and most preferably less than 100%. The lower limit of the rate of change is, for example, 90%. In the present invention, the stability of pigment dispersion is excellent, and the aggregation of pigments over time can be effectively suppressed.

The content ratio of the pigment is preferably 20 parts by weight to 500 parts by weight, more preferably 50 parts by weight to 400 parts by weight, still more preferably, with respect to 100 parts by weight of the alkali-soluble resin in the photosensitive resin composition. Is 80 parts by weight to 300 parts by weight, and particularly preferably 100 parts by weight to 200 parts by weight. In the present invention, since the pigment can be added with good dispersibility, the content ratio of the pigment can be increased. By using a photosensitive resin composition having a high pigment content, it is possible to form a color filter having desired properties but having a thin thickness.

In another embodiment, a dye is used as the coloring material. Examples of the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes and the like.

The content ratio of the dye is preferably 20 parts by weight to 500 parts by weight, more preferably 50 parts by weight to 400 parts by weight, still more preferably, based on 100 parts by weight of the alkali-soluble resin in the photosensitive resin composition. Is 80 parts by weight to 300 parts by weight, and particularly preferably 100 parts by weight to 200 parts by weight.

The pigment and the dye may be used in combination. In this case, the total content of the pigment and the dye (the content of the coloring material) is preferably 20 based on 100 parts by weight of the alkali-soluble resin in the photosensitive resin composition. It is by weight to 500 parts by weight, more preferably 50 parts by weight to 400 parts by weight, further preferably 80 parts by weight to 300 parts by weight, and particularly preferably 100 parts by weight to 200 parts by weight.

E. Additives The photosensitive resin composition may further contain additives. Examples of the additive include a dispersant, a photopolymerization initiator and the like.

E-1. Dispersant The dispersant is typically a pigment dispersant and can be used in combination with the pigment when the colorant is a pigment. As the dispersant, any suitable dispersant can be used. Examples of the dispersant include a resin type dispersant (polymer dispersant), a surfactant (low molecular weight dispersant), a dye derivative and the like.

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 the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group, salts thereof, and (meth) acrylic acid-styrene. Polymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, polyvinylpyrrolidones, polyesters, modified polyacrylates, ethylene oxide / polypropylene oxide adducts, etc. Be done.

Further, as a structure, a resin having a graft structure in which the main chain is an anchor chain having an interaction site with a pigment and the graft chain is a compatible chain having an interaction with a dispersion medium, or a phase with an anchor chain. A resin having a block structure of soluble chains is particularly preferably used.

Specific examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, and triethanolamine lauryl sulfate. Anionic surfactants such as ammonium lauryl sulfate, sodium stearate, sodium lauryl sulfate; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate Nonionic surfactants such as; Cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; Alkyl betaines such as alkyl dimethylamino acetate betaine, amphoteric surfactants such as alkyl imidazoline; etc. Be done.

A dye derivative is a compound having a structure in which a functional group is introduced into a dye, and examples of the functional group include a sulfonic acid group, a sulfanoamide group and a quaternary salt thereof, a dialkylamino group, a hydroxyl group, a carboxyl group, an amide group, and a phthalimide group. Examples of the structure of the dye as the base material include azo, anthraquinone, quinophthalone, phthalocyanine, quinacridone, benzimidazolone, isoindolin, dioxazine, indanslen, and perylene. , Diketopyrrolopyrrole type and the like.

The content ratio of the dispersant is preferably 5 parts by weight to 100 parts by weight, more preferably 10 parts by weight to 90 parts by weight, and further, with respect to 100 parts by weight of the alkali-soluble resin in the photosensitive resin composition. It is preferably 10 parts by weight to 85 parts by weight, and particularly preferably 20 parts by weight to 80 parts by weight. In the present invention, the dispersibility of the pigment can be enhanced by containing the alkali-soluble resin, so that the content ratio of the dispersant can be reduced. If a photosensitive resin composition containing a small amount of dispersant is used, a color filter in which discoloration is prevented can be formed. Further, the photosensitive resin composition containing less dispersant can contribute to the improvement of the brightness of the color filter.

The content ratio of the dispersant is preferably 2 parts by weight to 80 parts by weight, more preferably 5 parts by weight to 60 parts by weight, and further preferably 10 parts by weight to 50 parts by weight with respect to 100 parts by weight of the pigment. It is a part by weight.

E-2. Photopolymerization Initiator As the photopolymerization initiator, any suitable photopolymerization initiator can be used. Examples of the photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether and benzoin ethyl ether and their alkyl ethers; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone. Anthraquinones such as 2-methylanthraquinone, 2-amyl anthraquinone, 2-t-butyl anthraquinone and 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals; benzophenone and other benzophenones; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one, 2-benzyl-2-dimethyl Α-Aminoketones such as amino-1- (4-morpholinophenyl) -butanone-1; 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl}- Α-Hydroxyketones such as 2-methyl-propane-1-one; acylphosphine oxides, xanthones and the like can be mentioned. These photopolymerization initiators may be used alone or in combination of two or more.

The content ratio of the photopolymerization initiator is preferably 5 parts by weight to 50 parts by weight, more preferably 10 parts by weight to 40 parts by weight, based on 100 parts by weight of the alkali-soluble resin in the photosensitive resin composition. is there.

Further, a photopolymerization initiator may be used in combination with the photopolymerization initiator. A plurality of combinations of photopolymerization initiators can also be used. Specific examples of the photopolymerization initiator include 1,3,5-tris (3-mercaptopropionyloxyethyl) -isocyanurate and 1,3,5-tris (3-mercaptobutyloxyethyl) -isocyanurate (Showa). Trifunctional thiol compounds such as Karenz MT (registered trademark) NR1) and trimethylol propanthris (3-mercaptopropionate) manufactured by Denkosha; pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto). Butyrate) (manufactured by Showa Denko Co., Ltd., Karenz MT (registered trademark) PE1) and other tetrafunctional thiol compounds;

E-3. Other Additives The photosensitive resin compositions of the present invention may further comprise any suitable other additives, if desired. Other additives include, for example, fillers such as aluminum hydroxide, talc, clay, barium sulfate, defoaming agents, coupling agents, leveling agents, sensitizers, mold release agents, lubricants, plasticizers, antioxidants. Agents, UV absorbers, flame retardants, polymerization inhibitors, thickeners, organic fine particles, inorganic fine particles (zinc oxide-based, silicon oxide-based, talconia-based, titanium-based), porous fine particles such as silica, hollow fine particles such as silica And so on.

F. Solvent The photosensitive resin composition of the present invention may contain any suitable solvent. Examples of the solvent include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and 3-methoxy. Esters such as butyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene, ethylbenzene; chloroform, dimethyl sulfoxide, etc. Can be mentioned. The amount of solvent can be set to any suitable amount depending on the desired viscosity of the photosensitive resin composition. For example, the solvent is preferably contained in the pigment dispersion composition in a proportion of 50% by weight to 90% by weight, more preferably in a proportion of 60% by weight to 90% by weight.

G. Color filter A color filter can be obtained by using the above photosensitive resin composition. By using the photosensitive resin composition of the present invention, it is possible to form a color filter having excellent smoothness and adhesion to a substrate.

The color filter can be formed by photolithography. Specifically, the photosensitive resin composition is applied to a substrate and then dried, and a photomask is placed on the obtained coating film for exposure, the coating film is cured, and then the coating film is developed to obtain a color. A filter can be formed. According to photolithography, a color filter can be formed with a fine pattern. By using the photosensitive resin composition of the present invention, it is possible to obtain a color filter having excellent adhesion to the substrate even if it is formed in a fine pattern.

In one embodiment, a color material dispersion composition containing the alkali-soluble resin and the color material (hereinafter, also referred to as mill base) and a clear resist containing the alkali-soluble resin and the polyfunctional monomer are mixed. , The above photosensitive resin composition is prepared. The mill base may further contain a dispersant. In addition, the clear resist may further contain a photopolymerization initiator. Also, the mill base and / or clear resist may contain any suitable solvent.

In the above mill base, the content ratio of the coloring material is preferably 30 parts by weight to 500 parts by weight, more preferably 50 parts by weight to 500 parts by weight, and further, with respect to 100 parts by weight of the alkali-soluble resin in the mill base. It is preferably 80 parts by weight to 450 parts by weight, more preferably 100 parts by weight to 400 parts by weight, and particularly preferably 200 parts by weight to 350 parts by weight.

In the above mill base, the content ratio of the dispersant is preferably 2 parts by weight to 80 parts by weight, more preferably 5 parts by weight to 60 parts by weight, and further, with respect to 100 parts by weight of the alkali-soluble resin in the mill base. It is preferably 10 parts by weight to 50 parts by weight.

In the above clear resist, the content ratio of the polyfunctional monomer is preferably 50 parts by weight to 400 parts by weight, more preferably 100 parts by weight to 350 parts by weight, based on 100 parts by weight of the alkali-soluble resin in the clear resist. Yes, more preferably 150 parts by weight to 300 parts by weight.

In the above clear resist, the content ratio of the photopolymerization initiator is preferably 5 parts by weight to 200 parts by weight, more preferably 10 parts by weight to 150 parts by weight, based on 100 parts by weight of the alkali-soluble resin in the clear resist. It is more preferably 10 parts by weight to 120 parts by weight.

Examples of the method for applying the photosensitive resin composition include a method using a spin coater, a bar coater, a gravure coater, a roll coater, a knife coater, an applicator and the like. The drying temperature is preferably 40 ° C. to 200 ° C., more preferably 70 ° C. to 120 ° C. The drying time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes.

The position of the photomask is arranged at an arbitrary appropriate position according to the size of the desired color filter. The photomask is arranged on top of the coating film, and the distance between the coating film and the photomask is preferably 0 μm to 500 μm, more preferably 10 μm to 400 μm, still more preferably 20 μm to 300 μm, and particularly preferably 30 μm. It is ~ 200 μm.

UV radiation intensity during the exposure (365 nm intensity equivalent), preferably ^{10mJ / cm 2 ~200mJ / cm 2} , more preferably ^{20mJ / cm 2 ~150mJ / cm 2} , more preferably 30 mJ / cm ² It is ~ 100 mJ / cm ² .

In the above development, it is preferable to use an alkaline aqueous solution. This is because high-sensitivity development can be performed with less burden on the environment. As the alkaline component, for example, potassium hydroxide, sodium hydroxide, sodium carbonate and the like are used. The alkali concentration of the alkaline aqueous solution is preferably 0.01% by weight to 5% by weight, more preferably 0.02% by weight to 3% by weight, and further preferably 0.03% by weight to 1% by weight. .. Within such a range, the photosensitive resin composition can be appropriately dissolved to form a color filter with good developability. A surfactant may be further added to the alkaline aqueous solution.

Post-baking may be performed after development. The heating temperature during post-baking is preferably 150 ° C. to 300 ° C., more preferably 180 ° C. to 250 ° C. The heating time is preferably 10 to 90 minutes, more preferably 20 to 60 minutes. If the photosensitive resin composition contains a (meth) acrylic resin having a structural unit (D1) having two or more oxyalkylene groups in the side chain, a color filter having a high crosslink density is formed by post-baking. be able to.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. The evaluation method in the examples is as follows.

(1) Weight average molecular weight: Mw
The measurement was carried out using GPC (HLC-8220 GPC, manufactured by Tosoh Corporation) using THF as an eluent and TSKgel SuperHZM-N (manufactured by Tosoh Corporation) on the column, and calculated in terms of standard polystyrene.
(2) Solid content About 0.3 g of the copolymer solution prepared in the production example was weighed in an aluminum cup, about 1 g of acetone was added to dissolve the solution, and then the solution was naturally dried at room temperature. Then, using a hot air dryer (trade name: PHH-101, manufactured by ESPEC CORPORATION), the product was dried at 140 ° C. for 3 hours, allowed to cool in a desiccator, and weighed. The weight of the solid content (resin) of the polymer solution was calculated from the weight loss.
(3) Acid value 1.5 g of the copolymer solution prepared in the 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 KOH aqueous solution. The titration was carried out using an automatic titration device (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of the polymer was determined from the solid content concentration (mgKOH / g).
(4) Development time A photosensitive resin composition was applied on a 10 cm square glass substrate with a spin coater, and dried in an oven at 90 ° C. for 3 minutes. After drying, a photomask with a line and space of 15 μm is placed at a distance of 100 μm from the coating film, and a UV aligner (trade name “TME-150RNS”, manufactured by TOPCON) equipped with a 2.0 kW ultra-high pressure mercury lamp is used. Ultraviolet rays were irradiated at an intensity of 100 mJ / cm ² (converted to 365 nm illuminance). After irradiation with ultraviolet rays, a 0.05 wt% potassium hydroxide aqueous solution is sprayed on the coating film with a spin developer to dissolve and remove the unexposed portion, and the remaining exposed portion is washed with pure water for 10 seconds for development. Then, a line-and-space pattern was formed.
The time required to dissolve and remove the unexposed portion was measured, and this was taken as the development time.
(5) Adhesion The photosensitive resin composition was applied on a 10 cm square glass substrate with a spin coater, and dried in an oven at 90 ° C. for 3 minutes. After drying, a photomask with a line and space of 15 μm is placed at a distance of 100 μm from the coating film, and a UV aligner (trade name “TME-150RNS”, manufactured by TOPCON) equipped with a 2.0 kW ultra-high pressure mercury lamp is used. Ultraviolet rays were irradiated at an intensity of 100 mJ / cm ² (converted to 365 nm illuminance). After irradiation with ultraviolet rays, the coating film was subjected to alkaline development with a 0.05 wt% potassium hydroxide aqueous solution for 60 seconds, and then the presence or absence of pattern defects was observed.
In the table, the case where there is no defect is ⊚, the case where the defect area is less than 10% is ○, the case where the defect area is 10 or more and less than 50% is Δ, and the case where the defect area is 50% or more is x ..
(6) In-plane uniformity (Ra)
The photosensitive resin composition was applied on a 10 cm square glass substrate with a spin coater, and dried in an oven at 90 ° C. for 3 minutes. After drying, ultraviolet rays were irradiated at an intensity of 100 mJ / cm ² (365 nm illuminance conversion) with a UV aligner (trade name "TME-150RNS", manufactured by TOPCON) equipped with a 2.0 kW ultra-high pressure mercury lamp on the entire surface of the coating film. .. After irradiation with ultraviolet rays, a 0.05% aqueous potassium hydroxide solution was sprayed on the coating film with a spin developer for 20 seconds, and then washed with pure water for 10 seconds.
The arithmetic mean roughness Ra (according to JIS B 0601-2001) of the obtained cured film (range: 1400 μm × 1050 μm) was measured, and the in-plane uniformity was evaluated. A laser microscope (trade name "VK-9700", manufactured by KEYENCE CORPORATION) was used for the arithmetic mean roughness Ra.

[Manufacturing Example 1]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, in the monomer dropping tank, as the monomer composition, 15 g of benzyl maleimide (BzMI), 32 g of acrylic acid (AA), 1 molethoxylated phenylphenol acrylate (trade name "HRD-01", manufactured by Nippon Distillery Co., Ltd., hereinafter HRD- (01) 53 g, t-butyl peroxy-2-ethyl hexanoate (trade name "Perbutyl (registered trademark) O", manufactured by Nippon Oil & Fats Co., Ltd., hereinafter also referred to as PBO) 2 g, propylene glycol methyl ether acetate (PGMEA) 42 g and 18 g of propylene glycol monomethyl ether (PGME) were added and mixed by stirring. Further, 2.0 g of dodecyl mercaptan (nDM), 18.2 g of PGMEA and 7.8 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank, and the mixture was stirred and mixed.
98 g of PGMEA and 42 g of PGMEA were charged into the reaction vessel, replaced with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel became stable at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were each added dropwise over 180 minutes, keeping the temperature at 90 ° C. 30 minutes after the completion of the dropping, 0.5 g of PBO was added. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, in the reaction vessel, 41 g of glycidyl methacrylate (GMA), 0.3 g of 6-tert-butyl-2,4-xylenol (trade name "Topanol", manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor, and dimethylbenzyl as a catalyst. 0.5 g of amine (DMBA) was charged and reacted at 110 ° C. for 1 hour and at 115 ° C. for 7 hours. Then, the mixture was cooled to room temperature to obtain a copolymer solution (A-1) containing 38.6% by weight of an alkali-soluble resin (acrylic resin). The weight average molecular weight (Mw) of the alkali-soluble resin was 15,000, and the acid value was 70 mgKOH / g. The production conditions, solid content concentration, weight average molecular weight (Mw), and acid value of the copolymer solution are shown in Table 1 together with Production Examples 2 to 8.

[Manufacturing Example 2]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 15 g of BzMI, 21 g of AA, 64 g of HRD-01, 2 g of PBO, and 40 g of PGMEA were put into the monomer dropping tank as the monomer composition, and the mixture was stirred and mixed. Further, 0.5 g of nDM and 10 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank, and the mixture was stirred and mixed.
After charging 100 g of PGMEA into the reaction vessel and substituting with nitrogen, the temperature of the reaction vessel was raised to 90 ° C. by heating with an oil bath while stirring. After the temperature of the reaction vessel became stable at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were each added dropwise over 180 minutes, keeping the temperature at 90 ° C. 30 minutes after the completion of the dropping, 0.5 g of PBO was added. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 14 g of GMA, 0.3 g of topanol as a polymerization inhibitor, 0.5 g of DMBA and 21 g of PGMEA as a catalyst were charged in the reaction vessel and reacted at 110 ° C. for 1 hour and at 115 ° C. for 7 hours. Then, it cooled to room temperature, and obtained the copolymer solution (A-2) containing 39.4% by weight of an alkali-soluble resin (acrylic resin). The weight average molecular weight (Mw) of the alkali-soluble resin was 27,000, and the acid value was 97 mgKOH / g. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), and acid value of the copolymer solution.

[Manufacturing Example 3]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 15 g of BzMI, 42 g of AA, 43 g of HRD-01, 2 g of PBO, 42 g of PGMEA and 18 g of PGMEA were put into the monomer dropping tank as the monomer composition, and the mixture was stirred and mixed. Further, 2.0 g of nDM, 18.2 g of PGMEA and 7.8 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank, and the mixture was stirred and mixed.
98 g of PGMEA and 42 g of PGMEA were charged into the reaction vessel, replaced with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel became stable at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were each added dropwise over 180 minutes, keeping the temperature at 90 ° C. 30 minutes after the completion of the dropping, 0.5 g of PBO was added. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 41 g of GMA, 0.3 g of topanol as a polymerization inhibitor, and 0.5 g of DMBA as a catalyst were charged in the reaction vessel and reacted at 110 ° C. for 1 hour and at 115 ° C. for 7 hours. Then, the mixture was cooled to room temperature to obtain a copolymer solution (A-3) containing 38.5% by weight of an alkali-soluble resin (acrylic resin). The weight average molecular weight (Mw) of the alkali-soluble resin was 16000, and the acid value was 125 mgKOH / g. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), and acid value of the copolymer solution.

[Manufacturing Example 4]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 15 g of BzMI, 42 g of AA, 43 g of HRD-01, 2 g of PBO, 42 g of PGMEA and 18 g of PGMEA were put into the monomer dropping tank as the monomer composition, and the mixture was stirred and mixed. Further, 2.0 g of nDM, 18.2 g of PGMEA and 7.8 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank, and the mixture was stirred and mixed.
98 g of PGMEA and 42 g of PGMEA were charged into the reaction vessel, replaced with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel became stable at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were each added dropwise over 180 minutes, keeping the temperature at 90 ° C. 30 minutes after the completion of the dropping, 0.5 g of PBO was added. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 69 g of GMA, 0.3 g of topanol as a polymerization inhibitor, 0.5 g of DMBA as a catalyst, 19 g of PGMEA and 8.5 g of PGMEA were charged in a reaction vessel, and the reaction was carried out at 110 ° C. for 1 hour and 115 ° C. for 8 hours. Then, the mixture was cooled to room temperature to obtain a copolymer solution (A-4) containing 39.0% by weight of an alkali-soluble resin (acrylic resin). The weight average molecular weight (Mw) of the alkali-soluble resin was 18200, and the acid value was 45 mgKOH / g. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), and acid value of the copolymer solution.

[Manufacturing Example 5]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 15 g of BzMI, 32 g of AA, 53 g of HRD-01, 2 g of PBO, 42 g of PGMEA and 18 g of PGMEA were put into the monomer dropping tank as the monomer composition, and the mixture was stirred and mixed. Further, 5.0 g of nDM, 18.2 g of PGMEA and 7.8 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank, and the mixture was stirred and mixed.
98 g of PGMEA and 42 g of PGMEA were charged into the reaction vessel, replaced with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel became stable at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were each added dropwise over 180 minutes, keeping the temperature at 90 ° C. 30 minutes after the completion of the dropping, 0.5 g of PBO was added. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 41 g of GMA, 0.3 g of topanol as a polymerization inhibitor, and 0.5 g of DMBA as a catalyst were charged in the reaction vessel and reacted at 110 ° C. for 1 hour and at 115 ° C. for 7 hours. Then, the mixture was cooled to room temperature to obtain a copolymer solution (A-5) containing 38.5% by weight of an alkali-soluble resin (acrylic resin). The weight average molecular weight (Mw) of the alkali-soluble resin was 10400, and the acid value was 69 mgKOH / g. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), and acid value of the copolymer solution.

[Manufacturing Example 6]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, in the monomer dropping tank, as the monomer composition, 15 g of dimethyl-2, 2'-[oxybis (methylene)] bis-2-propenoate (MD), 32 g of AA, 53 g of HRD-01, 2 g of PBO, 42 g of PGMEA and 18 g of PGMEA were added. It was charged and mixed with stirring. Further, 2.0 g of nDM, 18.2 g of PGMEA and 7.8 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank, and the mixture was stirred and mixed.
98 g of PGMEA and 42 g of PGMEA were charged into the reaction vessel, replaced with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel became stable at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were each added dropwise over 180 minutes, keeping the temperature at 90 ° C. 30 minutes after the completion of the dropping, 0.5 g of PBO was added. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 41 g of GMA, 0.3 g of topanol as a polymerization inhibitor, and 0.5 g of DMBA as a catalyst were charged in the reaction vessel and reacted at 110 ° C. for 1 hour and at 115 ° C. for 7 hours. Then, the mixture was cooled to room temperature to obtain a copolymer solution (A-6) containing 38.5% by weight of an alkali-soluble resin (acrylic resin). The weight average molecular weight (Mw) of the alkali-soluble resin was 15200, and the acid value was 70 mgKOH / g. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), and acid value of the copolymer solution.

[Manufacturing Example 7]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 15 g of (α-allyloxymethyl) methyl acrylate (AMA), 32 g of AA, 53 g of HRD-01, 2 g of PBO, 42 g of PGMEA and 18 g of PGMEA were added to the monomer dropping tank as a monomer composition, and the mixture was stirred and mixed. Further, 2.0 g of nDM, 18.2 g of PGMEA and 7.8 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank, and the mixture was stirred and mixed.
98 g of PGMEA and 42 g of PGMEA were charged into the reaction vessel, replaced with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel became stable at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were each added dropwise over 180 minutes, keeping the temperature at 90 ° C. 30 minutes after the completion of the dropping, 0.5 g of PBO was added. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 41 g of GMA, 0.3 g of topanol as a polymerization inhibitor, and 0.5 g of DMBA as a catalyst were charged in the reaction vessel and reacted at 110 ° C. for 1 hour and at 115 ° C. for 7 hours. Then, the mixture was cooled to room temperature to obtain a copolymer solution (A-7) containing 38.6% by weight of an alkali-soluble resin (acrylic resin). The weight average molecular weight (Mw) of the alkali-soluble resin was 14900, and the acid value was 71 mgKOH / g. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), and acid value of the copolymer solution.

[Manufacturing Example 8]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 32 g of AA, 68 g of cyclohexyl methacrylate (CHMA), 2 g of PBO, 42 g of PGMEA and 18 g of PGMEA were put into the monomer dropping tank as the monomer composition, and the mixture was stirred and mixed. Further, 2.0 g of nDM, 18.2 g of PGMEA and 7.8 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank, and the mixture was stirred and mixed.
98 g of PGMEA and 42 g of PGMEA were charged into the reaction vessel, replaced with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel became stable at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were each added dropwise over 180 minutes, keeping the temperature at 90 ° C. 30 minutes after the completion of the dropping, 0.5 g of PBO was added. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 41 g of GMA, 0.3 g of topanol as a polymerization inhibitor, and 0.5 g of DMBA as a catalyst were charged in the reaction vessel and reacted at 110 ° C. for 1 hour and at 115 ° C. for 7 hours. Then, it cooled to room temperature, and obtained the copolymer solution (A-8) containing 38.8% by weight of an alkali-soluble resin (acrylic resin). The weight average molecular weight (Mw) of the alkali-soluble resin was 15500, and the acid value was 72 mgKOH / g. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), and acid value of the copolymer solution.

[Example 1]
9.07 g (that is, 3.5 g of alkali-soluble resin) of the above-mentioned copolymer solution (A-1), dispersant (manufactured by BIC Chemie Japan, trade name "DISPERBYK-2001", non-volatile content 1.3 g; hereinafter, 2.83 g of byk2001) and 8.0 g of a pigment as a coloring material (manufactured by Ciba Speciality Chemicals, trade name "CI Pigment Red 254"; hereinafter referred to as PR254) were mixed. The obtained mixture was diluted with PGMEA so that the non-volatile content concentration was 20% by weight to obtain mill base R1.
3.5 g of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., hereinafter referred to as DPHA), 4.66 g of the above copolymer solution (A-1) (that is, 1.8 g of alkali-soluble resin), and a photopolymerization initiator. 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one (manufactured by BASF Japan, trade name "IRGACURE® 907"; hereinafter referred to as Irg907) 1. 9 g and PGMEA were mixed to obtain clear resist R1.
Next, the mill base R1 and the clear resist R1 were mixed and diluted with PGMEA so that the non-volatile content concentration became 20% by weight to obtain a photosensitive resin composition R1.
The obtained photosensitive resin composition R1 was subjected to the above evaluations (4) to (6). The results are shown in Table 2.

[Examples 2 to 8]
The photosensitive resin compositions R2 to R8 were prepared in the same manner as in Example 1 except that the copolymer solution shown in Table 2 was used instead of the copolymer solution (A-1) contained in the clear resist. Obtained. In each of the experimental examples, the copolymer solution contained in the clear resist was used so that the amount of the alkali-soluble resin added to the clear resist was 1.8 g.
The obtained photosensitive resin compositions R2 to 8 were subjected to the above evaluations (4) to (6). The results are shown in Table 2.

[Example 9]
A photosensitive resin composition R9 was obtained in the same manner as in Example 1 except that the copolymer solution (A-8) was used instead of the copolymer solution (A-1) contained in the mill base. .. The copolymer solution (A-8) contained in the mill base was used so that the amount of the alkali-soluble resin added to the mill base was 3.5 g.
The obtained photosensitive resin composition R9 was subjected to the above evaluations (4) to (6). The results are shown in Table 2.

[Comparative Example 1]
The copolymer solution (A-8) was used instead of the copolymer solution (A-1) contained in the mill base, and the copolymer solution (A-1) contained in the clear resist was replaced. , A photosensitive resin composition R10 was obtained in the same manner as in Example 1 except that the copolymer solution (A-8) was used. The copolymer solution (A-8) contained in the mill base was used so that the amount of the alkali-soluble resin added to the mill base was 3.5 g. Further, the copolymer solution (A-8) contained in the clear resist was used so that the alkali-soluble resin added to the clear resist was 1.8.
The obtained photosensitive resin composition R10 was subjected to the above evaluations (4) to (6). The results are shown in Table 2.

[Example 10]
Instead of 8 g of the pigment "PR254", 4.8 g of a pigment (manufactured by Heubach, trade name "CI Pigment Green 36"; hereinafter referred to as PG36) and a pigment (manufactured by Lanxess, trade name "CI Pigment Green 36"). Pigment Yellow 150 ”; hereinafter, a mixture with 3.2 g of PY150) was used, and 2-benzyl-2-dimethylamino-1- (4-) was used instead of 1.9 g of the photopolymerization initiator“ Irg907 ”. Morphorinophenyl) -butanone-1 (manufactured by BASF Japan, trade name "IRGACURE (registered trademark) 369"; hereinafter referred to as Irg369), except that 1.9 g was used, the same as in Example 1. A sex resin composition G1 was obtained.
The obtained photosensitive resin composition G1 was subjected to the above evaluations (4) to (6). The results are shown in Table 3.

[Examples 11 to 17]
The photosensitive resin compositions G2 to G8 were prepared in the same manner as in Example 10 except that the copolymer solution shown in Table 3 was used instead of the copolymer solution (A-1) contained in the clear resist. Obtained. In each of the experimental examples, the copolymer solution contained in the clear resist was used so that the amount of the alkali-soluble resin added to the clear resist was 1.8 g.
The obtained photosensitive resin compositions G2 to 8 were subjected to the above evaluations (4) to (6). The results are shown in Table 3.

[Example 18]
A photosensitive resin composition G9 was obtained in the same manner as in Example 10 except that the copolymer solution (A-8) was used instead of the copolymer solution (A-1) contained in the mill base. .. The copolymer solution (A-8) contained in the mill base was used so that the amount of the alkali-soluble resin added to the mill base was 3.5 g.
The obtained photosensitive resin composition G9 was subjected to the above evaluations (4) to (6). The results are shown in Table 3.

[Comparative Example 2]
The copolymer solution (A-8) was used instead of the copolymer solution (A-1) contained in the mill base, and the copolymer solution (A-1) contained in the clear resist was replaced. , A photosensitive resin composition G10 was obtained in the same manner as in Example 10 except that the copolymer solution (A-8) was used. The copolymer solution (A-8) contained in the mill base was used so that the amount of the alkali-soluble resin added to the mill base was 3.5 g. Further, the copolymer solution (A-8) contained in the clear resist was used so that the alkali-soluble resin added to the clear resist was 1.8.
The obtained photosensitive resin composition G10 was subjected to the above evaluations (4) to (6). The results are shown in Table 3.

[Example 19]
Instead of 8 g of the pigment "PR254", 1.6 g of a pigment (manufactured by Clariant, trade name "CI Pigment Violet 23"; hereinafter referred to as PV23) and a dye (manufactured by MP Biomnicals, trade name "CI" 2. Solvent Blue 35 "; hereinafter referred to as SB35) using a mixture with 6.4 g, and in place of 1.9 g of the photopolymerization initiator" Irg907 ", 2-benzyl-2-dimethylamino-1- Same as in Example 1 except that 1.9 g of (4-morpholinophenyl) -butanone-1 (manufactured by BASF Japan, trade name "IRGACURE (registered trademark) 369"; hereinafter referred to as Irg369) was used. The photosensitive resin composition B1 was obtained.
The obtained photosensitive resin composition B1 was subjected to the above evaluations (4) to (6). The results are shown in Table 4.

[Examples 20 to 26]
The photosensitive resin compositions B2 to B8 were prepared in the same manner as in Example 19 except that the copolymer solution shown in Table 4 was used instead of the copolymer solution (A-1) contained in the clear resist. Obtained. In each of the experimental examples, the copolymer solution contained in the clear resist was used so that the amount of the alkali-soluble resin added to the clear resist was 1.8 g.
The obtained photosensitive resin compositions B2 to 8 were subjected to the above evaluations (4) to (6). The results are shown in Table 4.

[Example 27]
A photosensitive resin composition B9 was obtained in the same manner as in Example 19 except that the copolymer solution (A-8) was used instead of the copolymer solution (A-1) contained in the mill base. .. The copolymer solution (A-8) contained in the mill base was used so that the amount of the alkali-soluble resin added to the mill base was 3.5 g.
The obtained photosensitive resin composition B9 was subjected to the above evaluations (4) to (6). The results are shown in Table 4.

[Comparative Example 3]
The copolymer solution (A-8) was used instead of the copolymer solution (A-1) contained in the mill base, and the copolymer solution (A-1) contained in the clear resist was replaced. , A photosensitive resin composition B10 was obtained in the same manner as in Example 19 except that the copolymer solution (A-8) was used. The copolymer solution (A-8) contained in the mill base was used so that the amount of the alkali-soluble resin added to the mill base was 3.5 g. Further, the copolymer solution (A-8) contained in the clear resist was used so that the alkali-soluble resin added to the clear resist was 1.8.
The obtained photosensitive resin composition B10 was subjected to the above evaluations (4) to (6). The results are shown in Table 4.

As is clear from Tables 2 to 4, the photosensitive resin composition of the present invention can form a color filter having excellent development speed, surface smoothness and adhesion to a substrate.

Claims (5)

Contains an alkali-soluble resin, a coloring material, and a polyfunctional monomer,
The alkali-soluble resin contains a structural unit having a ring structure in the main chain, a structural unit having an aromatic ring group in the side chain, and a structural unit having a carbon double bond in the side chain .
The structural unit having a ring structure in the main chain is at least one selected from the structural units represented by the general formulas (1) to (7).
The structural unit having an aromatic ring in the side chain is a structural unit having a biphenyl group in the side chain.
The structural unit having a biphenyl group in the side chain is a structural unit derived from a monomer represented by the general formula (10) or (11).
Photosensitive resin composition for color filters (excluding those containing organic-inorganic hybrid materials) :

In formulas (4) to (7), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently linear or branched with hydrogen atoms or 1 to 30 carbon atoms. Alkyl group:

In formula (11), n1 is 1-10. Contains an alkali-soluble resin, a coloring material, and a polyfunctional monomer,
The alkali-soluble resin is a ( meth) acrylic resin containing a structural unit having a ring structure in the main chain, a structural unit having an aromatic ring group in the side chain, and a structural unit having a carbon double bond in the side chain. Oh it is,
The structural unit having a ring structure in the main chain is at least one selected from the structural units represented by the general formulas (1) to (7).
The structural unit having an aromatic ring in the side chain is a structural unit having a biphenyl group in the side chain.
The structural unit having a biphenyl group in the side chain is a structural unit derived from a monomer represented by the general formula (11).
Photosensitive resin composition for color filters:

In formulas (4) to (7), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently linear or branched with hydrogen atoms or 1 to 30 carbon atoms. Alkyl group:

In formula (11), n1 is 2-10. The alkali-soluble resin contains a structural unit having an acid group in the side chain.
The coloring material is a pigment,
The number average primary particle size of the pigment is 100 nm or less, and the content ratio of the pigment is 100 parts by weight to 500 parts by weight with respect to 100 parts by weight of the alkali-soluble resin.
The photosensitive resin composition for a color filter according to claim 1 or 2 . The photosensitive resin composition for a color filter according to claim 1 or 2 , wherein the coloring material is a pigment and / or a dye. The coloring material is a pigment,
The photosensitive resin composition for a color filter according to claim 1 or 2 , wherein the number average primary particle size of the pigment is 100 nm or less.