JP6886827B2 - Alkali-soluble resin, photosensitive resin composition and its uses - Google Patents

Description

The present invention relates to alkali-soluble resins, photosensitive resin compositions and their uses. More specifically, the present invention relates to an alkali-soluble resin, a photosensitive resin composition containing the same, and a cured product, as well as a display device member and a display device having the cured product.

Alkali-soluble resins are materials used in various fields from civil engineering and building materials to electronic information materials, and one of the main uses is an alkali-developed photosensitive resin composition. The photosensitive resin composition has a characteristic that the physical properties of the coating film 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 exhibits solubility. It is a composition. Utilizing these characteristics, various optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, etc. used for liquid crystal display devices, solid-state image sensors, etc., and electric / electronic devices, etc. Widely used in applications. Of these, for example, a color filter is generally composed of a substrate, pixels of at least three primary colors (red, green, blue), a resin black matrix that separates them, a protective film, and the like.

The photosensitive resin composition usually contains 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. When the photosensitive resin composition is used to form pixels of a color filter, for example, each pixel is formed by (1) a coating step of applying the photosensitive resin composition to a substrate and (2) a coating step. The resist film is pattern-exposed via a photomask to cure the exposed portion, and then the cured portion is insolubilized. (3) The unexposed portion is removed with a developing solution, and then the exposed portion is exposed by firing (baking). A method is adopted in which a development / firing process for further curing the portion is performed, and the same process is repeated for each color. As conventional photosensitive resin compositions, for example, the compositions described in Patent Documents 1 to 3 have been developed.

Japanese Unexamined Patent Publication No. 2014-210892 Japanese Unexamined Patent Publication No. 2011-145553 Japanese Unexamined Patent Publication No. 2012-032772

In a color filter, a compounding film such as a polyimide film is usually coated on a substrate in order to orient a liquid crystal, and the polyimide resin generally contains a highly polar solvent (for example, N-methylpyrrolidone). Therefore, the alkali-soluble resin and the photosensitive resin composition used for color filters and the like are required to have a cured portion (cured film) resistant to a solvent, that is, solvent resistance. Further, in recent years, in order to improve the display quality and the image quality of the liquid crystal display device, the image pickup tube element, etc., there is an increasing demand for high brightness and high contrast, and there is also a demand for thinning, so that the photosensitive property is photosensitive. There is a tendency to increase the concentration of the colorant in the resin composition. For the same reason, the miniaturization of the pixels constituting the color filter is also remarkable. However, as the concentration of the coloring material increases, there is a problem that the coloring material elutes into the cleaning solvent in the manufacturing process. Therefore, the alkali-soluble resin and the photosensitive resin composition are required to exhibit solvent resistance after curing. Be done.

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

The present invention has been made in view of the above situation, and it is possible to provide a cured product having excellent solvent resistance and heat resistance, and to provide an alkali-soluble resin which is particularly 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, and a color filter, a display device member, and a display device using the cured product.

The present inventor has various studies on an alkali-soluble resin, and has a structural unit containing a tetrahydropyran ring and a structural unit containing a long-chain linear or branched hydrocarbon group, and also contains an acid group. If the polymer has a structure in which the glass transition temperature (also referred to as Tg) and the double bond equivalent are within predetermined ranges, the heat resistance is extremely high and the solvent resistance is obtained when used in combination with a coloring material (coloring agent). It has been found that it provides a cured product that exhibits its properties and can sufficiently suppress the elution of the coloring material. In particular, the alkali-soluble resin is a low Tg resin having a long-chain linear or branched hydrocarbon group in the side chain, having a double bond in the side chain in a predetermined equivalent amount, and the hydrocarbon. It is considered that the three factors of the high density of the group and the side chain double bond greatly contribute to the effect of improving the solvent resistance, and further, having a tetrahydropyran ring structure in the main chain synergizes these. For the first time, it is considered that the effect is the realization of both solvent resistance and heat resistance. 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. The cured product, color filter, display device member, and display device obtained by using this photosensitive resin composition are considered to be able to sufficiently meet the demand for higher performance in recent years in the optical field and the electric / electronic field. We also found that it was extremely useful, and came up with the idea that the above problems could be solved brilliantly. In this way, the present invention was completed.

That is, the present invention is a polymer containing 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 containing an acid group. Therefore, it is an alkali-soluble resin having 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 represent the same or different hydrocarbon atoms or hydrocarbon groups having 1 to 25 carbon atoms. n represents the average number of repeating units of the structural units represented by the general formula (I), and is a number of 1 or more.

In the formula, R ³ represents a hydrogen atom or a methyl group, which is the same or different. R ⁴ may be the same or different, represent a linear or branched hydrocarbon group having 4 to 20 carbon atoms. m represents the average number of repeating units of the structural units 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, based on 100% by mass of the total amount of all the monomer units that provide 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 above 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, which is obtained by curing the photosensitive resin composition.
The present invention is also a color filter having the 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 provide a cured product having excellent 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 applications such as inks, printing plates, printed wiring boards, semiconductor elements, photoresists, and various optical members and electric / electronic devices in addition to color filters. be able to. Therefore, color filters, display device members, and display devices having a cured product (cured film) of such a photosensitive resin composition make a great contribution in various fields such as the optical field and the electric / electronic field. is there.

The present invention will be described in detail below. A form in which two or three or more of the individual 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 Tg is in this range, has a structural unit described later, and is an alkali-soluble resin having a double bond equivalent in a predetermined range, 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. The lower limit of Tg is not particularly limited, but from the viewpoint of heat resistance, it is preferably −30 ° C. or higher, for example. More preferably, it is -25 ° C or higher.
In the present specification, Tg can be obtained 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 thereof is 200 to 2000. When the double bond equivalent is within this range, the solvent resistance of the cured product is improved, and the 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. Further, it is preferably 1900 or less.
A polymer having no double bond in the 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. For compounds of the same molecular weight, the larger the value of double bond equivalent, the smaller the amount of double bond introduced.
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 polymer solid content by the double bond amount (mol) of the polymer (detailed determination). This method is described in Examples described later). It can also be measured using various analyses such as titration and elemental analysis, NMR and IR, and differential scanning calorimetry.

The alkali-soluble resin also preferably has an acid value of 20 to 300 mgKOH / g. As a result, the alkali solubility is further improved, and a cured product having better developability can be provided. In addition, the solvent resistance of the cured product is further improved, the developing speed is also moderated, the adhesion is 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, further 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 the present specification, the acid value can be determined by the method described in Examples described later.

The alkali-soluble resin preferably has a weight average molecular weight of 5,000 to 200,000. As a result, various performances such as solvent resistance, heat resistance, and developability are more exhibited. More preferably, it is 6000 or more, and it is preferable because the solvent resistance is particularly remarkably exhibited. It is more preferably 7,000 or more, still more preferably 8,000 or more, still more preferably 10,000 or more, particularly preferably 12,000 or more, and most preferably 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 the present specification, the weight average molecular weight can be determined by the method described in Examples described later.

As described above, the alkali-soluble resin has a double bond in the side chain, and has the structural unit represented by the general formula (I) (also referred to as the structural unit (A)) and the general formula (also referred to as the structural unit (A)) in the main chain. It is a polymer containing a structural unit represented by II) (also referred to as a structural unit (B)) and further containing an acid group.
Here, the acid group is introduced into the alkali-soluble resin by, for example, an alkali-soluble resin containing a structural unit (also referred to as a structural unit (C)) derived from the acid group-containing monomer (c). Is preferable. 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 the total amount of all the monomer units giving the main chain skeleton of the alkali-soluble resin. Is preferable. This improves heat resistance and storage stability. It is more preferably 1 to 40% by mass, still more preferably 5 to 30% by mass.
Note that n in the general formula (I) represents the average number of repeating units of the structural unit (A) in the alkali-soluble resin, but n so that the content ratio of the structural unit (A) is within the above-mentioned range. It is preferable to set.

The content ratio of the structural unit (B) is preferably 10 to 90% by mass with respect to 100% by mass of the total amount of all the monomer units giving the main chain skeleton of the alkali-soluble resin, for example. As a result, the solvent resistance is further improved. It is more preferably 20 to 80% by mass, still more preferably 30 to 75% by mass.
In addition, m in the said general formula (II) represents the average number of repeating units of the constituent unit (B) in an alkali-soluble resin, but m so that the content ratio of the constituent unit (B) is within the above-mentioned range. It is preferable to set.

The content ratio of the structural unit (C) is preferably 0.5 to 50% by mass with respect to 100% by mass of the total amount of all the monomer units giving the main chain skeleton of the alkali-soluble resin, for example. As a result, the solubility in the alkaline substance and the solubility in the solvent are improved, and the viscosity of the polymer is improved. It is more preferably 2 to 50% by mass, still more preferably 5 to 45% by mass.

The alkali-soluble resin is, for example, 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. A polymer (also referred to as a base polymer) obtained by polymerizing a monomer component containing (c) is reacted with a compound (X) having a functional group capable of binding to an acid group and a polymerizable double bond. It is preferable to obtain it. Each reaction raw material can be used alone or in combination of two or more.
Hereinafter, each monomer and compound (X) that give the base polymer will be further described.

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 the formula (I). When the monomer (a) is used in the polymerization reaction, it is presumed that the monomer (a) undergoes a cyclization reaction during the polymerization to form a tetrahydropyran ring structure in the structural unit of the polymer.

In the general formulas (I) and (i), R ¹ and R ² represent the same or different hydrogen atoms or hydrocarbon groups having 1 to 25 carbon atoms. Examples of the hydrocarbon group having 1 to 25 carbon atoms include a linear or branched alkyl group, aryl group, alicyclic group, and alkoxy substituted, as exemplified in JP2013-61599A. Alkyl groups substituted; alkyl groups substituted with aryl groups; and the like. Of these, hydrocarbon groups of primary or secondary carbon, such as methyl, ethyl, cyclohexyl, and benzyl, which are difficult to be desorbed by acid or heat, 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, and the like. Di (n-propyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n-) Butyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2 , 2'-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (stearyl) -2,2'- [Oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) -2,2'-[oxybis (methylene)] )] Bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] Bis-2-propenoate, di (1-ethoxyethyl) -2,2'-[oxybis (methylene)] )] Bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2, 2'-[oxybis (methylene)] bis-2-propenoate, di (t-butylcyclohexyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2 , 2'-[oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2' -[Oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2'-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2'-[ Oxybis (methylene)] Bis-2-propenoate and the like can be mentioned.

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 viewpoint of less coloring, dispersibility, and easy availability in the industry, dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate is more preferable.

The content ratio of the monomer (a) is preferably 0.5 to 50% by mass with respect to 100% by mass of the total amount of the monomer components giving the base polymer, for example. This improves dispersibility and storage stability. It is more preferably 1 to 40% by mass, still more preferably 5 to 30% by 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 the formula (II). The structural unit (B) is formed from the monomer (b).

In the general formula (II) and (ii), ^{R 3} are the same or different, represent a hydrogen atom or a methyl group. R ⁴ may be the same or different, represent 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 chain hydrocarbon group and that it has a relatively long chain having 4 to 20 carbon atoms. If the number of carbon atoms exceeds 20, there is a concern that 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 sufficiently exhibit solvent resistance. The hydrocarbon groups represented by above R ^4, linear or branched alkyl group is preferable. The number of carbon atoms is preferably 4 to 16, more preferably 4 to 12.
The hydrocarbon group may have a substituent, but it is preferable that the hydrocarbon group does not 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, and 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 thereof 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, an alkyl (meth) acrylate compound is preferable from the viewpoint of improving solvent resistance.

The content ratio of the monomer (b) is preferably 10 to 90% by mass with respect to 100% by mass of the total amount of the monomer components giving the base polymer, for example. As a result, the solvent resistance is further improved. It is more preferably 20 to 80% by mass, still more preferably 30 to 75% by 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 a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, and a sulfonic acid group. Among them, a carboxyl group or a carboxylic acid anhydride group is preferable, a carboxyl group is more preferable, and a (meth) acrylic acid group is more preferable.

Examples of the monomer (c) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, silicic acid, and vinyl benzoic acid; maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Unsaturated polycarboxylic acids such as monosuccinate (2-acryloyloxyethyl), monosuccinate (2-methacryloyloxyethyl) and other unsaturated groups in which the chain is extended between the unsaturated group and the carboxyl group. 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 Co., Ltd.); and the like. Among these, carboxylic acid-based monomers (unsaturated monocarboxylic acids, unsaturated polyvalent carboxylic acids, unsaturated acid anhydrides) are preferable from the viewpoint of versatility, availability, and the like. Unsaturated monocarboxylic acids are more preferable, and (meth) acrylic acid is more preferable in terms of reactivity, alkali solubility and the like.
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 above-mentioned preferable range. For example, it is preferably 0.5 to 50% by mass with respect to 100% by mass of the total amount of the monomer components giving the base polymer. As a result, the solubility in the alkaline substance and the solubility in the solvent are improved, and the viscosity of the polymer is improved. It is more preferably 2 to 50% by mass, still more preferably 5 to 45% by 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).

Wherein, R ⁵ are the same or different, represent a hydrogen atom or a methyl group. p represents the average number of repeating units of the structural units 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 other monomers (also referred to as monomer (d)) copolymerizable with the above-mentioned monomers (a), (b) and / or (c). May be contained alone or in combination of two or more. That is, the monomer component that gives the base polymer may further contain the monomer (d).

The monomer (d) is not particularly limited, and has, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and the like having 1 to 3 carbon atoms. Alkyl (meth) acrylate compounds; aromatic vinyl compounds such as styrene, vinyl toluene, α-methylstyrene; ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride, acrylonitrile; vinyl esters such as vinyl acetate; etc. Can be mentioned. Above all, it is preferable to use an alkyl (meth) acrylate compound having 1 to 3 carbon atoms because it has good transparency and does not easily impair solvent resistance and heat resistance.

The content ratio of the monomer (d) is not particularly limited, but for example, it is preferably 0 to 50% by mass with respect to 100% by mass of the total amount of the monomer components giving the base polymer. It is more preferably 0 to 25% by mass, still more preferably 0 to 10% by mass.

Here, in the present invention, from the viewpoint of improving solvent resistance, the smaller the content ratio of the ring structure present in the side chain, the more preferable. That is, specifically, it has a monomer (for example, 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 the monomer components that give the base polymer. The content ratio of (monomer, etc.) is preferably 5% by mass or less. It is more preferably 1% by mass or less, still more preferably 0.1% by mass or less.

As a method for polymerizing the above-mentioned monomer components, commonly used methods such as bulk polymerization, solution polymerization, and emulsion polymerization can be used, and may be appropriately selected depending on the purpose and application. Above all, solution polymerization is industrially advantageous, and structural adjustment such as molecular weight is easy, so that it is preferable. Further, as the polymerization mechanism of the above-mentioned monomer component, a polymerization method based on a mechanism such as radical polymerization, anion polymerization, cationic polymerization, or coordination polymerization can be used, but the polymerization method based on the radical polymerization mechanism is industrial. It is also preferable because it is advantageous for. Preferred forms of the polymerization reaction are as described in Japanese Patent Application Laid-Open No. 2016-29151 [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 metalyl group, and the like, and the compound has one or more of these. Is preferable. Of these, the (meth) acryloyl group is preferable in terms of reactivity. Examples of the functional group that can be bonded to the acid group include a hydroxy group, an epoxy group, an oxetanyl group, an isocyanate group, and the like, and a compound having one or more of these is preferable. Of these, an epoxy group (including a glycidyl group) is preferable from the viewpoint of speed of transformation 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. Acrylic acid (3,4-epoxycyclohexyl) methyl, vinylcyclohexene oxide and the like can be mentioned. Above all, it is preferable to use a compound (monomer) having an epoxy group and a (meth) acryloyl group. In particular, glycidyl (meth) acrylate and / or ( Methyl (meth) acrylic acid (3,4-epoxycyclohexyl) is more preferred.

The amount of the compound (X) added is not particularly limited as long as the double bond equivalent of the alkali-soluble resin is within the above range, but for example, 2 to 2 to 100 parts by mass of the total amount of the monomer components giving the base polymer. It is preferably 60 parts by mass. It is more preferably 10 to 55 parts by mass, further preferably 10 to 50 parts by mass, and particularly preferably 10 to 45 parts by mass.

The method for reacting the compound (X) with (a part of) the acid group in the base polymer is not particularly limited as long as a known addition method or the like is adopted. The reaction temperature is preferably, for example, 60 ° C to 140 ° C. Further, it is 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, or an amide compound such as dimethylformamide;

Since the alkali-soluble resin of the present invention can provide a cured product having excellent solvent resistance and heat resistance as well as curability and transparency, it can be used in various applications such as resist materials, various coating agents, and paints. It can be preferably used. Since it also has good developability, it is useful as an alkali-developable negative resist material for producing colored pixels of color filters, black matrices, overcoats, photo spacers, optical waveguides, and the like. Further, since it has good color material dispersibility, it is also useful for a color curable resin composition for a color filter. The alkali-soluble resin is particularly preferably used as a binder resin for a color resist, a resin for a solder resist, or the like, and the alkali-soluble resin is extremely useful as a main component of a photosensitive resin composition.

2. Photosensitive resin composition The photosensitive resin composition of the present invention (also simply referred to as “resin composition”) contains the above-mentioned alkali-soluble resin of the present invention. If necessary, other components may be further contained. As each contained component, one kind or two or more kinds can be used respectively.

In the present specification, the "total solid content of the photosensitive resin composition (resin composition)" refers to a component that forms a cured product (a solvent that volatilizes when the cured product is formed, etc.) among the components contained in the resin composition. (Excluding) means the total amount.

1) Alkali-soluble resin The alkali-soluble resin is as described above. An alkali-soluble resin other than the alkali-soluble resin of the present invention described above may be used in combination.
These alkali-soluble resins can act as binder resins in the photosensitive resin composition.

The content ratio of the alkali-soluble resin (the total amount when two or more kinds are contained) is not particularly limited, but is preferably 5 to 70% by mass with respect to 100% by mass of the total solid content of the resin composition, for example. It is more preferably 10 to 65% by mass, still more preferably 15 to 60% by mass.

2) Colorant (coloring material)
The resin composition preferably contains a colorant. This makes it more useful for color filter applications. The resin composition can exhibit particularly excellent solvent resistance when it contains a coloring material, and can sufficiently suppress the exudation of the 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 a dye. Such a form in which the colorant is a pigment and / or a dye is one of the preferred forms of the present invention. For example, when forming red, blue, and green pixels of a color filter, a method of demonstrating desired color characteristics by combining color materials such as blue and purple and green and yellow is preferably used to form a black matrix. Can be formed using a black coloring material.

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

Examples of the pigments include azo pigments, phthalocyanine pigments, and polycyclic pigments (for example, 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.), organic pigments such as dye lake type pigments; white / extender pigments (for example, titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), Yes Color pigments (eg yellow lead, cadmium, chrome vermillion, nickel titanium, chrome 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 (eg carbon black, bone black, graphite, iron black, titanium black, etc.), bright material pigments (eg pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments (eg zinc sulfide, strontium sulfide, strontium aluminate, etc.) Etc.) and other inorganic pigments. Examples of the 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-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc., depending on the purpose and application.

Specific examples of the above pigments include, for example, C.I. I. Pigment Yellow 1, 138 and other yellow pigments; C.I. I. Pigment Orange 1 and other orange pigments; C.I. I. Pigment Violet 1 etc. purple pigment; C.I. I. Pigment Red 1 and other red pigments; C.I. I. Blue pigments such as Pigment Blue 1; C.I. I. Pigment Green 1, 58 and other green pigments; C.I. I. Pigment Brown 5 and other brown pigments; aniline black, carbon black, lamp black, bone black, black iron, titanium black, C.I. I. Black pigments such as Pigment Black 1; C.I. I. Pigment White 1 and other white pigments; and the like. "CI" means a color index (CI; published by The Society of Dyers and Colorists), and the number means a color index number.

As the dye, for example, the organic dyes described in JP-A-2010-9033, JP-A-2010-21198, JP-A-2009-51896, and JP-A-2008-50599 can be used. it can. Among them, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine 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, with respect to 100% by mass of the total solid content of the photosensitive resin composition. It is preferably 3 to 70% by mass. It is more preferably 5 to 60% by mass, still more preferably 10 to 50% by mass.

3) Dispersant When the resin composition contains a coloring material (coloring agent), it is preferable to further contain a dispersant. The dispersant has a site of interaction with the coloring material and a site of interaction with the 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 weight dispersant), and a dye derivative. The resin composition preferably contains a dispersant together with a coloring material.

The resin type dispersant is not particularly limited, but for example, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkyl amines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydrogen group-containing polycarboxylic acid esters, amides formed by the reaction of poly (lower alkyleneimine) 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-based, modified polyacrylate, ethylene oxide / polypropylene oxide Additives and the like can be mentioned.

The structure of the resin-type dispersant includes 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. A resin in which the anchor chain and the compatible chain have a block structure is particularly preferably used.

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

The surfactant is not particularly limited, but for example, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate. , Anionic surfactants such as ammonium lauryl sulfate, sodium stearate, sodium lauryl sulfate; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate. Nonionic surfactants such as rates; Cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; Alkyl betaines such as alkyl dimethylamino acetate betaine, amphoteric surfactants such as alkyl imidazoline; etc. Can be mentioned.

The dye derivative is a compound having a structure in which a functional group is introduced into the dye, and 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. , A phthalimide group and the like. The maternal pigment structure includes, for example, azo, anthraquinone, quinophthalone, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrone, perylene, and diketopyrrolopyrrole. The system etc. can be mentioned.

The content ratio of the above dispersant (that is, resin type dispersant, surfactant and / or pigment derivative) may be appropriately set according to the purpose and application, but dispersion stability and durability (heat resistance, light resistance). , Weather resistance, etc.) 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. It is more preferably 0.1 to 50% by mass, still more preferably 0.3 to 40% by mass.

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

Examples of the monofunctional polymerizable monomer include N-substituted maleimide-based monomers; (meth) acrylic acid esters; (meth) acrylamides; unsaturated monocarboxylic acids; unsaturated polyvalent carboxylic acids; Unsaturated monocarboxylic acids with chain extensions between saturated and carboxyl groups; unsaturated acid anhydrides; aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; unsaturated Isocyanates; etc. Further, 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, and bisphenol F alkylene oxide di (meth) acrylate;

Trimethylolpropane tri (meth) acrylate, trimethylolpropane tetra (meth) acrylate, glycerin 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 trimethylolpropane tetra (meth) acrylate, ethylene oxide Addition pentaerythritol tetra (meth) acrylate, ethylene oxide-added dipentaerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (Meta) acrylate, propylene oxide-added dipentaerythritol hexa (meth) acrylate, ε-caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added dimethylolpropane tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra Trifunctional or higher functional (meth) acrylate compounds such as (meth) acrylate and ε-caprolactone-added dipentaerythritol 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, trimetyl propanetrivinyl ether, ditri Methylolpropan tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropanetrivinyl ether, ethylene oxide-added ditrimethylolpropanetetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide Polyfunctional vinyl ethers such as added dipentaerythritol hexavinyl ether;

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

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 Falkylene oxide diallyl ether, trimethylolpropantriallyl ether, Ditrimethylol propanetetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylol propanetriallyl ether, ethylene oxide-added ditrimethylol propanetetraallyl ether, Polyfunctional allyl ethers such as ethylene oxide-added pentaerythritol tetraallyl ether and ethylene oxide-added dipentaerythritol hexaallyl ether;

Allyl group-containing (meth) acrylic acid esters such as allyl (meth) acrylate; 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 urethane (meth) acrylates obtained by reacting the polyfunctional isocyanate of (meth) with hydroxyl group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; Polyfunctional aromatic vinyls such as divinylbenzene; etc.

Among the above-mentioned polymerizable compounds, it is preferable to use a polyfunctional polymerizable compound from the viewpoint of further enhancing 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 further 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 from the viewpoint of handling, for example, 2000 or less is preferable.

When a polyfunctional polymerizable compound is used as the polymerizable compound, among the polymerizable compounds, a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate are used from the viewpoints of reactivity, economy, availability and the like. 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, which makes the resin composition more excellent in photosensitivity and curability, and makes it possible to obtain a cured product having even higher hardness and high transparency. More preferably, a trifunctional or higher functional (meth) acrylate compound is used.

In the above resin composition, the content ratio of the polymerizable compound may be appropriately set according to the type of the polymerizable compound and the alkali-soluble resin to be used, as well as the purpose and application, but from the viewpoint of being superior in developability and plate-making property. The total solid content of the resin composition is preferably 2 to 80% by mass with respect to 100% by mass. It is more preferably 5 to 70% by mass, further preferably 8 to 60% by mass, particularly preferably 10 to 50% by mass, and most preferably 10 to 40% by mass.

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

The radically polymerizable photoinitiator 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. Further, if necessary, one or more photosensitizers, photoradical polymerization accelerators and the like may be used in combination. A photosensitizer and / or a photoradical polymerization accelerator may or may not be used together with the photopolymerization initiator. The effects of the present invention can be sufficiently exhibited without the combined use of a photosensitizer and / or a photoradical polymerization accelerator, but when used in combination, the 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-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4- (2) -Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl}- 2-Methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Alkylphenone compounds such as butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; benzophenone, 4, Benzophenone compounds such as 4'-bis (dimethylamino) benzophenone and 2-carboxybenzophenone; benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; thioxanthone, 2-ethylthioxanthone, 2- Thioxanthone compounds such as 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) Halomethylated triazine compounds such as −ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-ethoxycarbokynylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine 2-Trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5-[β- (2'-benzofuryl) vinyl] -1,3,4- Halomethylated oxaziazole compounds such as oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; 4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1, Biimidazole compounds such as 2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Il] -, 1- (O-acetyloxime) and other oxime ester compounds; oxime ether compounds; bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3) -Titanosen compounds such as-(1H-pyrrole-1-yl) -phenyl) titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; aclysin compounds such as 9-phenylaclydin; etc.

Among the above photopolymerization initiators, it is preferable to use an alkylphenone-based compound, an oxime ester-based compound, and / or an oxime ether-based compound. Oxime ester compounds and oxime ether compounds are collectively referred to as "oxime compounds", but when oxime compounds are used, the curability of the resin composition is significantly improved, and the solvent resistance of the obtained cured product is improved. It will improve dramatically.

In the above resin composition, the content of the photopolymerization initiator may be appropriately set according to the purpose, application, etc. and is not particularly limited, but is based on 100 parts by mass of the total solid content of the resin composition excluding the photopolymerization initiator. , 0.1 part by mass or more is preferable. As a result, a cured product having better adhesion can be obtained. It is more preferably 0.5 parts by mass or more, further preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more. Further, in consideration of the influence of the decomposition product of the photopolymerization initiator and the balance with economic efficiency, the amount is preferably 30 parts by mass or less. It is more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less.

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

The photosensitizer and the photoradical polymerization accelerator may not be used as described above, but when they are used, the resin composition is used from the viewpoint of the balance between curability, influence of decomposition products and economic efficiency. It is preferably 0.001 to 20% by mass with respect to 100% by mass of the total solid content of the above. It is more preferably 0.01 to 15% by mass, still more preferably 0.05 to 10% by mass.

6) Solvent The resin composition preferably also contains a solvent. The solvent is preferably used as a diluent or the like. That is, specifically, it is suitably used for lowering the viscosity and improving the handleability; forming a coating film by drying; as a dispersion medium for a coloring material; and dissolving each component in the resin composition. Alternatively, it is a low-viscosity organic solvent or water that can be dispersed.

As the solvent, one or two types that are normally used can be used, and the solvent may be appropriately selected depending on the purpose and application and is not particularly limited. For example, monoalcohols; glycols; cyclic ethers; glycol monoethers; glycol ethers; glycol monoether esters; alkyl esters; ketones; aromatic hydrocarbons; aliphatic hydrocarbons; amides ; Water; etc. are preferable. Specific examples of these solvents include the compounds described in JP-A-2015-42697 [0042]. For example, as esters of glycol monoether, 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 Examples thereof include 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 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 contained in an amount of 10 to 90% by mass in the total amount of the resin composition of 100% by mass. More preferably, it is 20 to 80% by mass.

7) Other components The above resin composition further has, for example, a heat resistance improver; a leveling agent; a developing aid; inorganic fine particles such as silica fine particles; silane-based, aluminum, depending on the required properties of each application to which the resin composition is applied. Coupling agents such as based and titanium; thermosetting resins such as fillers, epoxy resins, phenol resins and polyvinylphenols; curing aids such as polyfunctional thiol compounds; plasticizers; polymerization inhibitors; ultraviolet absorbers; antioxidants Agents; matting agents; antifoaming agents; antistatic agents; slip agents; surface modifiers; rocking agents; rocking aids; quinonediazide compounds; polyhydric phenol compounds; cationically polymerizable compounds; acid generators; etc. Further may be included.

The method for producing the photosensitive resin composition of the present invention is not particularly limited, and for example, it can be prepared by mixing and dispersing the above-mentioned contained components using various mixers and dispersers. The mixing / dispersing step is not particularly limited, and it may be carried out by a usual method. Moreover, it may further include other steps which are usually performed. When the resin composition contains a coloring material, it is preferably produced through a process of dispersing the coloring material.

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

3. Cured product The photosensitive resin composition of the present invention provides a cured product having excellent solvent resistance, heat resistance, and photosensitivity. This cured product is also excellent in curability, developability, adhesion to a substrate, transparency, image forming property, surface smoothness, and the like. is there. A cured product obtained by curing such a resin composition is one of the present inventions.

The cured product (cured film) preferably has a film thickness (thickness) of 0.1 to 20 μm. As a result, it is possible to sufficiently meet the demand for lowering the height of members, display devices, and the like using the cured product. It is more preferably 0.5 to 10 μm, still more preferably 0.5 to 8 μm.

The cured product is used for various optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, etc. used for liquid crystal display devices, solid-state image sensors, etc., and for electric / electronic devices, etc. It is preferably used for. Above all, it is preferable to use it as a color filter. A color filter using the resin composition as described above, that is, specifically, a color filter having the cured product on a substrate is also one of the present inventions.
The color filter will be further described below.

4. Color filter The color filter of the present invention has a form in which the cured product is contained on a substrate.
In the above color filter, the cured product formed by the photosensitive resin composition of the present invention is particularly suitable as a black matrix or a segment requiring coloring such as each pixel of red, green, blue, yellow, etc. However, it is also suitable as a segment such as a photo spacer, a protective layer, and an orientation control rib that does not necessarily require coloring.

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

To obtain the color filter, for example, a step of arranging the resin composition on a substrate (also referred to as an arranging step) for each pixel color (that is, for each pixel of one color) and a step of arranging the resin composition on the substrate are performed. A method including a step of irradiating the resin composition with light (also referred to as a light irradiation step), a step of developing with a developing solution (also referred to as a developing step), and a step of heat treatment (also referred to as a heating step) is adopted. , It is preferable to adopt a manufacturing method in which the same method is repeated for each color. The order of forming the pixels of each color is not particularly limited.

Preferred forms of each of the above steps are as described in Japanese Patent Application Laid-Open No. 2016-29151 [0125] to [0137]. In the development step, it is preferable to use an ether solvent, an alcohol solvent or an alkaline aqueous solution as a developing solution, and the alkaline aqueous solution preferably contains an inorganic alkaline agent or amines as an alkaline agent. When an alkaline aqueous solution is used, it is preferable to wash it with water after development.

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

As the display device, for example, a liquid crystal display device, a solid-state image sensor, a touch panel type display device, or the like is suitable.
When the cured product (cured film) is used as a display device member, the member may be a film-like single-layer or multilayer member composed of the cured film, or the single-layer or multilayer member. It may be a member in which another layer is further combined with the member of the above, or it may be a member including the cured film in the composition.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass". Various physical properties were measured as follows.

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

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 titrator (manufactured by Hiranuma Sangyo Co., Ltd., trade name: COM-555) using a 0.1N KOH aqueous solution as a titrator. ), The acid value of the polymer solution was measured, and the acid value (AV) per 1 g 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 in an aluminum cup, about 3 g of acetone was added to dissolve the solution, and then the solution was naturally dried at room temperature. Then, using a vacuum dryer (manufactured by Tokyo Rika Kikai Co., Ltd., trade name: VOS-301SD type), the product was dried under vacuum at 120 ° C. for 1.5 hours, then allowed to cool in a desiccator, and the mass was measured. The solid content (mass%) of the polymer solution was calculated from the amount of mass reduction.

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

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

2. Solvent resistance (NMP elution test)
The resin composition was spin-coated on a 5 cm square glass substrate, dried at 90 ° C. for 3 minutes, exposed at 100 mJ with a high-pressure mercury lamp, and heat-treated at 230 ° C. for 30 minutes to obtain a thin film having a film thickness of 5 μm. .. Then, it 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 by the spectrophotometer UV3100 (manufactured by Shimadzu Corporation). The absorbance at 670 nm was determined.
Since NMP used for the evaluation of solvent resistance has high solubility, it is used as a solvent for various substances mainly in the field of polymer chemistry.

3. The 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, measure the yellow index (YI) value after the heat resistance test using a color measurement color difference meter ("ZE-6000", manufactured by Nippon Denshoku Kogyo Co., Ltd.), and determine the degree of coloring according to the following criteria. evaluated.
<Evaluation>
◯: YI value is 5 or less Δ: YI value is 5 to 10
X: YI value is 10 or more

Synthesis Example 1 (Polymer A)
A separable flask with a cooling tube was prepared as a reaction tank, while 10 parts of dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate (hereinafter referred to as "MD") was prepared 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-butylper. Two parts of oxy-2-ethylhexanoate (trade name "Perbutyl O", manufactured by Nippon Yushi, hereinafter referred to as "PBO") and 29 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") were thoroughly stirred and mixed. As a chain transfer agent dropping tank, 5.5 parts of n-dodecanethiol (hereinafter referred to as "n-DM") and 33 parts of PGMEA were well stirred and mixed.
101 parts of PGMEA was 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 tank became stable at 90 ° C., dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was carried out over 150 minutes while keeping the temperature at 90 ° C. The temperature was raised to 110 ° C. 60 minutes after the dropping was completed. The temperature was maintained at 110 ° C. for 3 hours.
After the internal temperature was once cooled to room temperature, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 5/95 (v / v) mixed gas was started. Next, in the reaction vessel, 41.3 parts of glycidyl methacrylate (hereinafter referred to as "GMA"), 0.05 part of 6-t-butyl-2,4-xylenol, and 0.4 parts of triethylamine (hereinafter referred to as "TEA"). The parts were charged and reacted at 110 ° C. for 9 hours. Then, the mixture was cooled to room temperature to obtain a polymer solution A having a concentration of 44%. The physical characteristics of the polymer A are shown in Table 1.

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 shown in Table 1 were used and the amount of GMA added was the amount shown in Table 1. The physical characteristics of each polymer are shown in Table 1.

Production Example 1 (Pigment Dispersion 1)
18.2 parts of PGMEA, 1.43 parts of DISPERBYK-2001 (manufactured by BYK Adaptives & Instruments) as a dispersant, 1 part of pigment (manufactured by Clariant, trade name "CI Pigment Violet 23") as a coloring material, A pigment dispersion 1 was obtained by mixing 4 parts of a dye (manufactured by MP Biomnicals, trade name "CI Solvent Blue 35") and dispersing it with a paint shaker for 3 hours.

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 Ltd.), 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 are solid contents). This resin composition was subjected to the above-mentioned solvent resistance test. Table 2 shows the absorbance of the NMP solution in 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, and subjected to the above-mentioned 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 (homopolymer Tg) : -10 ° C)
LMA: Lauryl Methacrylate (Homopolymer Tg: -65 ° C)
nBMA: n-butyl methacrylate (Tg of homopolymer: 20 ° C)
MMA: Methyl Methacrylate MAA: GMA Methacrylate: Glycidyl Methacrylate

From the results of Examples and Comparative Examples, the following items were confirmed.
The polymers A to E obtained in Synthesis Examples 1 to 5 are polymers containing the above-mentioned structural units (A) and (B) and further containing an acid group, and have a glass transition temperature of 60 ° C. or lower. It corresponds to the alkali-soluble resin of the present invention having a double bond equivalent of 200 to 2000. On the other hand, the polymer F obtained in Synthesis Example 6 has a higher Tg than the present invention and does not contain the structural unit (B), and the polymer G obtained in Synthesis Example 7 has a double bond equivalent of the present invention. In that 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, the polymer I obtained in Synthesis Example 9 is larger than the above. It differs from polymers A to E in that it does not have a double bond in the side chain.

Under such a difference, when the solvent resistance when used in combination with the coloring material is compared, Examples 1 to 5 using the polymers A to E are compared 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 larger the elution of the coloring material, the higher the absorbance of the eluate. Therefore, it can be judged that the remarkably small absorbance means that the solvent resistance is excellent. Therefore, it was found that the alkali-soluble resin of the present invention has excellent solvent resistance.
The alkali-soluble resin of the present invention can sufficiently suppress elution even when a coloring material (pigment, dye) different from the coloring 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 above-mentioned heat resistance test, the result was "◯", confirming 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 above-mentioned heat resistance test, the result was "x". It was confirmed that there was a difference in heat resistance. Further, the cured products of the resin compositions obtained in Examples 1 to 5 were also excellent in various physical properties such as transparency, developability, and adhesion to the substrate.

Claims (11)

A polymer containing 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 containing an acid group.
The glass transition temperature is 60 ° C or less,
An alkali-soluble resin having a double bond equivalent of 200 to 2000.

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

In the formula, R ³ represents a hydrogen atom or a methyl group, which is the same or different. R ⁴ may be the same or different, represent a linear or branched hydrocarbon group having 8 to 20 carbon atoms. m represents the average number of repeating units of the structural units represented by the general formula (II), and is a number of 1 or more. The content ratio of the structural unit (A) is 0.5 to 50% by mass with respect to 100% by mass of the total amount of all the monomer units giving the main chain skeleton of the alkali-soluble resin, and the content of the structural unit (A) is 0.5 to 50% by mass. The alkali-soluble resin according to claim 1, wherein the content ratio is 10 to 90% by mass. The alkali-soluble resin according to claim 1 or 2, wherein the weight average molecular weight is 12800 or more. A photosensitive resin composition comprising the alkali-soluble resin according to any one of claims 1 to 3. The photosensitive resin composition according to claim 4 , further comprising a colorant. The photosensitive resin composition according to claim 5 , wherein the colorant is a pigment and / or a dye. The photosensitive resin composition according to any one of claims 4 to 6 , further comprising a polymerizable compound. The photosensitive resin composition according to any one of claims 4 to 7 , wherein the photosensitive resin composition is used for a color filter. A cured product obtained by curing the photosensitive resin composition according to any one of claims 4 to 8. A color filter comprising the cured product according to claim 9 on a substrate. A display device member or display device comprising the color filter according to claim 10.