JP6912909B2 - Photosensitive resin composition - Google Patents

Description

The present invention relates to a photosensitive resin composition.

The photosensitive resin composition is a material used in a photolithography method and whose solubility in a developing solution changes depending on the presence or absence of exposure, and a molded product having a predetermined pattern can be obtained by using this material. The photolithography method is often used in the manufacture of members for image display devices, the manufacture of circuit boards for electronic devices, the manufacture of semiconductor devices, and the like. In such a technical field, it is required that the molded product can be obtained in a fine pattern, the developing speed is high, and the like.

One of the uses of the photosensitive resin composition is a material for a color filter used in an image display device such as a liquid crystal display device. A color filter is usually manufactured by a photolithography method or the like after applying a photosensitive resin composition containing a coloring material such as a pigment and a photocurable resin to a transparent substrate. In recent years, with the demand for higher performance of image display devices, a photosensitive resin composition capable of forming a color filter formed of a fine pattern has been required so as to contribute to improvement of brightness, contrast and the like. There is. Further, in order to improve processability, there is a demand for a photosensitive resin composition capable of forming a color filter in an appropriate development time.

Examples of the method of forming a color filter that can contribute to the improvement of brightness and contrast include a method of refining a pigment as a coloring material in a photosensitive resin composition, a method of using a dye as a coloring material, and the like. However, when such a method is adopted, the development margin (the difference between the shortest development time that allows pattern formation during development and the longest development time that allows pattern formation without loss) becomes short, and processing is performed. The above problem arises. Further, the cross-sectional shape of the formed pattern becomes a reverse taper type that is thinner toward the lower part, which causes problems such as disconnection when the electrode material is applied and bubbles when the liquid crystal material is applied.

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 resin composition having a long development margin and capable of forming a tapered (thicker lower part) molded body. Is to provide.

式（２）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、主鎖に環構造を有する構成単位（Ｂ）をさらに含む。
１つの実施形態においては、上記アルカリ可溶性樹脂が、側鎖に酸基を有する構成単位をさらに含む。
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さらに含む。
本発明の別の局面によれば、硬化物が提供される。この硬化物は、上記感光性樹脂組成物を硬化してなることを特徴とする。
本発明のさらに別の局面によれば、カラーフィルターが提供される。このカラーフィルターは、基板と上記硬化物を有することを特徴とする。 The photosensitive resin composition of the present invention contains an alkali-soluble resin, a coloring material, a dispersant, a polyfunctional monomer, a photopolymerization initiator, and a solvent, and the alkali-soluble resin has a biphenyl group in the side chain. The acid value of the dispersant is 15 mgKOH / g or less.
In one embodiment, the amine value of the dispersant is 25 mgKOH / g or less.
In one embodiment, the alkali-soluble resin is a (meth) acrylic resin.
In one embodiment, the structural unit having a biphenyl group in the side chain is a structural unit derived from a monomer represented by the general formula (1) or (2).

In formula (2), n1 is 1-10.
In one embodiment, the alkali-soluble resin further comprises a structural unit (B) having a ring structure in the main chain.
In one embodiment, the alkali-soluble resin further comprises a structural unit having an acid group in the side chain.
In one embodiment, the alkali-soluble resin further comprises a building block having a carbon double bond in the side chain.
According to another aspect of the invention, a cured product is provided. This cured product is characterized in that the photosensitive resin composition is cured.
According to yet another aspect of the present invention, a color filter is provided. This color filter is characterized by having a substrate and the cured product.

According to the present invention, it is possible to provide a photosensitive resin composition having a long development margin and capable of forming a tapered type (thicker toward the lower part) molded body. Further, by using the photosensitive resin composition, a molded product having excellent surface smoothness can be obtained.

A. Outline of Photosensitive Resin Composition The photosensitive resin composition of the present invention contains an alkali-soluble resin, a coloring material, a dispersant, a polyfunctional monomer, a photopolymerization initiator, and a solvent. The alkali-soluble resin contains a structural unit having a biphenyl group in the side chain. The dispersant has an acid value of 15 mgKOH / g or less. In the present invention, by using an alkali-soluble resin containing a structural unit having a biphenyl group in the side chain and a dispersant having an acid value of 15 mgKOH / g or less in combination, the development margin is long and the productivity is excellent. , A photosensitive resin composition capable of forming a tapered molded product (also referred to as a cured product) can be obtained. In addition, the molded product obtained from the photosensitive resin composition has excellent surface smoothness. In the photosensitive resin composition of the present invention, even if a fine pigment or dye is used as the coloring material, a sufficient development margin can be secured and a tapered molded product can be obtained. Since such performance is exhibited even when a fine pigment or dye is used, the photosensitive resin composition of the present invention can be used to form a molded product in a fine pattern. The tapered molded body means a molded body in which the upper part is thinner than the lower part in a cross-sectional view, and is a concept including a molded body having substantially no diameter difference in the height direction.

In one embodiment, the photosensitive resin composition of the present invention is a mixture of a color material dispersion composition (mil base) containing a color material and a dispersant, and a clear resist containing a polyfunctional monomer and a photopolymerization initiator. Provided. The alkali-soluble resin containing a structural unit having a biphenyl group in the side chain may be contained in the color material dispersion composition or the clear resist, and both the color material dispersion composition and the clear resist. May be included in. Preferably, the alkali-soluble resin is included in the colorant dispersion composition. The color material dispersion composition containing the alkali-soluble resin is advantageous in that the dispersion stability of the color material (for example, pigment) is very excellent and the color material is less likely to aggregate over time. In such a color material dispersion composition, deterioration of dispersibility can be suppressed even if the color material is made finer. In addition, the colorant dispersion composition and / or clear resist contains any suitable solvent.

The photosensitive resin composition of the present invention is mainly used as a negative photosensitive resin composition, and is suitable for, for example, color filters, photo spacers, overcoats, black matrices, black column spacers, inks, paints, sealants and the like. Can be used. In one embodiment, a cured product can be provided by curing the photosensitive resin composition. According to the photosensitive resin composition of the present invention, as described above, it is possible to form a molded body with a fine pattern. Therefore, for example, when the photosensitive resin composition is used as a material for a color filter, the brightness is increased. And a color filter that can contribute to the improvement of contrast can be formed.

B. Alkali-soluble resin As described above, the alkali-soluble resin contains a structural unit having a biphenyl group in the side chain. When the alkali-soluble resin has a structural unit (A) having a biphenyl group in the side chain, a photosensitive resin composition having excellent dispersion stability of the coloring material can be obtained. Further, if an alkali-soluble resin having a structural unit (A) having a biphenyl group in the side chain is used, a photosensitive resin composition having an excellent developing speed can be obtained. Further, a molded product (for example, a color filter) produced by using a photosensitive resin composition containing an alkali-soluble resin having a structural unit (A) having a biphenyl group in the side chain has excellent adhesion to a substrate. Moreover, it is also excellent in smoothness. The alkali-soluble resin is typically a (meth) acrylic resin. The (meth) acrylic resin is particularly limited as long as it is a resin obtained by polymerizing a monomer composition containing at least 10% by weight (mass%) or more of a (meth) acrylic monomer such as a (meth) acrylic acid ester. However, the monomer composition may contain other monomers copolymerizable with the (meth) acrylic monomer.

In one embodiment, the alkali-soluble resin may further comprise a structural unit (B) having a ring structure in the main chain. Further, the alkali-soluble resin may further contain a structural unit (C) having an acid group in the side chain. Further, the alkali-soluble resin may further contain another structural unit (D), if necessary.

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

B-1. Constituent unit (A) having a biphenyl group in the side chain
When the alkali-soluble resin has a structural unit (A) having a biphenyl group in the side chain, a photosensitive resin composition having excellent dispersion stability of the coloring material can be obtained. Preferably, the structural unit (A) having a biphenyl group in the side chain is a structural unit derived from a (meth) acrylic monomer.

式（２）中、ｎ１は１〜１０であり、好ましくは１または２である。 Examples of the structural unit (A) having a biphenyl group in the side chain include biphenyl (meth) acrylate, o-biphenyloxyethyl (meth) acrylate (ethoxylated o-phenylphenol (meth) acrylate), and 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) Examples thereof include structural units derived from the monomer (a) having a biphenyl group on the side chain such as acryloyloxyethyl-m-biphenyl = carbamate, o-phenylphenol glycidyl ether acrylate, and o-biphenyloxypropyl (meth) acrylate. Of these, it is a structural 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 that can be used as a material for a photosensitive resin composition having a high developing speed can be obtained. In one embodiment, the structural unit (A) having a biphenyl group in the side chain is a structural unit derived from the monomer (a) represented by the general formula (1) or (2). More preferably, the structural unit (A) having a biphenyl group in the side chain is a structural unit derived from the monomer (a) represented by the general formula (2). The above-mentioned monomers may be used alone or in combination of two or more.

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

The content ratio of the structural unit (A) having a biphenyl group in the side chain is preferably 10 parts by weight to 80 parts by weight, and more preferably 15 parts by weight to 100 parts by weight with respect to 100 parts by weight (mass part) of the alkali-soluble resin. It is 70 parts by weight, 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 forming the alkali-soluble resin, the content ratio of the monomer (a) having a biphenyl group in the side chain is preferably 20 parts by weight to 20 parts by weight with respect to 100 parts by weight of all the monomers in the monomer composition I. It is 80 parts 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-2. Structural unit (B) having a ring structure in the main chain
When the alkali-soluble resin has a structural unit (B) having a ring structure in the main chain, a resin having high solubility in alkali can be obtained.

Examples of the structural unit (B) 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 resin having high solubility in alkali can be obtained. Specifically, the structural unit (B) having a ring structure in the main chain is preferably at least one selected from the structural units represented by the general formulas (3) to (5), and is preferably the general formula (3). ) Is more preferable. By using an alkali-soluble resin (preferably (meth) acrylic resin) having a structural unit represented by the general formula (3), a photosensitive resin composition capable of forming a cured product having high strength can be obtained. ..

式（６）〜（９）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 (B) having a ring structure in the main chain may be at least one selected from the structural units represented by the general formulas (6) to (9). Of these, the structural unit represented by the general formula (6) or (9) is preferable.

In formulas (6) to (9), 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 (B) having a ring structure in the main chain may be composed of the monomer (b) having a ring structure in the main chain. Examples of the monomer (b) 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（１０）および（１１）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 (B) having a ring structure in the main chain, a monomer (b') capable of forming a ring structure by an intramolecular cyclization step may be used. According to the monomer (b'). The structural units represented by the general formulas (6) to (9) are formed. Examples of the monomer (b') include 1,6-dienes represented by the general formula (10) or (11).

In the formula (10) and ^{(11), R 1, R} 2 and ^{R 3} are as described above.

The content ratio of the structural unit (B) having a ring structure in the main chain is preferably 5 parts by weight to 50 parts by weight, and more preferably 8 parts by weight to 30 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. Yes, more preferably 10 to 25 parts by weight.

In the above-mentioned monomer composition I forming the alkali-soluble resin, the content ratio of the monomer (b) having a ring structure in the main chain is preferably 5 parts by weight to 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. Further, in the above-mentioned monomer composition I for forming the alkali-soluble resin, the content ratio of the monomer (b') capable of forming a ring structure is preferably 5% by weight with respect to 100 parts by weight of all the monomers in the monomer composition I. It is parts to 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-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 thereof 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 , Maleic anhydride and other acid anhydrides 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 fat-forming an alkali-soluble tree is preferably 15 parts by weight to 60 parts by weight with respect to 100 parts by weight of all the monomers in the monomer composition I. It is, more preferably 20 parts by weight to 50 parts by weight, and further preferably 20 parts by weight to 45 parts by weight. Further, in the above-mentioned monomer composition I forming the alkali-soluble resin, the content ratio of the monomer (c') into which an acid group can be introduced is preferably 15% by weight with respect to 100 parts by weight of all the monomers in the monomer composition I. It is parts to 60 parts by weight, more preferably 20 parts by weight to 50 parts by weight, and further 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成形体（例えば、カラーフィルター）を形成し得る感光性樹脂組成物の材料となり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, which 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, it is possible to obtain a photosensitive resin composition that can be used as a material for a photosensitive resin composition capable of forming a molded product (for example, a color filter) having excellent adhesion to a base material.

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 forming the alkali-soluble resin, the content ratio of the monomer (d1) having two or more oxyalkylene groups in the side chain is preferably with respect to 100 parts by weight of all the monomers in the monomer composition I. It is 1 part by weight to 10 parts by weight, more preferably 2 parts by weight to 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). Acrylate, 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-ethylhexylethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate , Biphenoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tricyclodecyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclodecyloxyethyl (meth) acrylate, nonylphenoxyethylene (Meta) acrylic acid esters such as glycol (meth) acrylate, nonylphenoxypropylene glycol, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acryloylmorpholin (morpholino (meth) acrylate), (meth) ) Acrylate, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, N-t-butyl (meth) acrylamide, N-t-octyl (Meta) acrylamide, diacetone (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl ( (Meta) Acrylate amides such as meta) acrylamide, N-triphenylmethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, butadiene , Acrylate or substituted butadiene compounds such as isoprene, ethylene, propylene, vinyl chloride, Examples thereof include ethylene or substituted ethylene compounds such as acrylonitrile; and constituent units derived from a 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 comprise 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; side chain polyfunctional mercapto having mercapto-modified side chains. 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 that ensures heat resistance and has 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. 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 adding the compound having a carbon double bond). 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. 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-based, perylene-based, perinone-based, isoindolinone-based, isoindolin-based, dioxazine-based, thioindigo-based, anthraquinone-based, and quinophthalone-based pigments. 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 pigment 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, 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. 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.

D. Dispersant The acid value of the dispersant is 15 mgKOH / g or less, preferably 13 mgKOH / g or less, more preferably 10 mgKOH / g or less, still more preferably 8 mgKOH / g or less, and most preferably 5 mgKOH or less. It is less than / g. Within such a range, a photosensitive resin composition having excellent dispersion stability of the coloring material can be obtained. The method for measuring the acid value will be described later.

The amine value of the dispersant is preferably 25 mgKOH / g or less, more preferably 20 mgKOH / g or less, and even more preferably 15 mgKOH / g or less. Within such a range, a photosensitive resin composition having more excellent dispersion stability can be obtained. The method for measuring the amine value will be described later.

As the dispersant, any suitable dispersant can be used as long as the effects of the present invention can be obtained. In one embodiment, as the dispersant, an anionic dispersant, a nonionic dispersant, a cationic dispersant, a polymer (resin type) dispersant and the like are used. Of these, a polymer (resin type) dispersant is preferable.

Specific examples of the polymer (resin type) dispersant include polyacrylic polymers, polyether polymers, polyester polymers, polyurethane polymers, polyphosphate ester polymers, polyethyleneimine polymers, and polyallylamine polymers. Polymers composed of monomers having amino groups and macromonomers, polyoxyethylene alkyl ether-based polymers, polyoxyethylene diester-based polymers, polyether phosphoric acid-based polymers, polyester phosphoric acid-based polymers, sorbitan aliphatic ester-based polymers, Examples thereof include aliphatic modified polyester polymers. Further, as a polymer (resin type) dispersant, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkyl amine salts, Polysiloxane, long-chain polyaminoamide phosphate, hydrogen group-containing polycarboxylic acid ester, amide and its salt formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group, (meth) acrylic acid. -Sterene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, polyester-based, modified polyacrylate, ethylene oxide / polypropylene oxide adduct Etc. may be used. As the copolymer, a block copolymer is preferably used.

Among the above dispersants, acrylic polymers, block copolymers, and urethane polymers are preferably used.

A commercially available product may be used as the dispersant. Specific examples of commercially available products include the trade names "Disperbyk-103", "Disperbyk-108", "Disperbyk-109", "Disperbyk-112", "Disperbyk-116", and "Disperbyk-130" manufactured by Big Chemie Japan. , "Disperbyk-161", "Disperbyk-162", "Disperbyk-163", "Disperbyk-164", "Disperbyk-166", "Disperbyk-167", "Disperbyk-168", "Disperbyk-170" "Disperbyk-171", "Disperbyk-182", "Disperbyk-183", "Disperbyk-185", "Disperbyk-184", "Disperbyk-2000", "Disperbyk-2050", "Discerbyk-2050" -2096 "," Disperbyk-2150 ", BYK-9077"; Ajinomoto's product names "Ajispar PB822", "Ajisper PN411"; Kusumoto Kasei's product names "Disparon DA-375", "Disparon ED-251" "; Product name" Nusperth 657NA "manufactured by Elementis; Product name" TEG Disper 650 "," TEG Disper 652 "," TEG Disper 662C "," TEG Disper 670 "," TEG Disper 710 "," TEG Disper 710 "," TEG Disper 670 " Examples thereof include "TEG Disper 752W". Among them, from the viewpoint of heat resistance, electrical reliability, and dispersibility, "Disperbyk-161", "Disperbyk-162", "Disperbyk-163", "Disperbyk-164", "Disperbyk-166", and "Disperbyk-167" , "Disperbyk-168", "Disperbyk-170", "Disperbyk-171", "Disperbyk-182", "Disperbyk-183", "Disperbyk-185", "Disperbyk-184", "Disperbyk-2000" "Disparon ED-251" is preferable.

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 coloring material and the graft chain is a compatible chain having an interaction with a dispersion medium, or an anchor chain. A resin having a block structure of compatible chains is particularly preferably used.

The content ratio of the dispersant is preferably 5 parts by weight to 100 parts by weight, more preferably 10 parts by weight to 70 parts by weight, and further preferably 10 parts by weight to 50 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. It is a part by weight, and particularly preferably 20 parts by weight to 40 parts by weight.

The content ratio of the dispersant is preferably 1 part by weight to 80 parts by weight, more preferably 1 part by weight to 60 parts by weight, and further preferably 1 part by weight to 100 parts by weight with respect to 100 parts by weight of the coloring material. 50 parts by weight.

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, diallylphthalate, and diallylbenzenephosphonate; (di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and trimethyl propanedi. (Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Di (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, Dipentaerythritol Di (Meta) 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 , Tripenta erythritol tetra (meth) acrylate, tripenta erythritol penta (meth) acrylate, tripenta erythritol hexa (meth) acrylate, tripenta erythritol hepta (meth) acrylate, tripenta erythritol octa (meth) acrylate, tris (hydroxyethyl) ) Polyfunctional (meth) acrylates such as tri (meth) acrylate of isocyanurate; polyfunctional monomers in which these monomers are caprolactone-modified or alkylene oxide-modified can be mentioned. 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. Photopolymerization Initiator As the photopolymerization initiator, any suitable photopolymerization initiator can be used. Typically, a radical photopolymerization initiator is 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, 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; 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; 1,2-octanedione, 1- [4- (phenylthio)-, 2-, (O-benzoyloxime)], ethanone, 1-[ Oxime esters such as 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), IRGACUREOXE03, IRGACUREOXE04 (manufactured by BASF); acylphosphine oxides And xanthones and the like. 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. be.

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 Karens MT (registered trademark) NR1) and trimethylol propanthris (3-mercaptopropionate) manufactured by Denkosha; pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto). Butylate) (manufactured by Showa Denko, Inc., Karenz MT (registered trademark) PE1) and other tetrafunctional thiol compounds; and polyfunctional thiols such as dipentaerythritol hexakis (3-propionate) and other hexafunctional thiol compounds can be mentioned.

E. 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, dimethylsulfoxide, 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 photosensitive resin 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. 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. Further, other resins other than the alkali-soluble resin containing a structural unit having a biphenyl group in the side chain may be contained. When other resins are included, the content ratio of the alkali-soluble resin containing a structural unit having a biphenyl group in the side chain is preferably 30 parts by weight or more, more preferably 50 parts by weight, based on 100 parts by weight of the total weight of the resin. It is 5 parts by weight or more, more preferably 65 parts by weight or more, and particularly preferably 65 parts by weight or more and less than 100 parts by weight.

H. Color filter A color filter can be obtained by using the above photosensitive resin composition. In one embodiment, the color filter comprises a cured product of the photosensitive resin composition and has a substrate and a cured product formed on the substrate. 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. As described in Section A, the alkali-soluble resin containing a structural unit having a biphenyl group in the side chain in the side chain can be contained in both the mill base and / or the clear resist.

In the above mill base, the content ratio of the coloring material is preferably 15 parts by weight to 500 parts by weight, more preferably 20 parts by weight to 400 parts by weight, and further, with respect to 100 parts by weight of the alkali-soluble resin in the mill base. It is preferably 20 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 ~ 100 mJ / cm ² .

In the above development, it is preferable to use an alkaline aqueous solution. This is because the load on the environment is small and high-sensitivity development can be performed. 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 minutes to 90 minutes, more preferably 20 minutes 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 measurement method of each characteristic value in the production example and the example is as follows.

(A) 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.
(B) 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), the mixture 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, amine value Acid value of alkali-soluble resin: 1.5 g of the alkali-soluble resin prepared in the production example is precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and with a 0.1 N KOH aqueous solution. Titrated. 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).
Acid value of pigment dispersant: 1.5 g of pigment dispersant 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 pigment dispersant was determined from the solid content concentration (mgKOH / g).
Amine value: 5 g of a sample (pigment dispersant non-volatile content) was precisely weighed, 50 ml of ethanol and 1 ml of a bromophenol blue reagent were added to dissolve the sample, and the solution was titrated with 0.5 mol / L hydrochloric acid until the solution turned green. The amine value was calculated by the following formula (mgKOH / g).
Amine value = 28.05 x b / c
b: Amount of 0.5 mol / L hydrochloric acid consumed by titration (ml)
c: Amount of sample (g)

[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, benzylmaleimide (BzMI) 15 g, acrylic acid (AA) 32 g, 1 molethoxylated phenylphenol acrylate (trade name "HRD-01", manufactured by Nippon Distillery Co., Ltd., hereinafter HRD- 53 g (also referred to as 01), t-butylperoxy-2-ethylhexanoate (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 PGME 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 added dropwise over 180 minutes while maintaining the temperature at 90 ° C., respectively. 0.5 g of PBO was added 30 minutes after the completion of the dropping. 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, it cooled to room temperature, and obtained the copolymer solution (A-1) containing 38.6% by weight of the acrylic resin. The weight average molecular weight (Mw) of the acrylic 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 9.

[Manufacturing Example 2]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, as a monomer composition, 64 g of BzMI, 21 g of AA, and 64 g of HRD-01, 2 g of PBO, and 40 g of PGMEA were put into the monomer dropping tank, 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 added dropwise over 180 minutes while maintaining the temperature at 90 ° C., respectively. 0.5 g of PBO was added 30 minutes after the completion of the dropping. 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 the acrylic resin. The weight average molecular weight (Mw) of the acrylic 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, 143 g of BzMI, 42 g of AA and 143 g of HRD-0, 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 PGME 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 added dropwise over 180 minutes while maintaining the temperature at 90 ° C., respectively. 0.5 g of PBO was added 30 minutes after the completion of the dropping. 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 the copolymer solution (A-3) containing 38.5% by weight of the acrylic resin was obtained. The weight average molecular weight (Mw) of the acrylic 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, as a monomer composition, 43 g of BzMI, 42 g of AA and 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 and mixed by 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 PGME 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 added dropwise over 180 minutes while maintaining the temperature at 90 ° C., respectively. 0.5 g of PBO was added 30 minutes after the completion of the dropping. 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, it cooled to room temperature, and obtained the copolymer solution (A-4) containing 39.0% by weight of the acrylic resin. The weight average molecular weight (Mw) of the acrylic 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, as a monomer composition, 53 g of BzMI, 32 g of AA and 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 and mixed by stirring. 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 PGME 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 added dropwise over 180 minutes while maintaining the temperature at 90 ° C., respectively. 0.5 g of PBO was added 30 minutes after the completion of the dropping. 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-5) containing 38.5% by weight of the acrylic resin. The weight average molecular weight (Mw) of the acrylic 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, 153 g of HRD-0, 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 PGME 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 added dropwise over 180 minutes while maintaining the temperature at 90 ° C., respectively. 0.5 g of PBO was added 30 minutes after the completion of the dropping. 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-6) containing 38.5% by weight of the acrylic resin. The weight average molecular weight (Mw) of the acrylic 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, as a monomer composition, 15 g of methyl (α-allyloxymethyl) 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 put into the monomer dropping tank and mixed by 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 PGME 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 added dropwise over 180 minutes while maintaining the temperature at 90 ° C., respectively. 0.5 g of PBO was added 30 minutes after the completion of the dropping. 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-7) containing 38.6% by weight of the acrylic resin. The weight average molecular weight (Mw) of the acrylic 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, 15 g of BzMI, 32 g of AA, 53 g of benzyl acrylate (BzA), 2 g of PBO, 42 g of PGMEA and 18 g of PGMEA were put into the monomer dropping tank and mixed by 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 PGME 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 added dropwise over 180 minutes while maintaining the temperature at 90 ° C., respectively. 0.5 g of PBO was added 30 minutes after the completion of the dropping. 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 38.7% by weight of the acrylic resin. The weight average molecular weight (Mw) of the acrylic resin was 15600, 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 9]
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 PGME 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 added dropwise over 180 minutes while maintaining the temperature at 90 ° C., respectively. 0.5 g of PBO was added 30 minutes after the completion of the dropping. 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-9) containing 38.8% by weight of the acrylic resin. The weight average molecular weight (Mw) of the acrylic 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]
As an alkali-soluble resin, 9.07 g of the above-mentioned copolymer solution (A-1) (that is, 3.5 g of resin), and as a dispersant, DISPERBYK-2000 (nonvolatile content 1.3 g, acid value: 0 mgKOH / g, amine value: 4 mgKOH / g; manufactured by Big Chemie Japan Co., Ltd., hereinafter referred to as byk2000) 3.25 g, C.I. I. 8.0 g of Pigment Red 254 (manufactured by Chivas Specialty Chemicals, hereinafter referred to as PR254) was weighed in a 225 ml mayonnaise bottle and diluted with PGMEA so that the non-volatile content concentration was 20% by weight. 64 g of zirconia beads having a diameter of 1.0 mm was added thereto, and the lid was closed. This was shaken with a paint shaker for 3 hours, and after 3 hours, the pigment dispersion composition and the zirconia beads were separated, 64 g of 0.5 mm zirconia beads were added, and the mixture was shaken with a paint shaker for another 3 hours. Then, the pigment dispersion composition and the zirconia beads were separated, 64 g of 0.3 mm zirconia beads were added, and the mixture was further shaken with a paint shaker for 3 hours to obtain a pigment dispersion composition r (mil base).
To this pigment dispersion composition r, 3.5 g of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., hereinafter referred to as DPHA) as a polyfunctional monomer, and 4.66 g of the above-mentioned copolymer solution (A-1) as an alkali-soluble resin (A-1). That is, resin 1.8 g) and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one (IRGACURE907, manufactured by BASF Japan, Inc., hereinafter referred to as Irg907) as a photopolymerization initiator. ) Clear resist I containing 1.9 g was added, and the mixture was diluted with PGMEA so that the non-volatile content concentration was 20% by weight. Then, the zirconia beads were removed and filtered through a filter having a pore size of 1.0 μm to prepare a photosensitive resin composition R1.

[Examples 2 to 10, Comparative Examples 1 and 2]
The photosensitive resin compositions R2 to R12 are the same as in Example 1 except that the alkali-soluble resin and dispersant contained in the pigment dispersion composition and the alkali-soluble resin contained in the clear resist are the resins shown in Table 2. Got In the table, "byk2001" is a trade name "DISPERBYK-2001" manufactured by Big Chemie Japan Co., Ltd., the acid value of the dispersant is 19 mgKOH / g, and the amine value is 29 mgKOH / g.

[Example 11]
As an alkali-soluble resin, 9.07 g of the above-mentioned copolymer solution (A-1) (that is, 3.5 g of resin), 3.25 g of byk2000 as a dispersant (1.3 g of non-volatile content), and C.I. I. Pigment Green 36 (manufactured by Heubach, hereinafter referred to as PG36) 4.8 g and C.I. I. 3.2 g of Pigment Yellow 150 (manufactured by Lanxess, hereinafter referred to as PY150) was weighed in a 225 ml mayonnaise bottle and diluted with PGMEA so that the non-volatile content concentration was 20% by weight. 64 g of zirconia beads having a diameter of 1.0 mm was added thereto, and the lid was closed. This was shaken with a paint shaker for 3 hours, and after 3 hours, the pigment dispersion composition and the zirconia beads were separated, 64 g of 0.5 mm zirconia beads were added, and the mixture was shaken with a paint shaker for another 3 hours. Then, the pigment dispersion composition and the zirconia beads were separated, 64 g of 0.3 mm zirconia beads were added, and the mixture was further shaken with a paint shaker for 3 hours to obtain a pigment dispersion composition g.
The pigment dispersion composition g contains 3.5 g of DPHA as a polyfunctional monomer, 4.66 g of the above-mentioned copolymer solution (A-1) as a binder resin (that is, 1.8 g of a resin), and 2-benzyl- as a photopolymerization initiator. Add 1.9 g of 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name "IRGACURE (registered trademark) 369", manufactured by BASF Japan, hereinafter referred to as Irg369). , Diluted with PGMEA so that the non-volatile content concentration was 20% by weight. After removing the zirconia beads, the mixture was filtered through a filter having a pore size of 1.0 μm to prepare a photosensitive resin composition G1.

[Examples 12 to 20, Comparative Examples 3 and 4]
The photosensitive resin compositions G2-12 are the same as in Example 11 except that the alkali-soluble resin and dispersant contained in the pigment dispersion composition and the alkali-soluble resin contained in the clear resist are the resins shown in Table 3. Got

[Example 21]
As an alkali-soluble resin, 9.07 g of the above-mentioned copolymer solution (A-1) (that is, 3.5 g of resin), 3.25 g of byk2000 as a dispersant (1.3 g of non-volatile content), and C.I. I. Pigment Violet 23 (manufactured by Clariant, hereinafter referred to as PV23) 1.6 g, dye C.I. I. 6.4 g of Solvent Blue 35 (manufactured by MP Biomnicals, hereinafter referred to as SB35) was weighed in a 225 ml mayonnaise bottle and diluted with PGMEA so that the non-volatile content concentration was 20% by weight. 64 g of zirconia beads having a diameter of 1.0 mm was added thereto, and the lid was closed. This was shaken with a paint shaker for 3 hours, and after 3 hours, the pigment dispersion composition and the zirconia beads were separated, 64 g of 0.5 mm zirconia beads were added, and the mixture was shaken with a paint shaker for another 3 hours. Then, the pigment dispersion composition and the zirconia beads were separated, 64 g of 0.3 mm zirconia beads were added, and the mixture was further shaken with a paint shaker for 3 hours to obtain a pigment dispersion composition b.
The pigment dispersion composition b contains 3.5 g of DPHA as a polyfunctional monomer, 4.66 g of the above-mentioned copolymer solution (A-1) as a binder resin (that is, 1.8 g of resin), and a photopolymerization initiator (Irg369). Clear resist II containing 9 g was added and diluted with PGMEA so that the non-volatile content concentration was 20% by weight. After removing the zirconia beads, the photosensitive resin composition B1 was prepared by filtering through a filter having a pore size of 1.0 μm.

[Examples 22 to 30, Comparative Examples 5 and 6]
The photosensitive resin compositions B2 to 12 are the same as in Example 21 except that the alkali-soluble resin and dispersant contained in the pigment dispersion composition and the alkali-soluble resin contained in the clear resist are the resins shown in Table 4. Got

[Example 31]
As an alkali-soluble resin, 9.07 g of the above-mentioned copolymer solution (A-1) (that is, 3.5 g of resin), and as a dispersant, DISPERBYK-164 (nonvolatile content 1.3 g, acid value: 0 mgKOH / g, amine value: 18 mgKOH / g; manufactured by Big Chemie Japan, hereinafter referred to as byk164) is 2.17 g, and 8.0 g of pigment Printex 45 (manufactured by Orion Engineered Carbons, hereinafter referred to as PT45) as a coloring material is placed in a 225 ml mayonnaise bottle. It was weighed and diluted with PGMEA so that the non-volatile content concentration was 20% by weight. To this, 64 g of zirconia beads having a diameter of 1.0 mm was added, and the mixture was shaken with a paint shaker for 3 hours. After 3 hours, the pigment dispersion composition and the zirconia beads were separated, 64 g of 0.5 mm zirconia beads were added, and the mixture was shaken with a paint shaker for another 3 hours. Then, the pigment dispersion composition and the zirconia beads were separated, 64 g of 0.3 mm zirconia beads were added, and the mixture was further shaken with a paint shaker for 3 hours to obtain a pigment dispersion composition k.
In this pigment dispersion composition k, 3.5 g of DPHA as a polyfunctional monomer, 4.66 g of the above-mentioned copolymer solution (A-1) as a binder resin (that is, 1.8 g of a resin), and etanone, 1- as a photopolymerization initiator. [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) (trade name "IRGACUREOXE02", manufactured by BASF Japan, hereinafter referred to as OXE02) 1 Clear resist III containing .9 g 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 through a filter having a pore size of 1.0 μm to prepare a photosensitive resin composition K1.

[Examples 32 to 40, Comparative Example 7]
The photosensitive resin composition K2-11 is the same as in Example 31 except that the alkali-soluble resin and dispersant contained in the pigment dispersion composition and the alkali-soluble resin contained in the clear resist are the resins shown in Table 5. Got

[Example 41]
As an alkali-soluble resin, 9.07 g of the above-mentioned copolymer solution (A-1) (that is, 3.5 g of resin), and as a dispersant, DISPERBYK-182 (nonvolatile content 1.3 g, acid value: 0 mgKOH / g, amine value: 13 mgKOH / g; manufactured by Big Chemie Japan, hereinafter referred to as byk182) 3.02 g, and as a coloring material, titanium oxide TTO-51 (manufactured by Ishihara Sangyo, hereinafter referred to as TTO-51) 8.0 g was weighed into a 225 ml mayonnaise bottle. It was diluted with PGMEA so that the non-volatile content concentration was 20% by weight. To this, 64 g of zirconia beads having a diameter of 1.0 mm was added, and the mixture was shaken with a paint shaker for 3 hours. After 3 hours, the pigment dispersion composition and the zirconia beads were separated, 64 g of 0.5 mm zirconia beads were added, and the mixture was shaken with a paint shaker for another 3 hours. Then, the pigment dispersion composition and the zirconia beads were separated, 64 g of 0.3 mm zirconia beads were added, and the mixture was further shaken with a paint shaker for 3 hours to obtain a pigment dispersion composition w.
In this pigment dispersion composition w, 3.5 g of DPHA as a polyfunctional monomer, 4.66 g of the above-mentioned copolymer solution (A-1) as a binder resin (that is, 1.8 g of resin), and a photopolymerization initiator (Irg907) 1. Clear resist I containing 9 g 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 through a filter having a pore size of 1.0 μm to prepare a photosensitive resin composition W1.

[Examples 42 to 50, Comparative Examples 8 and 9]
The photosensitive resin compositions W2-12 are the same as in Example 41, except that the alkali-soluble resin and dispersant contained in the pigment dispersion composition and the alkali-soluble resin contained in the clear resist are the resins shown in Table 6. Got

<Evaluation>
Using the photosensitive resin compositions obtained in Examples and Comparative Examples, line-and-pace patterns were formed according to the following developing methods, and the following evaluations (1) to (4) were performed. The results are shown in Tables 2-6.
(Development method)
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 UV aligner (trade name "TME-150RNS", manufactured by TOPCON) equipped with a 2.0 kW ultra-high pressure mercury lamp by arranging a photomask having a line and space of 15 μm at a distance of 100 μm from the coating film 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% potassium hydroxide aqueous solution is sprayed on the coating film with a spin developing machine to dissolve and remove the unexposed part, and the remaining exposed part is washed with pure water for 10 seconds to develop. And formed a line-and-space pattern.
(1) Break time The shortest development time (potassium hydroxide aqueous solution spraying time) at which pattern formation was possible during development was evaluated as the break time.
(2) Time at which peeling occurs During development, spraying of potassium hydroxide aqueous solution was continued, and the time until peeling began to occur in the pattern was evaluated.
(3) Development Margin The time obtained by subtracting the break time from the development time at which the peeling starts to occur was evaluated as the development margin.
(4) Pattern cross-sectional shape The shape of the pattern was measured using FE-SEM (trade name "JSM-7600FA", manufactured by JEOL Ltd.). When the pattern obtained with a 15 μm line-and-space photomask is measured from the horizontal direction of the glass surface and the upper base width of the pattern is X and the lower base width of the pattern is Y, the case where X / Y is 1 or more is determined. The taper type was defined as the reverse taper type when it was less than 1.
In this evaluation, the photosensitive resin compositions R1 to 12, the photosensitive resin compositions G1 to 12, the photosensitive resin compositions B1 to 12, and the photosensitive resin compositions W1 to 12 were samples after an alkaline development time of 40 seconds. The photosensitive resin compositions K1 to 11 were measured, and samples were measured after an alkaline development time of 60 seconds.

(5) In-plane uniformity 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, 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. Then, it was heated in an oven at 230 ° C. for 30 minutes.
The arithmetic mean surface roughness Ra of the sample obtained as described above was measured using a laser microscope (trade name "VK-9700", manufactured by KEYENCE CORPORATION), and the in-plane uniformity was evaluated. The measurement range was 1400 μm × 1050 μm. The results are shown in Tables 2-6.

As is clear from Tables 2 to 6, the photosensitive resin composition of the present invention has a long development margin and can form a tapered molded product.

Claims (8)

It contains an alkali-soluble resin, a coloring material, a dispersant, a polyfunctional monomer, a photopolymerization initiator, and a solvent.
The alkali-soluble resin contains a structural unit having a biphenyl group in the side chain, a structural unit (B) having a ring structure in the main chain, and a structural unit having a carbon double bond 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 (1) or (2).
The structural unit (B) having a ring structure in the main chain is at least one selected from the structural units represented by the general formulas (3) and (6) to (9).
The acid value of the dispersant is 0 mgKOH / g.
Photosensitive resin composition:

In formula (2), n1 is 1-10.

The photosensitive resin composition according to claim 1, wherein the amine value of the dispersant is 25 mgKOH / g or less. The photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble resin is a (meth) acrylic resin. The photosensitive resin composition according to any one of claims 1 to 3, wherein the alkali-soluble resin further contains a structural unit (B) having a ring structure in the main chain. The photosensitive resin composition according to any one of claims 1 to 4, wherein the alkali-soluble resin further contains a structural unit having an acid group in the side chain. In the alkali-soluble resin , the proportion of the structural unit having a carbon double bond in the side chain is 15 parts by weight or more and 150 parts by weight with respect to 100 parts by weight of the alkali-soluble resin before adding the compound having a carbon double bond. The photosensitive resin composition according to any one of claims 1 to 5 , which is less than or equal to a portion. A cured product, which is obtained by curing the photosensitive resin composition according to any one of claims 1 to 6. A color filter comprising a substrate and the cured product according to claim 7, which is arranged on the substrate.