JP2018123274A - Alkali-soluble resin, photosensitive resin composition and use therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkali-soluble resin which can give a cured product having excellent solvent resistance and heat resistance and is particularly useful as a main component of a photosensitive resin composition. Further, a photosensitive resin composition containing such an alkali-soluble resin, a cured product thereof, and a color filter using the cured product, a member for a display device, and a display device are also provided. SOLUTION: The polymer contains a structural unit (A) represented by the general formula (I) and a structural unit (B) represented by the general formula (II), and further contains an acid group, and is a glass. An alkali-soluble resin having a transition temperature of 60 ° C. or lower and a double bond equivalent of 200 to 2000. [Selection diagram] None

Description

The present invention relates to an alkali-soluble resin, a photosensitive resin composition and use thereof. Specifically, the present invention relates to an alkali-soluble resin, a photosensitive resin composition including the alkali-soluble resin, a cured product, a display device member having the cured product, and a display device.

Alkali-soluble resins are materials used in various fields from civil engineering and building materials to electronic information materials. One of the main uses is an alkali development type photosensitive resin composition. The photosensitive resin composition is a composition whose physical properties are changed by irradiating the coating film with light or an electron beam, that is, for example, the exposed portion is cured and the other portion is soluble. It is a composition. Utilizing such characteristics, various optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, etc. used in liquid crystal display devices and solid-state imaging devices, and electrical / electronic devices, etc. Widely used in applications. Among these, for example, the color filter is generally composed of a substrate, pixels of at least three primary colors (red, green, and blue), a resin black matrix that separates them, a protective film, and the like.

The photosensitive resin composition usually comprises a composition containing a colorant (also referred to as a colorant) such as a pigment or a dye in addition to an alkali-soluble resin or the like. For example, when forming a pixel of a color filter using the photosensitive resin composition, for each pixel color, (1) an application process for applying the photosensitive resin composition to the substrate, and (2) an application process. The resist film is exposed to a pattern through a photomask to cure the exposed portion, and then the exposure step in which the cured portion is insolubilized. (3) The unexposed portion is removed with a developer and then exposed by baking (baking). A method is employed in which a development / firing process for further curing the part is performed, and the same process is repeated for each color. As conventional photosensitive resin compositions, for example, compositions described in Patent Documents 1 to 3 have been developed.

JP 2014-210892 A JP 2011-145553 A JP 2012-032772 A

In a color filter, a compound film such as a polyimide film is usually applied to a substrate in order to align a liquid crystal, and the polyimide resin generally contains a highly polar solvent (for example, N-methylpyrrolidone). Therefore, alkali-soluble resins and photosensitive resin compositions used for color filters and the like are required to have a cured portion (cured film) resistant to a solvent, that is, solvent resistance. In recent years, in order to improve the display quality and imaging quality of liquid crystal display devices and image pickup tube elements, there has been an increasing demand for higher brightness and higher contrast, and there is also a demand for thinner films, which is photosensitive. It tends to increase the colorant concentration in the resin composition. For the same reason, the miniaturization of pixels constituting the color filter is also remarkable. However, as the colorant concentration increases, there is a problem that the colorant elutes into the washing solvent in the manufacturing process. Therefore, alkali-soluble resins and photosensitive resin compositions are required to exhibit solvent resistance after curing. It is done.

The alkali-soluble resin and photosensitive resin composition are also required to have heat resistance so that the cured product can stably exhibit various physical properties even after exposure to high temperatures. However, the conventional resin compositions described in Patent Documents 1 to 3 have room for improvement in order to further improve heat resistance as well as solvent resistance.

The present invention has been made in view of the above-described situation, and can provide a cured product excellent in solvent resistance and heat resistance, and particularly provides an alkali-soluble resin useful as a main component of a photosensitive resin composition. With the goal. Another object of the present invention is to provide a photosensitive resin composition containing such an alkali-soluble resin, a cured product thereof, a color filter using the cured product, a member for a display device, and a display device.

The present inventor has made various studies on alkali-soluble resins, has a structural unit containing a tetrahydropyran ring and a structural unit containing a long-chain linear or branched hydrocarbon group, and contains an acid group. When the polymer has a glass transition temperature (also referred to as Tg) and a double bond equivalent within a predetermined range, the heat resistance is remarkably high, and when used in combination with a coloring material (coloring agent), it is solvent resistant. It has been found that a cured product capable of exhibiting the properties and sufficiently suppressing the elution of the coloring material can be obtained. In particular, the alkali-soluble resin is a low Tg resin having a long-chain linear or branched hydrocarbon group in the side chain, a double bond in the side chain at a predetermined equivalent, and the hydrocarbon It is thought that the three elements of the group and the high density of the side chain double bond contribute greatly to the effect of improving the solvent resistance, and further, the main chain has a tetrahydropyran ring structure. For the first time, it is considered that the heat resistance as well as the solvent resistance has been realized. The present inventor has also found that a photosensitive resin composition containing such an alkali-soluble resin is particularly useful for color filter applications, and is particularly suitable as a resin composition for forming pixels of a color filter. It was. In addition, cured products, color filters, display device members and display devices obtained using this photosensitive resin composition can be used in the optical, electrical, and electronic fields as sufficient to meet the recent demand for higher performance. It has also been found that it is extremely useful, and has come up with the idea that the above problems can be solved brilliantly. Thus, the present invention has been completed.

That is, the present invention is a polymer comprising a structural unit (A) represented by the following general formula (I) and a structural unit (B) represented by the following general formula (II), and further comprising an acid group. The alkali-soluble resin has a glass transition temperature of 60 ° C. or lower and a double bond equivalent of 200 to 2000.

In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms. n represents the average number of repeating units of the structural unit represented by the general formula (I), and is a number of 1 or more.

In formula, R < ³ > is the same or different and represents a hydrogen atom or a methyl group. R ⁴ is the same or different and represents a linear or branched hydrocarbon group having 4 to 20 carbon atoms. m represents the average number of repeating units of the structural unit represented by the general formula (II), and is a number of 1 or more.

The content ratio of the structural unit (A) is preferably 0.5 to 50% by mass with respect to 100% by mass of the total amount of all monomer units giving the main chain skeleton of the alkali-soluble resin. The content ratio of B) is preferably 10 to 90% by mass.

The present invention is also a photosensitive resin composition containing the alkali-soluble resin.
The photosensitive resin composition preferably further contains a colorant. The colorant is preferably a pigment and / or a dye.
The photosensitive resin composition preferably further contains a polymerizable compound.
The photosensitive resin composition is preferably used for a color filter.

The present invention is also a cured product obtained by curing the photosensitive resin composition.
The present invention is also a color filter having the above cured product on a substrate.
The present invention is also a display device member or display device including the color filter.

The alkali-soluble resin of the present invention can give a cured product excellent in solvent resistance and heat resistance, and is particularly useful as a main component of a photosensitive resin composition. The photosensitive resin composition using this is suitably applied to various uses such as various optical members, electrical machines and electronic devices such as ink, printing plates, printed wiring boards, semiconductor elements, and photoresists in addition to color filters. be able to. Therefore, the color filter, the display device member and the display device having such a cured product (cured film) of the photosensitive resin composition make a great contribution in various fields such as the optical field, the electric field, and the electronic field. is there.

The present invention is described in detail below. A form in which two or three or more preferred forms of the present invention described below are combined is also a preferred form of the present invention.

1. Alkali-soluble resin The alkali-soluble resin of the present invention has a Tg of 60 ° C. or lower. Only when the Tg is in this range and has a structural unit to be described later and the double bond equivalent is in the predetermined range is an alkali-soluble resin, a cured product having both excellent solvent resistance and heat resistance is provided. be able to. Tg is preferably 58 ° C. or lower, more preferably 55 ° C. or lower. Moreover, although the minimum of Tg is not specifically limited, From a heat resistant viewpoint, it is preferable that it is -30 degreeC or more, for example. More preferably, it is −25 ° C. or higher.
In the present specification, Tg can be determined by the method described in Examples described later.

The alkali-soluble resin has a double bond equivalent of 200 to 2000. That is, the alkali-soluble resin is a polymer containing a double bond (that is, an ethylenically unsaturated group) in the side chain, and the double bond equivalent is 200 to 2000. When the double bond equivalent is in this range, the solvent resistance of the cured product is improved, and storage stability, sensitivity to light, developability, and the like are also improved. The double bond equivalent is preferably 300 or more, more preferably 400 or more, still more preferably 450 or more, and particularly preferably 490 or more. Moreover, it is preferably 1900 or less.
In addition, the polymer which does not have a double bond in a side chain does not have a double bond equivalent.

In the present specification, the double bond equivalent is a measure of the amount of double bonds contained in the molecule, and means the molecular weight per double bond of the polymer. If the compounds have the same molecular weight, the amount of double bonds introduced decreases as the double bond equivalent value increases.
The double bond equivalent can be calculated from the charged amount of the raw material, and can be obtained by dividing the mass (g) of the solid content of the polymer by the double bond amount (mol) of the polymer (detailed request) The method was described in the examples described later). Moreover, it can also measure using various analysis, such as titration and elemental analysis, NMR, IR, and a differential scanning calorimeter method.

The alkali-soluble resin preferably has an acid value of 20 to 300 mgKOH / g. Thereby, alkali-solubility improves more and the hardened | cured material which is excellent in developability can be given. Moreover, the solvent resistance of the cured product can be further improved, the development speed can be moderated, the adhesion can be further improved, and the possibility of surface roughness during development can be further suppressed. The acid value is more preferably 40 mgKOH / g or more, still more preferably 60 mgKOH / g or more, and particularly preferably 80 mgKOH / g or more. Further, it is more preferably 200 mgKOH / g or less, further preferably 150 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less.
In this specification, an acid value can be calculated | required by the method as described in the Example mentioned later.

The alkali-soluble resin preferably further has a weight average molecular weight of 5,000 to 200,000. Thereby, various performances, such as solvent resistance, heat resistance, developability, are exhibited more. More preferably, it is 6000 or more, and is particularly preferable because the solvent resistance is particularly remarkable. More preferably, it is 7000 or more, More preferably, it is 8000 or more, More preferably, it is 10,000 or more, Especially preferably, it is 12000 or more, Most preferably, it is 12800 or more. Further, it is more preferably 150,000 or less, further preferably 100,000 or less, particularly preferably 50,000 or less, and most preferably 30,000 or less.
In this specification, a weight average molecular weight can be calculated | required by the method as described in the Example mentioned later.

The alkali-soluble resin has a double bond in a side chain as described above, and the main chain includes a structural unit represented by the general formula (I) (also referred to as a structural unit (A)) and the general formula ( II), and a polymer further containing an acid group.
Here, the acid group is introduced into the alkali-soluble resin, for example, when the alkali-soluble resin contains a structural unit (also referred to as a structural unit (C)) derived from the acid group-containing monomer (c). It is preferable that That is, the alkali-soluble resin is preferably a polymer containing at least the structural units (A), (B), and (C) in the main chain skeleton.

In the alkali-soluble resin, the content ratio of the structural unit (A) is, for example, 0.5 to 50% by mass with respect to 100% by mass of all monomer units that give the main chain skeleton of the alkali-soluble resin. Is preferred. Thereby, heat resistance and storage stability improve. More preferably, it is 1-40 mass%, More preferably, it is 5-30 mass%.
In addition, n in the said general formula (I) represents the average number of repeating units of the structural unit (A) in alkali-soluble resin, but it is n so that the content rate of a structural unit (A) may become in the range mentioned above. Is preferably set.

It is preferable that the content rate of a structural unit (B) is 10-90 mass% with respect to 100 mass% of the total amount of all the monomer units which give the principal chain skeleton of alkali-soluble resin, for example. Thereby, solvent resistance improves more. More preferably, it is 20-80 mass%, More preferably, it is 30-75 mass%.
In addition, m in the said general formula (II) represents the average number of repeating units of the structural unit (B) in alkali-soluble resin, but it is m so that the content rate of a structural unit (B) may become in the range mentioned above. Is preferably set.

It is preferable that the content rate of a structural unit (C) is 0.5-50 mass% with respect to 100 mass% of the total amount of all the monomer units which give the principal chain skeleton of alkali-soluble resin, for example. Thereby, the solubility in an alkali substance and the solubility in a solvent are improved, and the viscosity of the polymer is improved. More preferably, it is 2-50 mass%, More preferably, it is 5-45 mass%.

Examples of the alkali-soluble resin include a monomer (a) represented by the following general formula (i), a monomer (b) represented by the following general formula (ii), and an acid group-containing monomer. (C) a polymer obtained by polymerizing a monomer component (also referred to as a base polymer), and a compound (X) having a functional group capable of bonding to an acid group and a polymerizable double bond is reacted. It is preferable to obtain. Each reaction raw material can be used individually or in combination of two or more.
Hereinafter, each monomer, compound (X), etc. which give a base polymer are further demonstrated.

1) Monomer (a)
The monomer (a) is a monomer represented by the following general formula (i). The symbols in the formula are the same as the symbols in formula (I). When the monomer (a) is used for the polymerization reaction, it is presumed that the monomer (a) undergoes a cyclization reaction during the polymerization and a tetrahydropyran ring structure is formed in the structural unit of the polymer.

In the general formulas (I) and (i), R ¹ and R ² are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms. Examples of the hydrocarbon group having 1 to 25 carbon atoms include linear or branched alkyl groups, aryl groups, alicyclic groups, and alkoxy groups exemplified in JP2013-61599A [0037]. An alkyl group substituted with an aryl group; and the like. Of these, primary or secondary carbon hydrocarbon groups which are difficult to be removed by acid or heat, such as methyl, ethyl, cyclohexyl, benzyl and the like, are preferable in terms of heat resistance.
The hydrocarbon group may have a substituent.

Examples of the monomer (a) include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, Di (n-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n- Butyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2 , 2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di ( Thearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) -2 , 2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxyethyl) -2 , 2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis (methylene)] bis- 2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butylcyclo Xyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tricyclo Decanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 ′ -[Oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate and the like.

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

It is preferable that the content rate of the said monomer (a) is 0.5-50 mass% with respect to 100 mass% of total amounts of the monomer component which gives a base polymer, for example. Thereby, dispersibility and storage stability are improved. More preferably, it is 1-40 mass%, More preferably, it is 5-30 mass%.

2) Monomer (b)
The monomer (b) is a monomer represented by the following general formula (ii). The symbols in the formula are the same as the symbols in formula (II). The structural unit (B) is formed from the monomer (b).

In the general formulas (II) and (ii), R ³ is the same or different and represents a hydrogen atom or a methyl group. R ⁴ is the same or different and represents a linear or branched hydrocarbon group having 4 to 20 carbon atoms. This hydrocarbon group may have a substituent.

Here, in the present invention, it is important that R ⁴ represents a linear or branched hydrocarbon group and a relatively long chain having 4 to 20 carbon atoms. If the number of carbon atoms exceeds 20, coloring or heat resistance may be lowered when used in combination with a coloring material, and if the number of carbon atoms is less than 4, the cured product may not exhibit sufficient solvent resistance. The hydrocarbon group represented by R ⁴ is preferably a linear or branched alkyl group. The carbon number is preferably 4 to 16, more preferably 4 to 12.
In addition, although the said hydrocarbon group may have a substituent, it is suitable not to have a substituent.

Examples of the monomer (b) include butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, Alkyl (meth) acrylate compounds such as octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, Examples include hydroxyl group-containing (meth) acrylate compounds such as 4-hydroxybutyl (meth) acrylate; ether group-containing (meth) acrylate compounds such as 2-ethoxyethyl (meth) acrylate; and the like. Of these, alkyl (meth) acrylate compounds are preferred from the viewpoint of improving solvent resistance.

It is preferable that the content rate of the said monomer (b) is 10-90 mass% with respect to 100 mass% of total amounts of the monomer component which gives a base polymer, for example. Thereby, solvent resistance improves more. More preferably, it is 20-80 mass%, More preferably, it is 30-75 mass%.

3) Monomer (c)
The monomer (c) is an acid group-containing monomer.
The acid group is not particularly limited, and examples thereof include functional groups that neutralize with alkaline water, such as carboxyl groups, phenolic hydroxyl groups, carboxylic anhydride groups, phosphoric acid groups, and sulfonic acid groups. Of these, a carboxyl group or a carboxylic anhydride group is preferable, a carboxyl group is more preferable, and a (meth) acrylic acid group is still more preferable.

Examples of the monomer (c) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, and vinyl benzoic acid; maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid Unsaturated polycarboxylic acids such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), etc. Carboxylic acids; Unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; Phosphoric acid group-containing unsaturated compounds such as light ester P-1M (manufactured by Kyoeisha Chemical); and the like. Among these, carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polyvalent carboxylic acids, unsaturated acid anhydrides) are preferable from the viewpoints of versatility and availability. More preferred are unsaturated monocarboxylic acids in terms of reactivity and alkali solubility, and (meth) acrylic acid is still more preferred.
Here, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

The content ratio of the monomer (c) is preferably set so that the acid value is within the preferable range described above. For example, it is preferable that it is 0.5-50 mass% with respect to 100 mass% of the total amount of the monomer component which gives a base polymer. Thereby, the solubility in an alkali substance and the solubility in a solvent are improved, and the viscosity of the polymer is improved. More preferably, it is 2-50 mass%, More preferably, it is 5-45 mass%.

When (meth) acrylic acid is used as the monomer (c), the alkali-soluble resin of the present invention is a polymer having a structural unit (C) represented by the following general formula (III).

In formula, R < ⁵ > is the same or different and represents a hydrogen atom or a methyl group. p represents the average number of repeating units of the structural unit represented by the general formula (III), and is a number of 1 or more.

4) Monomer (d)
The alkali-soluble resin is also a structural unit derived from the above-mentioned monomer (a), (b) and / or other monomer copolymerizable with (c) (also referred to as monomer (d)). 1 type or 2 types or more may be included. That is, the monomer component that gives the base polymer may further contain the monomer (d).

It does not specifically limit as a monomer (d), For example, carbon numbers 1-3, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, etc. Alkyl (meth) acrylate compounds; aromatic vinyl compounds such as styrene, vinyl toluene and α-methyl styrene; ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride and acrylonitrile; vinyl esters such as vinyl acetate; Can be mentioned. Especially, it is suitable to use a C1-C3 alkyl (meth) acrylate compound at the point which transparency is favorable and it is hard to impair solvent resistance and heat resistance.

Although the content rate of the said monomer (d) is not specifically limited, For example, it is preferable that it is 0-50 mass% with respect to 100 mass% of total amounts of the monomer component which gives a base polymer. More preferably, it is 0-25 mass%, More preferably, it is 0-10 mass%.

Here, in this invention, it is so suitable that the content rate of the ring structure which exists in a side chain is small from a viewpoint of solvent-resistant improvement. That is, specifically, a monomer (for example, having a cyclic hydrocarbon group such as cyclohexyl (meth) acrylate) that gives a ring structure to the polymer side chain with respect to 100% by mass of the total amount of monomer components giving the base polymer. It is preferable that the content ratio of the monomer or the like is 5% by mass or less. More preferably, it is 1 mass% or less, More preferably, it is 0.1 mass% or less.

As a method for polymerizing the monomer component, a commonly used technique such as bulk polymerization, solution polymerization, emulsion polymerization or the like can be used, and it may be appropriately selected according to the purpose and application. Among these, solution polymerization is preferred because it is industrially advantageous and structural adjustments such as molecular weight are easy. The polymerization mechanism of the monomer component may be a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization, but the polymerization method based on the radical polymerization mechanism is industrial. Is also preferable. A preferable form of the polymerization reaction is as described in JP-A-2006-29151 [0062] to [0072].

As described above, the alkali-soluble resin of the present invention can be obtained by reacting the base polymer with a compound having a functional group capable of binding to an acid group and a polymerizable double bond (also referred to as compound (X)). preferable.

Examples of the polymerizable double bond of the compound (X) include a (meth) acryloyl group, a vinyl group, an allyl group, a methallyl group, and the like, and those compounds having one or more of these as the compound Is preferred. Of these, a (meth) acryloyl group is preferable in terms of reactivity. Moreover, as a functional group which can couple | bond with an acid group, a hydroxyl group, an epoxy group, oxetanyl group, an isocyanate group etc. are mentioned, for example, What has these 1 type (s) or 2 or more types as the said compound is suitable. Of these, epoxy groups (including glycidyl groups) are preferred from the viewpoint of the speed of the modification treatment reaction, heat resistance, and dispersibility.

Examples of the compound (X) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, vinylbenzyl glycidyl ether, allyl glycidyl ether, and (meth) acrylic. Examples include acid (3,4-epoxycyclohexyl) methyl, vinylcyclohexene oxide and the like. Among these, it is preferable to use a compound (monomer) having an epoxy group and a (meth) acryloyl group. In particular, glycidyl (meth) acrylate and / or (and) having high reactivity and being easy to control, easily available, and capable of introducing not only radical polymerizable double bonds but also hydroxyl groups at the same time. (Meth) acrylic acid (3,4-epoxycyclohexyl) methyl is more preferred.

The addition amount of the compound (X) is not particularly limited as long as the double bond equivalent of the alkali-soluble resin falls within the above-mentioned range. For example, the addition amount of the compound (X) is 2 to 2 parts by mass with respect to 100 parts by mass of the monomer components giving the base polymer. 60 parts by mass is preferred. More preferably, it is 10-55 mass parts, More preferably, it is 10-50 mass parts, Most preferably, it is 10-45 mass parts.

The method for reacting the compound (X) with (a part of) the acid groups in the base polymer is not particularly limited as long as a known addition method or the like is employed. The reaction temperature is preferably, for example, 60 ° C to 140 ° C. It is also preferable to use a known catalyst such as an amine compound such as triethylamine or dimethylbenzylamine; an ammonium salt such as tetraethylammonium chloride; a phosphonium salt such as tetraphenylphosphonium bromide; an amide compound such as dimethylformamide;

Since the alkali-soluble resin of the present invention can give a cured product having excellent solvent resistance and heat resistance, as well as excellent curability and transparency, for example, for various applications such as resist materials, various coating agents, and paints. It can be used suitably. Since it also has good developability, it is useful as a negative resist material of an alkali development type for producing colored pixels of a color filter, black matrix, overcoat, photospacer, optical waveguide and the like. Moreover, since it also has favorable color material dispersibility, it is useful also for the colored curable resin composition for color filters. The alkali-soluble resin is particularly preferably used as a color resist binder resin, a solder resist resin, or the like, and the alkali-soluble resin is extremely useful as a main component of the photosensitive resin composition.

2. Photosensitive resin composition The photosensitive resin composition of the present invention (also simply referred to as “resin composition”) contains the alkali-soluble resin of the present invention described above. If necessary, it may further contain other components. Each component can be used alone or in combination of two or more.

In this specification, “the total amount of the solid content of the photosensitive resin composition (resin composition)” means a component that forms a cured product (a solvent that volatilizes at the time of formation of the cured product) among the components contained in the resin composition. Excluding)).

1) Alkali-soluble resin The alkali-soluble resin is as described above. In addition, you may use together alkali-soluble resin other than the alkali-soluble resin of this invention mentioned above.
These alkali-soluble resins can act as a binder resin in the photosensitive resin composition.

Although the content rate of the said alkali-soluble resin (when 2 or more types are included, the total amount) is not specifically limited, For example, it is preferable that it is 5-70 mass% with respect to 100 mass% of solid content total amount of a resin composition. More preferably, it is 10-65 mass%, More preferably, it is 15-60 mass%.

2) Colorant (coloring material)
The resin composition preferably contains a colorant. This makes it more useful for color filter applications. In addition, the said resin composition can exhibit the especially outstanding solvent resistance, when it contains a coloring material, and can fully suppress the bleeding of a coloring material.

As the colorant (coloring material), for example, pigments and dyes are preferably used. These may be used alone or in combination of two or more. Moreover, you may combine a pigment and dye. Thus, the form in which the colorant is a pigment and / or a dye is one of the preferred forms of the present invention. In addition, for example, when forming red, blue, and green pixels of a color filter, a technique that exhibits color characteristics obtained by combining color materials such as blue and purple, green and yellow is preferably used, and a black matrix is formed. Can be formed using a black color material.

Among pigments and dyes, for example, pigments (for example, organic pigments or inorganic pigments) are excellent in terms of durability, and, for example, dyes are excellent in terms of improving luminance of panels and the like. May be selected or used in combination. Among the pigments, an organic pigment is more preferable.

Examples of the pigment include azo pigments, phthalocyanine pigments, polycyclic pigments (for example, quinacridone, perylene, perinone, isoindolinone, isoindoline, dioxazine, thioindigo, anthraquinone, quinophthalone). , Metal complex, diketopyrrolopyrrole, etc.), organic pigments such as dye lake pigments; white and extender pigments (eg, titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.) Chromatic pigment (for example, chrome lead, cadmium, chromium vermilion, nickel titanium, chromium titanium, yellow iron oxide, bengara, zinc chromate, red lead, ultramarine, bitumen, cobalt blue, chromium green, chromium oxide, bismuth vanadate, etc.) , Black pigments (eg carbon black, bone black, graphs) Ito, iron black, titanium black, etc.), the luminous material pigments (e.g. pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments (such as zinc sulfide, strontium sulfide, and inorganic pigments strontium aluminate, etc.) and the like. Examples of pigment colors that can be used include yellow, red, purple, blue, green, brown, black, and white.

The pigment may also be subjected to surface treatment such as rosin treatment, surfactant treatment, resin dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc. depending on the purpose and application.

Specific examples of the pigment include C.I. described in paragraph numbers 0103 to 0107 of JP-A-2015-42697. I. Yellow pigments such as CI Pigment Yellow 1 and 138; I. Orange pigments such as CI Pigment Orange 1; I. A purple pigment such as CI Pigment Violet 1; I. Red pigments such as CI Pigment Red 1; I. Blue pigments such as CI Pigment Blue 1; I. Green pigments such as CI Pigment Green 1 and 58; I. Brown pigments such as CI Pigment Brown 5; aniline black, carbon black, lamp black, bone black, black iron, titanium black, C.I. I. Black pigments such as CI Pigment Black 1; I. And white pigments such as CI Pigment White 1. “CI” means a color index (CI; issued by The Society of Dyers and Colorists), and a number means a color index number.

As the dye, for example, organic dyes described in JP 2010-9033 A, JP 2010-211198 A, JP 2009-51896 A, and JP 2008-50599 A may be used. it can. Of these, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like are preferable.

The content ratio of the colorant (preferably the total ratio of the pigment and the dye) can be appropriately set according to the purpose and application. For example, the total solid content of the photosensitive resin composition is 100% by mass. It is preferable to set it as 3-70 mass%. More preferably, it is 5-60 mass%, More preferably, it is 10-50 mass%.

3) Dispersant When the resin composition includes a colorant (colorant), it is preferable that the resin composition further include a dispersant. A dispersant has an interaction site to a color material and an interaction site to a dispersion medium (for example, a solvent or a binder resin), and has a function of stabilizing the dispersion of the color material in the dispersion medium. Generally, it is classified into a resin-type dispersant (for example, a polymer dispersant), a surfactant (for example, a low molecular dispersant), and a pigment derivative. It is preferable that the resin composition contains a dispersant along with the coloring material.

The resin-type dispersant is not particularly limited, and examples thereof include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydrogen group-containing polycarboxylic acid esters, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and salts thereof (meth) Acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, polyester, modified polyacrylate, ethylene oxide / polypropylene oxide Id adducts.

The structure of the resin-type dispersant is a resin having a graft structure in which the main chain is an anchor chain having an interaction site with a coloring material, and the graft chain is a compatible chain having an interaction property with a dispersion medium, A resin in which an anchor chain and a compatible chain have a block structure is particularly preferably used.

Specific examples of the resin-type dispersant include products described in paragraph No. 0112 of JP-A-2015-42697.

The surfactant is not particularly limited, and examples thereof include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, and lauryl sulfate triethanolamine. , Anionic surfactants such as ammonium lauryl sulfate, sodium stearate, sodium lauryl sulfate; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaur Nonionic surfactants such as rate; addition of alkyl quaternary ammonium salts and their ethylene oxide Alkyl betaines such as alkyl dimethylamino acetic acid betaine, and amphoteric surfactants such as alkyl imidazolines; cationic surfactants etc., and the like.

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

The content of the dispersant (that is, the resin-type dispersant, the surfactant and / or the pigment derivative) may be appropriately set according to the purpose and application, but the dispersion stability and durability (heat resistance, light resistance) From the viewpoint of balance between weather resistance and the like) and transparency, for example, it is preferably 0.01 to 60% by mass with respect to 100% by mass of the total solid content of the resin composition. More preferably, it is 0.1-50 mass%, More preferably, it is 0.3-40 mass%.

4) Polymerizable compound The resin composition preferably contains a polymerizable compound.
The polymerizable compound is also referred to as a polymerizable monomer, and can be polymerized by irradiation with active radicals such as free radicals, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays), electron beams, etc. A low molecular compound having a polymerizable unsaturated group). For example, the monofunctional compound which has one polymerizable unsaturated group in a molecule | numerator, and the polyfunctional compound which has 2 or more are mentioned.

Examples of the monofunctional polymerizable monomer include N-substituted maleimide monomers; (meth) acrylic acid esters; (meth) acrylamides; unsaturated monocarboxylic acids; unsaturated polycarboxylic acids; Unsaturated monocarboxylic acids in which the chain between a saturated group and a carboxyl group is extended; unsaturated acid anhydrides; aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; Isocyanates; and the like. A monomer having an active methylene group or an active methine group can also be used.

Examples of the polyfunctional polymerizable monomer include the following compounds.
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol Bifunctional (meth) acrylate compounds such as di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate;

Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added ditrimethylolpropane tetra (meth) acrylate, ethylene oxide Addition pentaerythritol tetra (meth) acrylate, ethylene oxide addition dipe Taerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added ditrimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (meth) acrylate, propylene oxide-added dipentaerythritol hexa (Meth) acrylate, ε-caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol Trifunctional or higher polyfunctional (meth) acrylate compounds such as hexa (meth) acrylate;

Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrile Methylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethyl Lumpur propane tetravinyl ether, ethylene oxide adduct of pentaerythritol tetravinyl ether, polyfunctional vinyl ethers such as ethylene oxide adduct of dipentaerythritol hexavinyl ether;

(Meth) acrylic acid 2-vinyloxyethyl, (meth) acrylic acid 3-vinyloxypropyl, (meth) acrylic acid 1-methyl-2-vinyloxyethyl, (meth) acrylic acid 2-vinyloxypropyl, (meth) acrylic acid 4 -Vinyloxybutyl, 4-vinyloxycyclohexyl (meth) acrylate, 5-vinyloxypentyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, ( Vinyl ether group-containing (meth) acrylic such as p-vinyloxymethylphenylmethyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, and 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate Acid esters;

Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, Ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethyl Lumpur propane tetra allyl ether, ethylene oxide adduct of pentaerythritol tetra-allyl ether, polyfunctional allyl ethers such as ethylene oxide adduct of dipentaerythritol hexa-allyl ether;

Allyl group-containing (meth) acrylic acid esters such as (meth) acrylic acid allyl; tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri (acryloyloxyethyl) isocyanurate, alkylene Polyfunctional (meth) acryloyl group-containing isocyanurates such as oxide-added tri (methacryloyloxyethyl) isocyanurate; polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, etc. Polyfunctional isocyanate and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and other hydroxyl-containing (meth) acrylate esters Multifunctional urethane (meth) acrylates obtained by reaction of a; polyfunctional aromatic vinyl compounds such as divinylbenzene; and the like.

Among the polymerizable compounds, it is preferable to use a polyfunctional polymerizable compound from the viewpoint of further improving the curability of the resin composition. When a polyfunctional polymerizable compound is used as the polymerizable compound, the functional number is preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more. Further, from the viewpoint of further suppressing curing shrinkage, the functional number is preferably 10 or less, more preferably 8 or less.
The molecular weight of the polymerizable compound is not particularly limited, but is preferably 2000 or less from the viewpoint of handling.

When a polyfunctional polymerizable compound is used as the polymerizable compound, among the polymerizable compounds, from the viewpoint of reactivity, economy, availability, etc., a polyfunctional (meth) acrylate compound, a polyfunctional urethane (meth) acrylate It is preferable to use a compound having a (meth) acryloyl group such as a compound or a (meth) acryloyl group-containing isocyanurate compound. More preferably, it is a polyfunctional (meth) acrylate compound, whereby the resin composition becomes more excellent in photosensitivity and curability, and it becomes possible to obtain a cured product having higher hardness and transparency. More preferably, a trifunctional or higher polyfunctional (meth) acrylate compound is used.

In the above resin composition, the content ratio of the polymerizable compound may be appropriately set according to the purpose and application in addition to the type of the polymerizable compound and alkali-soluble resin to be used, but from the viewpoint of better developability and plate making properties. The total solid content of the resin composition is preferably 2 to 80% by mass with respect to 100% by mass. More preferably, it is 5-70 mass%, More preferably, it is 8-60 mass%, Most preferably, it is 10-50 mass%, Most preferably, it is 10-40 mass%.

5) Photopolymerization initiator The resin composition preferably also contains a photopolymerization initiator. The photopolymerization initiator is preferably a radical polymerizable photopolymerization initiator.

The radical polymerizable photopolymerization initiator is one that generates a polymerization initiating radical by irradiation with an active energy ray such as an electromagnetic wave or an electron beam, and one or more commonly used ones may be used. it can. Moreover, you may use together 1 type (s) or 2 or more types of photosensitizers, radical photopolymerization promoters, etc. as needed. A photosensitizer and / or photoradical polymerization accelerator may be used together with the photopolymerization initiator, or may not be used. Even if a photosensitizer and / or a radical photopolymerization accelerator are not used in combination, the effects of the present invention can be sufficiently exerted, but when used together, sensitivity and curability are further improved.

Specific examples of the photopolymerization initiator include the following compounds.
2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2 -Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl}- 2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) fur Nyl] -1-butanone and other alkylphenone compounds; benzophenone, 4,4′-bis (dimethylamino) benzophenone, benzophenone compounds such as 2-carboxybenzophenone; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin Benzoin compounds such as isobutyl ether; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone;

2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 -Ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarboquinylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine, and other halomethylated triazine compounds 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4 Halomethylated oxadiazole compounds such as oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; , 2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′ , 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 Biimidazole compounds such as' -biimidazole; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- ( Oxime ester compounds such as 2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); oxime ether compounds; bis (η5-2,4-cyclopentadien-1-yl ) -Bis (2 Titanocene compounds such as 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium; benzoate compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; 9-phenylacridine and the like An acridine compound;

Among the photopolymerization initiators, it is preferable to use an alkylphenone compound, an oxime ester compound, and / or an oxime ether compound. The oxime ester compound and the oxime ether compound are collectively referred to as “oxime compound”. However, when the oxime compound is used, the curability of the resin composition is remarkably improved, and the solvent resistance of the resulting cured product is improved. Improve dramatically.

In the above resin composition, the content of the photopolymerization initiator is not particularly limited as long as it is appropriately set depending on the purpose, application, etc., but the total solid content of the resin composition excluding the photopolymerization initiator is 100 parts by mass. The amount is preferably 0.1 parts by mass or more. Thereby, the hardened | cured material excellent in adhesiveness can be obtained. More preferably, it is 0.5 mass part or more, More preferably, it is 1 mass part or more, Most preferably, it is 2 mass part or more. In consideration of the balance between the influence of the decomposition product of the photopolymerization initiator, economy, and the like, the amount is preferably 30 parts by mass or less. More preferably, it is 25 mass parts or less, More preferably, it is 20 mass parts or less.

Examples of the photosensitizer and photoradical polymerization accelerator that may be used in combination with the photopolymerization initiator include dye compounds such as xanthene dyes, coumarin dyes, 3-ketocoumarin compounds, and pyromethene dyes; 4-dimethylamino And dialkylaminobenzene compounds such as ethyl benzoate and 2-ethylhexyl 4-dimethylaminobenzoate; mercaptan hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole; .

The photosensitizer and the photoradical polymerization accelerator do not have to be used as described above, but when used, from the viewpoint of balance between curability, influence of degradation products and economy. It is preferable that it is 0.001-20 mass% with respect to 100 mass% of solid content total amount. More preferably, it is 0.01-15 mass%, More preferably, it is 0.05-10 mass%.

6) Solvent The resin composition preferably also contains a solvent. A solvent is preferably used as a diluent or the like. Specifically, the viscosity is lowered to improve the handleability; the coating film is formed by drying; the dispersion medium of the colorant is used; and the like, and the components contained in the resin composition are dissolved. Or a low viscosity organic solvent or water that can be dispersed.

As the solvent, one or two commonly used solvents can be used, and the solvent is not particularly limited as long as it is appropriately selected according to the purpose and application. For example, monoalcohols; glycols; cyclic ethers; glycol monoethers; glycol ethers; esters of glycol monoethers; alkyl esters; ketones; aromatic hydrocarbons; Water; etc. are preferred. Specific examples of these solvents include compounds described in JP-A-2015-42697 [0042]. For example, glycol monoether esters include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl Le acetate and the like.

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

7) Other components The above resin composition further has, for example, a heat resistance improver; a leveling agent; a development aid; inorganic fine particles such as silica fine particles; Coupling agents such as titanium and titanium; thermosetting resins such as fillers, epoxy resins, phenolic resins and polyvinylphenols; curing aids such as polyfunctional thiol compounds; plasticizers; polymerization inhibitors; ultraviolet absorbers; Agent; matting agent; antifoaming agent; antistatic agent; slip agent; surface modifier; thixotropic agent; thixotropic agent; quinonediazide compound; polyhydric phenol compound; cationic polymerizable compound; Further, it may be included.

Although the manufacturing method of the photosensitive resin composition of this invention is not specifically limited, For example, it can prepare by mixing and disperse | distributing the component mentioned above using various mixers and a disperser. The mixing / dispersing step is not particularly limited, and may be performed by a normal method. Further, it may further include other steps that are normally performed. In addition, when the said resin composition contains a coloring material, it is suitable to manufacture through the dispersion processing process of a coloring material.

As the color material dispersion treatment step, for example, a predetermined amount of each of a color material (preferably an organic pigment), a dispersant, and a solvent is weighed, and paint conditioner, bead mill, roll mill, ball mill, jet mill, homogenizer, kneader, blender, etc. An example is a method of using a disperser to disperse fine particles of a color material to obtain a liquid color material dispersion (also referred to as a mill base). Preferably, after kneading and dispersing with a roll mill, kneader, blender or the like, fine dispersion is performed with a media mill such as a bead mill filled with 0.01 to 1 mm beads. A composition (preferably a transparent liquid) containing an alkali-soluble resin or the like that has been separately stirred and mixed is added to the obtained mill base and mixed to obtain a uniform dispersion solution, whereby a resin composition can be obtained.
The obtained resin composition is preferably filtered with a filter or the like to remove fine dust.

3. Hardened | cured material The photosensitive resin composition of this invention gives the hardened | cured material which is excellent in solvent resistance, heat resistance, and photosensitivity. This cured product is also excellent in curability, developability, adhesion to the substrate, transparency, image forming property, surface smoothness, etc., for example, there is no residue of unexposed areas or background stains after development. is there. A cured product obtained by curing such a resin composition is one aspect of the present invention.

The cured product (cured film) preferably has a film thickness (thickness) of 0.1 to 20 μm. Thereby, it can fully respond to the request | requirement of low profile, such as a member using the said hardened | cured material, and a display apparatus. More preferably, it is 0.5-10 micrometers, More preferably, it is 0.5-8 micrometers.

The cured product is used for various optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, etc. used in liquid crystal display devices, solid-state imaging devices, etc., and electrical / electronic devices. Are preferably used. Especially, it is preferable to use for a color filter. A color filter using the resin composition as described above, specifically, a color filter having the cured product on a substrate is also one aspect of the present invention.
Hereinafter, the color filter will be further described.

4. Color filter The color filter of this invention consists of a form which has the said hardened | cured material on a board | substrate.
In the above color filter, the cured product formed by the photosensitive resin composition of the present invention is particularly suitable as a segment that needs to be colored, such as a black matrix or pixels such as red, green, blue, and yellow. However, it is also suitable as a segment that does not necessarily require coloring such as a photospacer, a protective layer, and an orientation control rib.

Examples of the substrate used in the color filter include glass substrates such as white plate glass, blue plate glass, alkali tempered glass, and silica-coated blue plate glass; ring-opened polymers of polyester, polycarbonate, polyolefin, polysulfone, cyclic olefin, and hydrogen thereof. Sheet, film or substrate made of thermoplastic resin such as additive; sheet, film or substrate made of thermosetting resin such as epoxy resin or unsaturated polyester resin; metal substrate such as aluminum plate, copper plate, nickel plate, stainless steel plate A ceramic substrate; a semiconductor substrate having a photoelectric conversion element; a member made of various materials such as a glass substrate (for example, a color filter for LCD) having a color material layer on the surface; Among these, from the viewpoint of heat resistance, a glass substrate or a sheet, film or substrate made of a heat resistant resin is preferable. The substrate is preferably a transparent substrate. The substrate may be subjected to chemical treatment with a corona discharge treatment, an ozone treatment, a silane coupling agent, or the like, if necessary.

In order to obtain the color filter, for example, for each pixel color (that is, for each pixel of one color), a step of placing the resin composition on the substrate (also referred to as a placement step), and a placement on the substrate Adopting a method that includes a step of irradiating the resin composition with light (also referred to as a light irradiation step), a step of developing with a developer (also referred to as a development step), and a step of heating treatment (also referred to as a heating step). It is preferable to adopt a manufacturing method in which the same method is repeated for each color. Note that the order of forming the pixels of each color is not particularly limited.

The preferable form of each said process is as Unexamined-Japanese-Patent No. 2006-29151 [0125]-[0137]. In the development step, an ether solvent, an alcohol solvent or an alkaline aqueous solution is preferably used as the developer, and the alkaline aqueous solution preferably contains an inorganic alkaline agent or amine as an alkaline agent. When an alkaline aqueous solution is used, it is preferable to wash with water after development.

5. Display device member or display device The present invention is also a display device member or display device including the color filter.
The cured product (cured film) formed by the resin composition is excellent in solvent resistance and heat resistance, and has high transmittance, so it is particularly suitable as a transparent member, and in various display devices. It is also useful as a protective film or insulating film.

As the display device, for example, a liquid crystal display device, a solid-state imaging device, a touch panel display device, and the like are suitable.
In addition, when using the said hardened | cured material (cured film) as a member for display apparatuses, the said member may be a film-form single layer or multilayer member comprised from the said cured film, or this single layer or multilayer It may be a member in which another layer is further combined with the above member, or may be a member including the above-mentioned cured film in its constitution.

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

1. Polymer physical properties 1) Weight average molecular weight (Mw)
Weight average molecular weight was measured by GPC (gel permeation chromatography) method using HLC-8220GPC (manufactured by Tosoh Corporation) and column: TSKgel SuperHZM-M (manufactured by Tosoh Corporation) using polystyrene as a standard substance and tetrahydrofuran as an eluent.

2) Acid value (AV)
3 g of the resin solution is precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and an automatic titration apparatus (manufactured by Hiranuma Sangyo Co., Ltd., trade name: COM-555) using a 0.1 N aqueous KOH solution as a titrant. ), The acid value of the polymer solution was measured, and the acid value (AV) per gram of the solid content was determined from the acid value of the solution and the solid content of the solution.

3) About 1 g of the solid polymer solution was weighed into an aluminum cup, dissolved by adding about 3 g of acetone, and then naturally dried at room temperature. Then, using a vacuum dryer (trade name: VOS-301SD type, manufactured by Tokyo Rika Kikai Co., Ltd.), it was dried at 120 ° C. under vacuum for 1.5 hours, then allowed to cool in a desiccator, and the mass was measured. From the mass reduction amount, the solid content (% by mass) of the polymer solution was calculated.

4) The double bond equivalent was calculated by dividing the solid content (g) of the double bond equivalent polymer solution by the amount (mol) of compound (X) (glycidyl methacrylate in the following synthesis examples).

5) Glass transition temperature (Tg)
The solid content obtained by applying the copolymer solution onto a glass substrate and removing the volatile components by drying at room temperature under reduced pressure for 4 hours is used for DSC (Differential Scanning Calorimeter; manufactured by BRUKER AXS, trade name : DSC3100S) under a nitrogen stream.

2. Solvent resistance (NMP dissolution test)
The resin composition was spin-coated on a 5 cm square glass substrate, dried at 90 ° C. for 3 minutes, exposed to 100 mJ with a high-pressure mercury lamp, and heat-treated at 230 ° C. for 30 minutes to obtain a thin film having a thickness of 5 μm. . Thereafter, the resultant was immersed in 20 g of 1-methyl-2-pyrrolidone (N-methylpyrrolidone; also referred to as “NMP”) at 55 ° C. for 5 minutes, and the hue of NMP eluted from the coating film was measured with a spectrophotometer UV3100 (manufactured by Shimadzu Corporation). The absorbance at 670 nm was determined.
NMP used for the evaluation of solvent resistance has high solubility and is used as a solvent for various substances mainly in the field of polymer chemistry.

3. A heat resistance test resin was spin-coated on a 5 cm square glass substrate, dried at 100 ° C. for 3 minutes, and then heat treated at 230 ° C. for 3 hours. After cooling to room temperature, the color index difference meter (“ZE-6000”, manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the yellow index (YI) value after the heat resistance test, and the degree of coloring was determined according to the following criteria. evaluated.
<Evaluation>
○: YI value is 5 or less Δ: YI value is 5-10
X: YI value is 10 or more

Synthesis Example 1 (Polymer A)
A separable flask equipped with a cooling tube was prepared as a reaction tank, and 10 parts of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate (hereinafter referred to as “MD”) was used as a monomer dropping tank. , 40 parts of methacrylic acid (hereinafter referred to as “MAA”), 48.5 parts of lauryl methacrylate (hereinafter referred to as “LMA”), 1.5 parts of methyl methacrylate (hereinafter referred to as “MMA”), t-butyl par 2 parts of oxy-2-ethylhexanoate (trade name “Perbutyl O”, manufactured by NOF Corporation, hereinafter referred to as “PBO”) and 29 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as “PGMEA”) were well mixed with stirring. As a chain transfer agent dropping tank, 5.5 parts of n-dodecanethiol (hereinafter referred to as “n-DM”) and 33 parts of PGMEA are well stirred. A mixture was prepared.
The reaction vessel was charged with 101 parts of PGMEA and purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. The dropwise addition was performed over 150 minutes each while maintaining the temperature at 90 ° C. Sixty minutes after the completion of dropping, the temperature was raised and the reaction vessel was brought to 110 ° C. Maintained 110 ° C. for 3 hours.
Once the internal temperature was cooled to room temperature, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas was started. Then, 41.3 parts of glycidyl methacrylate (hereinafter referred to as “GMA”), 0.05 part of 6-t-butyl-2,4-xylenol, and 0.4% of triethylamine (hereinafter referred to as “TEA”) are added to the reaction vessel. The portion was charged and allowed to react at 110 ° C. for 9 hours. Then, it cooled to room temperature and obtained the polymer solution A with a density | concentration of 44%. Table 1 shows the physical properties of the polymer A.

Synthesis Examples 2 to 10 (Polymers B to J)
Polymer solutions B to J were obtained in the same manner as in Synthesis example 1 except that the monomers (monomers) shown in Table 1 were used and the amount of GMA added was changed to the amount shown in Table 1. Table 1 shows the physical properties of each polymer.

Production Example 1 (Pigment Dispersion 1)
18.2 parts of PGMEA, 1.43 parts of DISPERBYK-2001 (manufactured by BYK Additives & Instruments) as a dispersant, 1 part of pigment (manufactured by Clariant, trade name “CI Pigment Violet 23”) as a colorant In addition, 4 parts of a dye (trade name “CI Solvent Blue 35” manufactured by MP Biomedicals, Inc.) was mixed and dispersed in a paint shaker for 3 hours to obtain Pigment Dispersion 1.

Example 1
2.0 parts of the polymer solution A obtained in Synthesis Example 1, 0.89 parts of dipentaerythritol hexaacrylate, 0.30 parts of Irgacure 907 (manufactured by BASF Japan), and the pigment dispersion obtained in Production Example 1 4.36 parts of 1 and 7.22 parts of PGMEA were mixed to obtain a resin composition (all solid amounts). This resin composition was subjected to the solvent resistance test described above. Table 2 shows the absorbance of the NMP solution from which the coloring material was eluted.

Examples 2-5, Comparative Examples 1-4
Each resin composition was prepared in the same manner as in Example 1 except that the polymer solutions B to I were used instead of the polymer solution A, respectively, and subjected to the above-described test. The results are shown in Table 2.

The symbols in Table 1 are as follows.
MD: Dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate BzMI: N-benzylmaleimide BzMA: benzyl methacrylate CHMA: cyclohexyl methacrylate 2-EHMA: 2-ethylhexyl methacrylate (Tg of homopolymer) : -10 ° C)
LMA: lauryl methacrylate (Tg of homopolymer: −65 ° C.)
nBMA: n-butyl methacrylate (Tg of homopolymer: 20 ° C.)
MMA: Methyl methacrylate MAA: Methacrylic acid GMA: Glycidyl methacrylate

The following items were confirmed from the results of Examples and Comparative Examples.
Polymers A to E obtained in Synthesis Examples 1 to 5 include the above structural units (A) and (B) and further include an acid group, and have a glass transition temperature of 60 ° C. or lower. This corresponds to the alkali-soluble resin of the present invention having a heavy bond equivalent of 200 to 2,000. On the other hand, the polymer F obtained in Synthesis Example 6 has a Tg higher than that of the present invention and does not contain the structural unit (B), and therefore the polymer G obtained in Synthesis Example 7 has a double bond equivalent of the present invention. The polymer H obtained in Synthesis Example 8 does not contain the structural unit (B) and does not have a double bond in the side chain. It differs from the polymers A to E in that the side chain does not have a double bond.

Under such a difference, when comparing the solvent resistance when used in combination with a coloring material, Examples 1 to 5 using the polymers A to E are used in comparison with Comparative Examples 1 to 4 using the polymers F to I. Then, it can be seen that the absorbance is extremely small (see Table 2). The greater the elution of the coloring material, the higher the absorbance of the eluate. Therefore, it can be determined that the absorbance is extremely small, that is, the solvent resistance is excellent. Therefore, it turned out that the alkali-soluble resin of this invention is excellent in solvent resistance.
The alkali-soluble resin of the present invention can sufficiently suppress elution even when a color material (pigment, dye) different from the color material used above is used.

Although not shown in the table or the like, when the resin composition obtained in Example 1 was subjected to the heat resistance test described above, it became “◯” and it was confirmed that the resin composition was excellent in heat resistance. On the other hand, when the resin composition obtained in the same manner as in Example 1 except that the polymer solution J was used instead of the polymer solution A was subjected to the heat resistance test described above, it was “x”. It was confirmed that there was a difference in heat resistance. Moreover, the hardened | cured material of the resin composition obtained in Examples 1-5 was excellent also in various physical properties, such as transparency, developability, and adhesiveness with a board | substrate.

Claims (10)

A polymer comprising a structural unit (A) represented by the following general formula (I) and a structural unit (B) represented by the following general formula (II), and further comprising an acid group,
The glass transition temperature is 60 ° C. or lower,
An alkali-soluble resin having a double bond equivalent of 200 to 2,000.

In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms. n represents the average number of repeating units of the structural unit represented by the general formula (I), and is a number of 1 or more.

In formula, R < ³ > is the same or different and represents a hydrogen atom or a methyl group. R ⁴ is the same or different and represents a linear or branched hydrocarbon group having 4 to 20 carbon atoms. m represents the average number of repeating units of the structural unit represented by the general formula (II), and is a number of 1 or more. The content of the structural unit (A) is 0.5 to 50% by mass with respect to 100% by mass of the total monomer units giving the main chain skeleton of the alkali-soluble resin, and the structural unit (B) The alkali-soluble resin according to claim 1, wherein the content is 10 to 90% by mass. A photosensitive resin composition comprising the alkali-soluble resin according to claim 1. The photosensitive resin composition according to claim 3, further comprising a colorant. The photosensitive resin composition according to claim 4, wherein the colorant is a pigment and / or a dye. Furthermore, the polymeric compound is included, The photosensitive resin composition in any one of Claims 3-5 characterized by the above-mentioned. It is used for a color filter, The photosensitive resin composition in any one of Claims 3-6 characterized by the above-mentioned. Hardened | cured material formed by hardening | curing the photosensitive resin composition in any one of Claims 3-7. A color filter comprising the cured product according to claim 8 on a substrate. A member for a display device or a display device comprising the color filter according to claim 9.