Alkali-soluble resin, hydrogenated compound and method for producing the same, resin composition and cured film thereof, touch panel and optical filter

Abstract

The present invention relates to an alkali-soluble resin, a hydrogenated compound and a method for producing the same, a resin composition and a cured film thereof, a touch panel and an optical filter. Specifically, the present invention relates to a method for producing an alkali-soluble resin containing a polymerizable unsaturated group, which can obtain a photosensitive resin composition having a low refractive index and excellent light-resistant development characteristics. The solution to the problem of the present invention is a method for producing an alkali-soluble resin containing a polymerizable unsaturated group, which comprises: reacting a reactant of an epoxy compound (a) having a structure represented by the general formula (1) and a monocarboxylic acid containing an unsaturated group with a dicarboxylic acid or a tricarboxylic acid or a monoanhydride thereof (b), and a tetracarboxylic acid or a dianhydride thereof (c).

Description

Technical Field

[0001] The present invention relates to a method for producing an alkali-soluble resin containing a polymerizable unsaturated group, an alkali-soluble resin containing a polymerizable unsaturated group, a hydrogenated compound and a method for producing the same, a photosensitive resin composition, a cured film formed by curing the photosensitive resin composition, and a touch panel and a color filter containing the cured film as a constituent component. Background Art

[0002] In recent years, due to the development of portable terminals, the number of display devices such as touch panels and liquid crystal panels used outdoors or in vehicles has increased. In the above display devices, a light shielding film is provided on the outer frame of the touch panel to shield the light leakage around the rear liquid crystal panel, and a black matrix is ​​provided to suppress the light leakage from the screen when the above liquid crystal panel displays black and to suppress the mixing of adjacent color resists.

[0003] In display devices, etc., there are situations in which the concentration of black pigment in the light-shielding film is increased and the light-shielding property of the light-shielding film is increased (the light transmittance of the light-shielding film is reduced) in order to suppress light leakage and improve the visual confirmation of the screen of the above-mentioned display device, etc. Compared with the refractive index of the transparent substrate and the curable resin, the refractive index of the black pigment is higher, so if the concentration of the black pigment in the light-shielding film is increased, the reflectivity will increase when viewed from the surface formed by the light-shielding film of the transparent substrate and the opposite side of the surface formed by the light-shielding film. Therefore, the reflection of the interface between the light-shielding film formed on the transparent substrate and the transparent substrate will increase, resulting in the reflection on the light-shielding film, or the difference in reflectivity from the color filter coloring part, which makes the boundary of the black matrix conspicuous. In addition, the refractive index of the resin used for the photoresist for forming the black matrix of high image quality is high. Therefore, it is difficult to take into account both light-shielding property and low reflectivity by adjusting the concentration of black pigment alone.

[0004] Therefore, a photosensitive resin composition for black resist having a low refractive index is required.

[0005] For example, Patent Document 1 discloses a resin film, which contains at least two or more resins, a colorant, and a photoacid generator. In the light scattering measurement of the resin film, in a spectrum plotted with the horizontal axis being the scattering angle and the vertical axis being the scattered light intensity, when the half-value width of the spectrum peak is set to A1 and the scattering angle of the maximum light intensity of the spectrum peak is set to A2, there is a spectrum peak with a value of A1 / A2 exceeding 0.1 and not more than 2.5. The resin film can form a phase separation structure by two or more resins, so it is excellent in low reflectivity.

[0006] [Prior art literature]

[0007] [Patent Document]

[0008] Patent document 1: International Publication No. 2017 / 057192. Summary of the invention

[0009] [Problems to be solved by the invention]

[0010] However, the inventors of the present invention have found through review that the resin film described in Patent Document 1 can reduce the reflectivity, but may have a poor appearance due to the influence of surface irregularities, such as reduced surface smoothness or increased diffuse reflection. Therefore, there is an increasing demand for a photosensitive resin composition that can reduce the refractive index of the resin itself and achieve the required reflectivity, and has the required development characteristics when used in a photosensitive resin composition, or has heat resistance, adhesion and other characteristics when used as a cured film.

[0011] The present invention is studied in view of the above points, and the first purpose is to provide a method for producing an alkali-soluble resin containing a polymerizable unsaturated group, and an alkali-soluble resin containing a polymerizable unsaturated group, wherein the aforementioned production method can obtain a photosensitive resin composition having a low refractive index and excellent light-resistant development characteristics. In addition, the second purpose is to provide a hydrogenated compound and a method for producing the hydrogenated compound. In addition, the third purpose is to provide an alkali-soluble resin containing a polymerizable unsaturated group, a photosensitive resin composition containing the resin, and a cured film formed by curing the photosensitive resin composition, and a touch panel and a color filter containing the cured film as a constituent component.

[0012] [Methods to solve the problem]

[0013] The method for producing the alkali-soluble resin containing a polymerizable unsaturated group of the present invention:

[0014] A reaction product of an epoxy compound (a) having a structure represented by the following general formula (1) and a monocarboxylic acid containing an unsaturated group is reacted with a dicarboxylic acid or tricarboxylic acid or a monoanhydride of a dicarboxylic acid or tricarboxylic acid (b), and a tetracarboxylic acid or a dianhydride thereof (c).

[0015]

[0016] (In formula (1), R1 independently represents a hydrocarbon group having 2 to 4 carbon atoms, R2 independently represents a hydrocarbon group having 1 to 3 carbon atoms, X represents a divalent organic group having 1 to 20 carbon atoms which may contain a heteroelement, -CO-, -SO2-, -Si(CH3)2-, -O-, or a single bond, a represents a number having an average value of 0 to 10, and b represents a number having an average value of 0 to 4.)

[0017] The polymerizable unsaturated group-containing alkali-soluble resin of the present invention has a structure represented by the following general formula (2).

[0018]

[0019] (In formula (2), R1 independently represents a hydrocarbon group having 2 to 4 carbon atoms, R2 independently represents a hydrocarbon group having 1 to 3 carbon atoms, R3 represents a hydrogen atom or a methyl group, X represents a divalent organic group having 1 to 20 carbon atoms which may contain a heteroelement, -CO-, -SO2-, -Si(CH3)2-, -O-, or a single bond, Y represents a tetravalent carboxylic acid residue, Z represents a hydrogen atom or a substituent represented by general formula (3), but at least one of Z represents a substituent represented by general formula (3), G represents a hydrogen atom or a substituent represented by general formula (4), a independently represents a number having an average value of 0 to 10, b independently represents a number having an average value of 0 to 4, and n represents a number having an average value of 1 to 20.)

[0020]

[0021] (In formula (3) and (4), R4 represents a hydrogen atom or a methyl group, R5 independently represents a hydrocarbon group having 2 to 4 carbon atoms, L represents a divalent or trivalent carboxylic acid residue, c represents a number of 0 or 1, d and e represent a number of 0, 1 or 2, and d+e represents a number of 1 or 2.)

[0022] The hydrogenated compound of the present invention has a structure represented by the following general formula (5).

[0023]

[0024] (In formula (5), R 12 independently represent a hydrocarbon group having 2 to 4 carbon atoms, R 13 independently represent a hydrocarbon group having 1 to 3 carbon atoms, R 14 represents a glycidyl group or the following general formula (6), but R 14 At least one of them represents an epoxypropyl group, a independently represents a number with an average value of 0 to 10, b independently represents a number with an average value of 0 to 4, n represents a number with an average value of 0 to 10, A1 and A2 independently represent the following general formula (7) or general formula (8), A3 and A4 independently represent the following general formula (9) or general formula (10), and the presence rate of the general formula (8) and general formula (10) is 1 mol% or more and 100 mol% or less relative to the total of A1, A2, A3 and A4.)

[0025]

[0026] (In formula (9), * indicates the bonding position of the five-membered ring.)

[0027]

[0028] (In formula (10), * indicates the bonding position of the five-membered ring.)

[0029] The diol or polyol of the present invention has a structure represented by the following general formula (11).

[0030]

[0031] (In formula (11), R 12 independently represent a hydrocarbon group having 2 to 4 carbon atoms, R 13 independently represent a hydrocarbon group having 1 to 3 carbon atoms, R 15 represents a hydrogen atom or a methyl group, a independently represents a number with an average value of 0 to 10, b independently represents a number with an average value of 0 to 4, n represents a number with an average value of 0 to 10, A1 and A2 independently represent the following general formula (7) or general formula (8), A3 and A4 independently represent the following general formula (9) or general formula (10), and the presence ratio of the above general formula (8) and general formula (10) is 1 mol% or more and 100 mol% or less relative to the total of A1, A2, A3 and A4.)

[0032]

[0033] (In formula (9), * indicates the bonding position of the five-membered ring.)

[0034]

[0035] (In formula (10), * indicates the bonding position of the five-membered ring.)

[0036] The polymerizable unsaturated group-containing alkali-soluble resin of the present invention has a structure represented by the following general formula (12).

[0037]

[0038] (In formula (12), R 12 R1 independently represents a hydrocarbon group having 2 to 4 carbon atoms, R7 independently represents a hydrocarbon group having 1 to 3 carbon atoms, R 15 represents a hydrogen atom or a methyl group, R 16 represents a monovalent group obtained by reacting a glycidyl group with (meth)acrylic acid or a monovalent group formed by adding anhydride to the monovalent group, A1 and A2 independently represent the following general formula (7) or general formula (8), A3 and A4 independently represent the following general formula (9) or general formula (10), the presence rate of the above general formula (8) and general formula (10) relative to the total of A1, A2, A3 and A4 is 1 mol% or more and 100 mol% or less, Y represents a tetravalent carboxylic acid residue, G represents a hydrogen atom or a substituent represented by general formula (13), a independently represents a number with an average value of 0 to 10, b independently represents a number with an average value of 0 to 4, and m represents a number with an average value of 0 to 10.)

[0039]

[0040] (In formula (9), * indicates the bonding position of the five-membered ring.)

[0041]

[0042] (In formula (10), * indicates the bonding position of the five-membered ring.)

[0043]

[0044] (In formula (13), R 17 represents a hydrogen atom or a methyl group, R 18 independently represents a hydrocarbon group having 2 to 4 carbon atoms, and c represents a number of 0 or 1. )

[0045] The method for producing a hydrogenated compound of the present invention comprises: (i) preparing a compound represented by the following general formula (14), and (ii) hydrogenating a phenylene group or a fluorenyl group of the compound.

[0046]

[0047] (In formula (14), R 12 independently represents a hydrocarbon group having 2 to 4 carbon atoms, a independently represents a number having an average value of 0 to 10, and n represents a number of 0 to 10. )

[0048] The photosensitive resin composition of the present invention comprises (A) a polymerizable unsaturated group-containing alkali-soluble resin represented by the general formula (2) or (A) a polymerizable unsaturated group-containing alkali-soluble resin represented by the general formula (12), and (B) a photopolymerization initiator.

[0049]

[0050] (In formula (2), R1 independently represents a hydrocarbon group having 2 to 4 carbon atoms, R2 independently represents a hydrocarbon group having 1 to 3 carbon atoms, R3 represents a hydrogen atom or a methyl group, X represents a divalent organic group having 1 to 20 carbon atoms which may contain a heteroelement, -CO-, -SO2-, -Si(CH3)2-, -O-, or a single bond, Y represents a tetravalent carboxylic acid residue, Z represents a hydrogen atom or a substituent represented by general formula (3), but at least one of Z represents a substituent represented by general formula (3), G represents a hydrogen atom or a substituent represented by general formula (4), a independently represents a number having an average value of 0 to 10, b independently represents a number having an average value of 0 to 4, and n represents a number having an average value of 1 to 20.)

[0051]

[0052] (In formula (3) and (4), R4 represents a hydrogen atom or a methyl group, R5 independently represents a hydrocarbon group having 2 to 4 carbon atoms, L represents a divalent or trivalent carboxylic acid residue, c represents a number of 0 or 1, d and e represent a number of 0, 1 or 2, and d+e represents a number of 1 or 2.)

[0053]

[0054] (In formula (12), R 12 independently represent a hydrocarbon group having 2 to 4 carbon atoms, R 13 independently represent a hydrocarbon group having 1 to 3 carbon atoms, R 15 represents a hydrogen atom or a methyl group, R 16 represents a monovalent group obtained by reacting a glycidyl group with (meth)acrylic acid or a monovalent group formed by adding anhydride to the monovalent group, A1 and A2 independently represent the following general formula (7) or general formula (8), A3 and A4 independently represent the following general formula (9) or general formula (10), the presence rate of the above general formula (8) and general formula (10) relative to the total of A1, A2, A3 and A4 is 1 mol% or more and 100 mol% or less, Y represents a tetravalent carboxylic acid residue, G represents a hydrogen atom or a substituent represented by general formula (13), a independently represents a number with an average value of 0 to 10, b independently represents a number with an average value of 0 to 4, and m represents a number with an average value of 0 to 10.)

[0055]

[0056] (In formula (9), * indicates the bonding position of the five-membered ring.)

[0057]

[0058] (In formula (10), * indicates the bonding position of the five-membered ring.)

[0059]

[0060] (In formula (13), R 17 represents a hydrogen atom or a methyl group, R 18 independently represents a hydrocarbon group having 2 to 4 carbon atoms, and c is 0 or 1. )

[0061] The cured film of the present invention is obtained by patterning the photosensitive resin composition by photolithography and curing the patterned photosensitive resin composition.

[0062] The touch panel of the present invention contains the above-mentioned cured film as a constituent component.

[0063] The color filter of the present invention contains the above-mentioned cured film as a constituent component.

[0064] [Effects of the invention]

[0065] According to the present invention, a method for producing an alkali-soluble resin containing a polymerizable unsaturated group and an alkali-soluble resin containing a polymerizable unsaturated group can be provided, and the aforementioned production method can obtain a photosensitive resin composition having a low refractive index and excellent light-resistant development characteristics. In addition, a hydrogenated compound and a method for producing the hydrogenated compound can be provided. In addition, an alkali-soluble resin containing a polymerizable unsaturated group, a photosensitive resin composition containing the alkali-soluble resin, a cured film formed by curing the photosensitive resin composition, and a touch panel and a color filter containing the cured film as a constituent component can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Figure 1 This is a graph showing the relationship between the refractive index and the number of aromatic rings of a cured film according to one embodiment of the present invention.

[0067] Figure 2 A graph showing the yellowing degree (ΔYI) of the cured film before and after exposure of the cured film according to one embodiment of the present invention.

[0068] Explanation of symbols

[0069] none. DETAILED DESCRIPTION

[0070] The embodiments of the present invention are described below, but the present invention is not limited to the following embodiments. In addition, in the present invention, when the content of each component is 0 at the first decimal place, the indication after the decimal point is omitted.

[0071] The alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule represented by the following general formula (2) of the present invention can be obtained by reacting a reaction product of an epoxy compound (a) having two epoxy groups in one molecule and a monocarboxylic acid containing an unsaturated group with a dicarboxylic acid or a tricarboxylic acid or a monoanhydride of a dicarboxylic acid or a tricarboxylic acid (b) and a tetracarboxylic acid or a dianhydride thereof (c). In addition, the above-mentioned alkali-soluble resin containing a polymerizable unsaturated group uses an epoxy compound (a-1) as a raw material epoxy compound, and the epoxy compound (a-1) has several oxyalkylene groups and two cycloalkyl groups in one molecule.

[0072]

[0073] (In formula (2), R1 independently represents a hydrocarbon group having 2 to 4 carbon atoms, R2 independently represents a hydrocarbon group having 1 to 3 carbon atoms, R3 represents a hydrogen atom or a methyl group, X represents a divalent organic group having 1 to 20 carbon atoms which may contain a heteroelement, -CO-, -SO2-, -Si(CH3)2-, -O-, or a single bond, Y represents a tetravalent carboxylic acid residue, Z represents a hydrogen atom or a substituent represented by general formula (3), but at least one of Z represents a substituent represented by general formula (3), G represents a hydrogen atom or a substituent represented by general formula (4), a independently represents a number having an average value of 0 to 10, b independently represents a number having an average value of 0 to 4, and n represents a number having an average value of 1 to 20.)

[0074]

[0075] (In formula (3) and (4), R4 represents a hydrogen atom or a methyl group, R5 independently represents a hydrocarbon group having 2 to 4 carbon atoms, L represents a divalent or trivalent carboxylic acid residue, c represents a number of 0 or 1, d and e represent a number of 0, 1 or 2, and d+e represents a number of 1 or 2.)

[0076] A method for producing the alkali-soluble resin represented by the general formula (2) having a carboxyl group and a polymerizable unsaturated group in one molecule (hereinafter referred to as "alkali-soluble resin represented by the general formula (2)") is described in detail.

[0077] First, an epoxy compound (a-1) having two cyclooxyalkyl groups in one molecule and represented by the following general formula (1) (hereinafter, also simply referred to as "epoxy compound (a-1) represented by general formula (1)") is reacted with a monocarboxylic acid containing an unsaturated group (e.g., (meth)acrylic acid) to obtain epoxy (meth)acrylate.

[0078]

[0079] (In formula (1), R1 independently represents a hydrocarbon group having 2 to 4 carbon atoms, R2 independently represents a hydrocarbon group having 1 to 3 carbon atoms, X represents a divalent organic group having 1 to 20 carbon atoms which may contain a heteroelement, -CO-, -SO2-, -Si(CH3)2-, -O-, or a single bond, a independently represents a number having an average value of 0 to 10, and b independently represents a number having an average value of 0 to 4.)

[0080] Examples of the unsaturated group-containing monocarboxylic acid compound include, in addition to acrylic acid and methacrylic acid, compounds obtained by reacting acrylic acid or methacrylic acid with a monoanhydride such as succinic anhydride, maleic anhydride, or phthalic anhydride.

[0081] The reaction of the epoxy compound (a-1) represented by the general formula (1) and (meth) acrylic acid can be carried out by a known method. For example, Japanese Patent Publication No. 4-355450 discloses that a diol compound containing a polymerizable unsaturated group can be obtained by using about 2 moles of (meth) acrylic acid for 1 mole of an epoxy compound having two epoxy groups. In the present invention, the compound obtained by the above reaction is a diol (d) represented by the general formula (16).

[0082]

[0083] (In formula (16), R1 independently represents a hydrocarbon group having 2 to 4 carbon atoms, R2 independently represents a hydrocarbon group having 1 to 3 carbon atoms, R3 represents a hydrogen atom or a methyl group, and X represents a divalent organic group having 1 to 20 carbon atoms which may contain a heteroelement, -CO-, -SO2-, -Si(CH3)2-, -O-, or a single bond. However, a independently represents a number having an average value of 0 to 10, and b independently represents a number having an average value of 0 to 4.)

[0084] X of the epoxy compound (a-1) represented by the general formula (1) represents a divalent organic group having 1 to 20 carbon atoms which may contain a heteroelement inside, -CO-, -SO2-, -Si(CH3)2-, -O-, or a single bond. Examples of the divalent organic group having 1 to 20 carbon atoms which may contain a heteroelement inside include a divalent hydrocarbon group, a divalent group having a carboxyl group at one or both ends of the hydrocarbon group, and the like. In addition, the above-mentioned hydrocarbon group may have an ether-bonded oxygen atom or an ester bond inside.

[0085] Examples of divalent hydrocarbon groups include methylene, vinyl, propylene, isopropylene, isopropylidene The invention also includes a hydrocarbon group having a straight chain or a branched chain, such as a butylene group, a sec-butylene group, a methylisobutylene group, a hexenyl group, a decenyl group, and a dodecenyl group. Examples of the divalent group having an ester group at the end of the hydrocarbon group include divalent organic groups represented by formulas (17) to (20).

[0086]

[0087] (In formula (17), g represents an integer from 1 to 20.)

[0088]

[0089] (In formula (18), h represents an integer from 2 to 20, and i represents an integer from 0 to 10.)

[0090]

[0091] (In formula (19), j represents an integer from 1 to 20.)

[0092]

[0093] (In formula (20), k represents an integer from 0 to 18, and l represents an integer from 1 to 10.)

[0094] The two cyclohexane rings in the general formula (1) are bonded via X. The cyclohexane rings are bonded to oxygen atoms at the 1-position and the 2-position, respectively, and are bonded to X at the 4-position or the 5-position. X may be bonded to either the 4-position or the 5-position, or may be randomly bonded to the 4-position and the 5-position.

[0095] Specific examples of the epoxy compound (a-1) represented by the general formula (1) include epoxy compounds represented by formulas (21) to (27).

[0096]

[0097] (In formula (21), R1 independently represents a hydrocarbon group having 2 to 4 carbon atoms, and a independently represents a number having an average value of 0 to 10.)

[0098]

[0099] (In formula (22), R1 independently represents a hydrocarbon group having 2 to 4 carbon atoms, and a independently represents a number having an average value of 0 to 10.)

[0100]

[0101] (In formula (23), R1 independently represents a hydrocarbon group having 2 to 4 carbon atoms, and a independently represents a number having an average value of 0 to 10.)

[0102]

[0103] (In formula (24), R1 independently represents a hydrocarbon group having 2 to 4 carbon atoms, a independently represents a number having an average value of 0 to 10, and g represents an integer of 1 to 20.)

[0104]

[0105] (In formula (25), R1 independently represents a hydrocarbon group having 2 to 4 carbon atoms, a independently represents a number having an average value of 0 to 10, h represents an integer of 2 to 20, and i represents an integer of 0 to 10.)

[0106]

[0107] (In formula (26), R1 independently represents a hydrocarbon group having 2 to 4 carbon atoms, a independently represents a number having an average value of 0 to 10, and j represents an integer of 1 to 20.)

[0108]

[0109] (In formula (27), R1 independently represents a hydrocarbon group having 2 to 4 carbon atoms, a independently represents a number having an average value of 0 to 10, k represents an integer of 0 to 18, and l represents an integer of 1 to 10.)

[0110] In the production of the alkali-soluble resin containing a polymerizable unsaturated group represented by the general formula (2), a reaction is usually carried out in a solvent with the optional use of a catalyst. The production of the alkali-soluble resin containing a polymerizable unsaturated group represented by the above-mentioned formula (2) is produced by synthesizing a diol (d) represented by the general formula (16), and then subjecting the synthesized polycarboxylic acid or the anhydride of the polycarboxylic acid to an addition reaction, and then reacting with a monofunctional epoxy compound containing a polymerizable unsaturated group reactive with a carboxyl group.

[0111] Examples of the solvent include cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate; high-boiling-point ether or ester solvents such as diethylene glycol dimethyl ether (diglyme), ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; ketone solvents such as cyclohexanone and diisobutyl ketone, etc. In addition, the reaction conditions of the solvent, catalyst, etc. used are not particularly limited, but for example, it is more preferable to use a solvent having no hydroxyl group and having a boiling point higher than the reaction temperature as the reaction solvent.

[0112] In the reaction between the carboxyl group and the epoxy group, it is more preferable to use a catalyst. Japanese Patent Application Laid-Open No. 9-325494 describes ammonium salts such as tetraethylammonium bromide and benzyltriethylammonium chloride, and phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine.

[0113] Next, the diol (d) represented by the general formula (16) obtained by the reaction of the epoxy compound with (meth)acrylic acid is reacted with the acid components (b) and (c) to obtain an alkali-soluble resin represented by the general formula (28) having a carboxyl group and a polymerizable unsaturated group in one molecule (hereinafter referred to as the "alkali-soluble resin represented by the general formula (28)").

[0114]

[0115] (In formula (28), R1 independently represents a hydrocarbon group having 2 to 4 carbon atoms, R2 independently represents a hydrocarbon group having 1 to 3 carbon atoms, R3 represents a hydrogen atom or a methyl group, X represents a divalent organic group having 1 to 20 carbon atoms which may contain a heteroelement inside, -CO-, -SO2-, -C(CF3)2, -Si(CH3)2-, -O- or a single bond, Y represents a tetravalent carboxylic acid residue, and Z' represents a hydrogen atom or a substituent represented by general formula (29). However, a independently represents a number having an average value of 0 to 10, b independently represents a number having an average value of 0 to 4, and n represents a number having an average value of 1 to 20.)

[0116]

[0117] (In formula (29), L represents a divalent or trivalent carboxylic acid residue, and r represents a number of 1 or 2.)

[0118] The acid component used to synthesize the alkali-soluble resin represented by the general formula (28) is a polyacid component that can react with the hydroxyl group in the molecule of the diol (d) represented by the general formula (16), and it is necessary to use a dicarboxylic acid or a tricarboxylic acid or a monoanhydride (b) of a dicarboxylic acid or a tricarboxylic acid, and a tetracarboxylic acid or a dianhydride (c) thereof. The carboxylic acid residue of the above-mentioned acid component may be any of a saturated hydrocarbon group or an unsaturated hydrocarbon group. In addition, these carboxylic acid residues may include bonds containing heteroelements such as -O-, -S-, and a carbonyl group.

[0119] As the dicarboxylic acid or tricarboxylic acid or the monoanhydride of dicarboxylic acid or tricarboxylic acid (b), chain hydrocarbon dicarboxylic acid or tricarboxylic acid, alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid, or the monoanhydride of dicarboxylic acid or tricarboxylic acid can be used.

[0120] Examples of monoanhydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids include monoanhydrides such as succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid; and monoanhydrides of dicarboxylic acids or tricarboxylic acids introduced with any substituent, etc. In addition, examples of monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids include monoanhydrides such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and norbornanedicarboxylic acid; and monoanhydrides of dicarboxylic acids or tricarboxylic acids introduced with any substituent, etc. In addition, examples of monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids include monoanhydrides such as phthalic acid, isophthalic acid, trimellitic acid, and monoanhydrides of dicarboxylic acids or tricarboxylic acids introduced with any substituent, etc.

[0121] Among the monoanhydrides of dicarboxylic acids or tricarboxylic acids, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid are more preferred, and succinic acid, itaconic acid, and tetrahydrophthalic acid are more preferred. In addition, among the dicarboxylic acids or tricarboxylic acids, it is more preferred to use the monoanhydrides of dicarboxylic acids or tricarboxylic acids. The monoanhydrides of the above-mentioned dicarboxylic acids or tricarboxylic acids may be used alone or in combination of two or more.

[0122] Moreover, as the tetracarboxylic acid or its dianhydride (c), a chain hydrocarbon tetracarboxylic acid, an alicyclic hydrocarbon tetracarboxylic acid, an aromatic hydrocarbon tetracarboxylic acid, or a dianhydride of these tetracarboxylic acids can be used.

[0123] Examples of chain hydrocarbon tetracarboxylic acids include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and chain hydrocarbon tetracarboxylic acids into which substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups are introduced. In addition, examples of the above-mentioned alicyclic tetracarboxylic acids include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, and alicyclic tetracarboxylic acids into which substituents such as chain hydrocarbon groups and unsaturated hydrocarbon groups are introduced. In addition, examples of aromatic tetracarboxylic acids include pyromelitic acid, diphenyl ketone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, etc.

[0124] Among the tetracarboxylic acids or their dianhydrides, biphenyl tetracarboxylic acid, diphenyl ketone tetracarboxylic acid, and diphenyl ether tetracarboxylic acid are more preferred, and biphenyl tetracarboxylic acid and diphenyl ether tetracarboxylic acid are more preferred. In addition, among the tetracarboxylic acids or their dianhydrides, their dianhydrides are more preferably used. In addition, the above-mentioned tetracarboxylic acids or their dianhydrides may be used alone or in combination of two or more.

[0125] The reaction of the diol (d) represented by the general formula (16) and the acid components (b) and (c) is not particularly limited and a known method can be used. For example, Japanese Patent Application Laid-Open No. 9-325494 discloses a method of reacting epoxy (meth)acrylate with tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

[0126] Here, it is more preferred that the diol (d), dicarboxylic acid or tricarboxylic acid or the monoanhydride (b) of dicarboxylic acid or tricarboxylic acid, and the tetracarboxylic dianhydride (c) are reacted in a molar ratio of (d):(b):(c)=1:0.01 to 1.0:0.2 to 1.0, so that the terminal of the compound becomes a carboxyl group.

[0127] For example, when (b) a monoanhydride or (c) a dianhydride is used, it is more preferred that the molar ratio of the diol (d) containing a polymerizable unsaturated group to the acid component amount [(b) / 2+(c)] be 1:1.

[0128] The reaction is carried out in a manner such that [(b) / 2+(c)] becomes 0.5 to 1.0. Here, when the molar ratio is less than 1.0, since the content of the unreacted diol (d) containing a polymerizable unsaturated group will not increase, the temporal stability of the alkali-soluble resin composition can be improved. On the other hand, when the molar ratio exceeds 0.5, since the end of the alkali-soluble resin represented by the general formula (2) will not become anhydride, the increase in the content of the unreacted dianhydride can be suppressed, and the temporal stability of the alkali-soluble resin composition can be improved. In addition, the molar ratio of each component of (d), (b) and (c) can be arbitrarily changed within the above range for the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin represented by the general formula (2).

[0129] The alkali-soluble resin obtained by the reaction of the diol (d) shown in the general formula (16) with the acid components (b) and (c) has a structure of the general formula (28) in which G in the general formula (2) is a hydrogen atom. In the present embodiment, the carboxyl group of the general formula (28) is reacted with the epoxy compound containing an unsaturated group shown in the general formula (29). The reaction of the epoxy compound containing an unsaturated group shown in the formula (28) and the formula (30) can be carried out using a known method, for example, the method for producing epoxy (meth)acrylate shown in the formula (16) can be used. Thus, an alkali-soluble resin containing a polymerizable unsaturated group shown in the formula (2) can be obtained. In addition, the hydroxyl group of the above-mentioned alkali-soluble resin containing a polymerizable unsaturated group can also be reacted with a dicarboxylic acid or a tricarboxylic acid or a monoanhydride of a dicarboxylic acid or a tricarboxylic acid.

[0130]

[0131] (In formula (30), R4 is a hydrogen atom or a methyl group, R5 independently represents a hydrocarbon group having 2 to 4 carbon atoms, and c represents a number of 0 or 1.)

[0132] The molar ratio of the epoxy group of the epoxy compound containing an unsaturated group represented by the general formula (30) to the carboxyl group of the general formula (28) can be arbitrarily changed for the purpose of adjusting the photoreaction sensitivity (affected by the amount of polymerizable double bonds) or the acid value of the alkali-soluble resin represented by the general formula (2). In addition, if the molar number of the general formula (30) is less than 90% relative to the total molar number of the molar number of the component (b) and the molar number of the component (c) twice, alkali developability can be imparted, and it can be used in a photosensitive resin composition having photopatternability. In addition, in the case of imparting the effect of enhancing the photoreaction sensitivity, it must be 10% or more, so it is more preferably 10 to 90%, and more preferably 30 to 70%. In addition, the acid value of the alkali-soluble resin represented by the general formula (2) used is more preferably 20 to 180, and more preferably 30 to 120.

[0133] The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin represented by the general formula (2) of the present invention measured by colloid permeation chromatography (GPC) (HLC-8220GPC, manufactured by TOSOH Co., Ltd.) is usually 1,000 to 100,000, and preferably 2,000 to 20,000. When the weight average molecular weight is 1,000 or more, the reduction in pattern adhesion during alkaline development can be suppressed. In addition, when the weight average molecular weight is less than 100,000, it is easy to adjust the solution viscosity of the photosensitive resin composition to a viscosity suitable for coating without spending too much time on alkaline development. The colloid permeation chromatography (GPC) measurement of the above-mentioned alkali-soluble resin can be measured using "HLC-8220GPC" (manufactured by TOSOH Co., Ltd.).

[0134] Next, the alkali-soluble resin containing an unsaturated group of the general formula (31) (hereinafter referred to as "the alkali-soluble resin represented by the general formula (31)") is described. In addition, the alkali-soluble resin containing an unsaturated group represented by the general formula (31) is a mixture of the alkali-soluble resin containing a polymerizable unsaturated group represented by the general formula (2) and the alkali-soluble resin containing a polymerizable unsaturated group represented by the general formula (15).

[0135] The method for producing an alkali-soluble resin represented by the general formula (31) can be implemented by the method for producing an alkali-soluble resin represented by the general formula (2), but when an epoxy compound (a) having two epoxy groups in one molecule is reacted with a monocarboxylic acid containing an unsaturated group in the first step, the above-mentioned epoxy compound (a-1) and an epoxy resin (a-2) derived from a bisphenol can be used in combination as the (a) component.

[0136]

[0137] (In formula (31), Y is a tetravalent carboxylic acid residue, Z is a hydrogen atom or a substituent represented by general formula (3). However, at least one of Z is a substituent represented by general formula (3), G represents a hydrogen atom or a substituent represented by general formula (4), and W and W' represent a divalent organic group represented by a divalent organic group P represented by general formula (34) described later and / or a divalent organic group Q represented by general formula (35) described later. However, f represents a number with an average value of 1 to 20.)

[0138]

[0139] (In formula (3) and (4), R 4 represents a hydrogen atom or a methyl group, R 5 independently represent a hydrocarbon group having 2 to 4 carbon atoms, L represents a divalent or trivalent carboxylic acid residue, c represents a number of 0 or 1, d and e represent a number of 0, 1 or 2, and d+e represents a number of 1 or 2.

[0140] The epoxy resin (a-2) derived from bisphenols is represented by the general formula (32).

[0141]

[0142] (In formula (32), R6, R7, R8 and R9 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R 10 Each of the following independently represents a hydrocarbon group having 2 to 4 carbon atoms. In addition, M represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-diyl or a single bond, and d independently represents a number having an average value of 0 to 10 (but excluding 0).

[0143] The component (a-2) is an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. During the reaction, the diglycidyl ether compound is usually oligomerized, so that an oligomer as represented by the general formula (31) is obtained, but the m value of each molecule is different, and as mentioned above, the average value of m is greater than 0 and less than 10, and more preferably greater than 0.05 and less than 5.

[0144] Examples of bisphenols used as a raw material for the component (a-2) include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxy-3,5-dichlorophenyl)ketone, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl)sulfone, bis(4-hydroxy-3,5-dichlorophenyl)sulfone, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy- 3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxy-3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl) Fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 4,4'-biphenol, 3,3'-biphenol, and derivatives of these bisphenols. Among the above bisphenols, 2,2-bis(4-hydroxyphenyl)propane is more preferred. The bisphenols used as the raw material of the component (a-2) may be used alone or in combination of two or more.

[0145] In the first step of manufacturing the compound represented by the general formula (31), the components (a-1) and (a-2) are added in such a manner that the component (a-2) is 10 to 100 parts by mass (preferably 30 to 60 parts by mass) relative to 100 parts by mass of the component (a-1), and reacted with (meth)acrylic acid twice the total number of moles of the epoxy compounds (a-1) and (a-2) having two epoxy groups, thereby obtaining epoxy (meth)acrylate (d'). As described above, it is more preferred to implement this reaction using a catalyst in a solvent. Alternatively, epoxy (meth)acrylate (d') may be obtained by mixing an epoxy acrylate obtained by reacting 2 moles of (meth)acrylic acid to 1 mole of (a-1) with an epoxy acrylate obtained by reacting 2 moles of (meth)acrylic acid to 1 mole of (a-2).

[0146] In the second step, the epoxy (meth)acrylate (d') obtained in the first step is reacted with a dicarboxylic acid or a tricarboxylic acid or a monoanhydride (b) thereof and a tetracarboxylic acid or a dianhydride (c) thereof to obtain an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule of the general formula (33) (hereinafter referred to as "the alkali-soluble resin of the general formula (33)").

[0147]

[0148] (In formula (33), Y represents a tetravalent carboxylic acid residue, Z' represents a hydrogen atom or a substituent represented by general formula (29), and W and W' represent a divalent organic group represented by a divalent organic group P represented by general formula (34) described later and / or a divalent organic group Q represented by general formula (35) described later. However, f represents a number having an average value of 1 to 20.)

[0149]

[0150] (In formula (29), L represents a divalent or trivalent carboxylic acid residue, and r represents a number of 1 or 2.)

[0151] Here, when f in each molecule of the alkali-soluble resin represented by the general formula (34) is an integer, and the number of units represented by P and Q in the molecule is fP and fQ, respectively, f=fP+fQ. In addition, when W'=P, fQ≠0; when W'=Q, fP≠0; when W' is P, W must include Q; when W' is Q, W must include P.

[0152]

[0153] (In formula (34), R1 independently represents a hydrocarbon group having 2 to 4 carbon atoms, R2 independently represents a hydrocarbon group having 1 to 3 carbon atoms, R3 represents a hydrogen atom or a methyl group, and X represents a divalent organic group having 1 to 20 carbon atoms which may contain a heteroelement, -CO-, -SO2-, -Si(CH3)2-, -O-, or a single bond. However, a independently represents a number having an average value of 0 to 10, and b independently represents a number having an average value of 0 to 4.)

[0154]

[0155] (In formula (35), R6, R7, R8, and R9 independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group, and R 10 independently represent a hydrocarbon group having 2 to 4 carbon atoms, R 11 is a hydrogen atom or a methyl group. In addition, M is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-diyl or a direct bond. However, d independently represents a number with an average value of 0 to 10. )

[0156] In the second step, the types, addition amounts and reaction conditions of the acid components (b) and (c) used in the production of the alkali-soluble resin of the general formula (33) are the same as those used in the production of the alkali-soluble resin of the general formula (28).

[0157] In the third step, the alkali-soluble resin represented by the general formula (33) is reacted with the epoxy compound containing an unsaturated group represented by the general formula (30). The reaction is also carried out in the same manner as when the alkali-soluble resin represented by the general formula (2) is manufactured from the alkali-soluble resin represented by the general formula (28), and the alkali-soluble resin represented by the general formula (31) is obtained from the alkali-soluble resin represented by the general formula (33). If the molar number of the general formula (29) is less than 90% relative to the molar number of the component (b) and the molar number of the component (c) which is twice the total molar number, alkali developability can be imparted, and it can be used in a photosensitive resin composition having photopatternability. In addition, in the case of imparting the effect of enhancing the sensitivity of the photoreaction, the molar number of the general formula (29) needs to be more than 10%, so it is more preferably 10 to 90%, and more preferably 30 to 70%.

[0158] The weight average molecular weight of the alkali-soluble resin represented by the general formula (31) may be 1000 to 100000, and more preferably 2000 to 30000. In addition, the acid value of the alkali-soluble resin represented by the general formula (31) is preferably 20 to 180, and more preferably 30 to 120.

[0159] Next, the alkali-soluble resin represented by the general formula (12) having a carboxyl group and a polymerizable unsaturated group in one molecule (hereinafter referred to as "alkali-soluble resin represented by the general formula (12)") is described.

[0160]

[0161] (In formula (12), R 12 independently represent a hydrocarbon group having 2 to 4 carbon atoms, R 13 independently represent a hydrocarbon group having 1 to 3 carbon atoms, R 15 represents a hydrogen atom or a methyl group, R 16 represents a monovalent group obtained by reacting a glycidyl group with (meth)acrylic acid or a monovalent group formed by adding anhydride to the monovalent group, A1 and A2 independently represent the following general formula (7) or general formula (8), A3 and A4 independently represent the following general formula (9) or general formula (10), the presence rate of the above general formula (8) and general formula (10) relative to the total of A1, A2, A3 and A4 is 1 mol% or more and 100 mol% or less, Y represents a tetravalent carboxylic acid residue, G represents a hydrogen atom or a substituent represented by general formula (13), a independently represents a number with an average value of 0 to 10, b independently represents a number with an average value of 0 to 4, and m represents a number with an average value of 0 to 10.)

[0162]

[0163] (In formula (9), * indicates the bonding position of the five-membered ring.)

[0164]

[0165] (In formula (10), * indicates the bonding position of the five-membered ring.)

[0166]

[0167] (In formula (13), R 17 independently represents a hydrogen atom or a methyl group, R 18 independently represents a hydrocarbon group having 2 to 4 carbon atoms, and c is 0 or 1. )

[0168] First, the phenylene group or fluorenyl group of the epoxy resin represented by the general formula (14) is hydrogenated to obtain an epoxy compound (a-3) represented by the general formula (5) having two hydrogenated phenylene groups and two hydrogenated fluorenyl groups in one molecule.

[0169]

[0170] (In formula (14), R 12 independently represents a hydrocarbon group having 2 to 4 carbon atoms, a independently represents a number having an average value of 0 to 10, and n represents a number having an average value of 0 to 10. )

[0171]

[0172] (In formula (5), R 12independently represent a hydrocarbon group having 2 to 4 carbon atoms, R 13 independently represent a hydrocarbon group having 1 to 3 carbon atoms, R 14 represents a glycidyl group or the following general formula (6), but R 14 At least one of them represents an epoxypropyl group, a independently represents a number with an average value of 0 to 10, b independently represents a number with an average value of 0 to 4, n represents a number with an average value of 0 to 10, A1 and A2 independently represent the following general formula (7) or general formula (8), A3 and A4 independently represent the following general formula (9) or general formula (10), and the presence rate of the general formula (8) and general formula (10) is 1 mol% or more and 100 mol% or less relative to the total of A1, A2, A3 and A4.)

[0173]

[0174] (In formula (9), * indicates the bonding position of the five-membered ring.)

[0175]

[0176] (In formula (10), * indicates the bonding position of the five-membered ring.)

[0177] In the structure represented by the general formula (5), the presence ratio of the general formula (8) and the general formula (10) is preferably 1 mol% or more and less than 100 mol%, more preferably 10 mol% or more and 80 mol% or less, and even more preferably 30 mol% or more and 60 mol% or less relative to the total of A1, A2, A3 and A4. If the presence ratio of the general formula (8) and the general formula (10) is less than 100 mol%, the characteristics of the aromatic compound can be exerted in terms of heat resistance and the like. If the presence ratio of the general formula (8) and the general formula (10) is 1 mol% or more relative to the total of A1, A2, A3 and A4, the refractive index of the photosensitive resin composition can be reduced, and the composition can be used as a constituent component of a photosensitive resin composition having excellent light resistance.

[0178] In addition, in the present embodiment, the presence ratio of hydrogenated and ring-opened epoxy groups relative to the presence ratio of unhydrogenated epoxy groups in the epoxy compound (a-3) represented by the general formula (14) is preferably 10 mol% or less, and more preferably 1 mol% or less. If the presence ratio of hydrogenated and ring-opened epoxy groups is 10 mol% or less, the alkali-soluble resin containing a polymerizable unsaturated group used in the photosensitive resin composition of the present invention can be a resin having an appropriate molecular weight.

[0179] In addition, the hydrogenation of the epoxy compound (a-3) represented by the general formula (14) can be carried out by a known method (e.g., Japanese Patent Publication No. 11-217379, Japanese Patent Publication No. 2002-097251, etc.) In addition, the hydrogenation rate of the epoxy compound (a-3) represented by the general formula (14) can be adjusted by the reaction time and the reaction temperature.

[0180] Next, the epoxy compound (a-3) represented by the general formula (14) is reacted with a monocarboxylic acid containing an unsaturated group (for example, (meth)acrylic acid) to obtain epoxy (meth)acrylate.

[0181] The reaction of the epoxy compound (a-3) represented by the general formula (14) and (meth) acrylic acid can be carried out by a known method. For example, Japanese Patent Publication No. 4-355450 states that a diol or polyol compound containing a polymerizable unsaturated group can be obtained by using about 2 moles of (meth) acrylic acid for 1 mole of an epoxy compound having two epoxy groups. In the present invention, the compound obtained by the above reaction is a diol or polyol (d) represented by the general formula (11).

[0182]

[0183] (In formula (11), R 12 independently represent a hydrocarbon group having 2 to 4 carbon atoms, R 13 independently represent a hydrocarbon group having 1 to 3 carbon atoms, R 15 represents a hydrogen atom or a methyl group, a independently represents a number with an average value of 0 to 10, b independently represents a number with an average value of 0 to 4, n represents a number with an average value of 0 to 10, A1 and A2 independently represent the following general formula (7) or general formula (8), A3 and A4 independently represent the following general formula (9) or general formula (10), and the presence ratio of the above general formula (8) and general formula (10) is 1 mol% or more and 100 mol% or less relative to the total of A1, A2, A3 and A4.)

[0184]

[0185] (In formula (9), * indicates the bonding position of the five-membered ring.)

[0186]

[0187] (In formula (10), * indicates the bonding position of the five-membered ring.)

[0188] The alkali-soluble resin represented by the general formula (12) is produced by synthesizing a diol or polyol (d) represented by the general formula (11), and then subjecting the synthesized polycarboxylic acid or the anhydride of the polycarboxylic acid to an addition reaction, and optionally reacting with a monofunctional epoxy compound containing a polymerizable unsaturated group reactive with a carboxyl group. In the production, the reaction is usually carried out in a solvent using a catalyst as desired.

[0189] The above-mentioned solvent may be the same solvent as that used for producing the alkali-soluble resin represented by the general formula (2).

[0190] The reaction between the carboxyl group and the epoxy group can be carried out using the same catalyst as that used for producing the alkali-soluble resin represented by the general formula (2).

[0191] Subsequently, the diol or polyol (d) represented by the general formula (11) is reacted with a dicarboxylic acid or tricarboxylic acid or a monoanhydride (b) thereof and a tetracarboxylic acid or a dianhydride (c) thereof as an acid component to obtain an alkali-soluble resin represented by the general formula (36). The diol or polyol (d) represented by the general formula (11) is obtained by the reaction of an epoxy compound and (meth)acrylic acid.

[0192]

[0193] (In formula (36), R 12 independently represent a hydrocarbon group having 2 to 4 carbon atoms, R 13 independently represent a hydrocarbon group having 1 to 3 carbon atoms, R 14 represents a hydrogen atom or a methyl group, A1 and A2 independently represent the general formula (7) or the general formula (8), A3 and A4 independently represent the following general formula (9) or the general formula (10), the presence rate of the above general formula (8) and the general formula (10) relative to the total of A1, A2, A3 and A4 is 1 mol% or more and 100 mol% or less, Y represents a tetravalent carboxylic acid residue, and Z represents a hydrogen atom or a substituent represented by the following general formula (29). However, a represents a number with an average value of 0 to 10, b independently represents a number with an average value of 0 to 4, and m represents a number with an average value of 0 to 10.)

[0194]

[0195] (In formula (9), * indicates the bonding position of the five-membered ring.)

[0196]

[0197] (In formula (10), * indicates the bonding position of the five-membered ring.)

[0198]

[0199] (In formula (29), L independently represents a divalent or trivalent carboxylic acid residue, and r independently represents a number of 1 or 2.)

[0200] The acid component used to synthesize the alkali-soluble resin represented by the general formula (12) is a polyacid component that can react with the hydroxyl group in the diol or polyol (d) molecule represented by the general formula (11), and a dicarboxylic acid or a tricarboxylic acid or a monoanhydride (b) thereof, and a tetracarboxylic acid or a dianhydride (c) thereof are used in combination. The carboxylic acid residue of the above-mentioned acid component may be any of a saturated hydrocarbon group or an unsaturated hydrocarbon group. In addition, these carboxylic acid residues may include bonds containing hetero elements such as -O-, -S-, and a carbonyl group.

[0201] As the dicarboxylic acid or tricarboxylic acid or the monoanhydride thereof (b), and the tetracarboxylic acid or the dianhydride thereof (c), the same compounds as those used in the production of the alkali-soluble resin represented by the general formula (2) can be used.

[0202] The reaction of the diol or polyol (d) represented by the general formula (11) with the acid components (b) and (c) is not particularly limited, and a known method can be used. For example, Japanese Patent Application Laid-Open No. 9-325494 describes a method of reacting epoxy (meth)acrylate with tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

[0203] Here, it is more preferred to react the diol or polyol (d), dicarboxylic acid or tricarboxylic acid or their monoanhydrides (b), tetracarboxylic acid or their dianhydrides (c) in a molar ratio of (d):(b):(c)=1:0.01 to 1.0:0.2 to 1.0, so that the terminal of the compound becomes a carboxyl group.

[0204] For example, when monoanhydride (b) or dianhydride (c) is used, it is more preferred to react in such a manner that the molar ratio [(d) / [(b) / 2+(c)]] of the diol or polyol (d) containing a polymerizable unsaturated group relative to the amount of the acid component [(b) / 2+(c)] is 0.5 to 1.0. Here, when the molar ratio is less than 1.0, the content of the unreacted diol or polyol compound containing a polymerizable unsaturated group does not increase, so the temporal stability of the alkali-soluble resin composition can be improved. On the other hand, when the molar ratio exceeds 0.5, the end of the alkali-soluble resin represented by the general formula (36) does not become anhydride, so the increase in the content of the unreacted dianhydride can be suppressed, thereby improving the temporal stability of the alkali-soluble resin composition. In addition, the molar ratio of each component of (d), (b) and (c) can be arbitrarily changed within the above range for the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin represented by the general formula (36).

[0205] The alkali-soluble resin obtained by the reaction of the diol or polyol (d) represented by the general formula (11) with the above-mentioned acid components (b) and (c) has the structure of the general formula (36) in which G in the general formula (12) is a hydrogen atom. In addition, the epoxy compound containing an unsaturated group represented by the general formula (37) can be reacted with the carboxyl group of the general formula (36) and used as the alkali-soluble resin. The reaction of the general formula (36) with the epoxy compound containing an unsaturated group represented by the general formula (37) can be carried out using a known method, for example, the method for producing epoxy (meth)acrylate represented by the general formula (36) can be used. In this way, an alkali-soluble resin containing a polymerizable unsaturated group represented by the general formula (12) can be obtained. In addition, a dicarboxylic acid or a tricarboxylic acid or a monoanhydride thereof can be reacted with the hydroxyl group of the above-mentioned alkali-soluble resin containing a polymerizable unsaturated group.

[0206]

[0207] (In formula (37), R 17 represents a hydrogen atom or a methyl group, R 18 independently represents a hydrocarbon group having 2 to 4 carbon atoms, and c represents a number of 0 or 1. )

[0208] The molar ratio of the epoxy group of the epoxy compound containing an unsaturated group represented by the general formula (37) to the carboxyl group of the general formula (36) can be arbitrarily changed for the purpose of adjusting the sensitivity of the photoreaction of the alkali-soluble resin represented by the general formula (12) (due to the amount of polymerizable double bonds) or the acid value. In addition, if the molar number of the general formula (37) is less than 90% relative to the total molar number of the molar number of the component (b) and the molar number of the component (c) which is twice the total molar number, it can impart alkali developability and can be used for a photosensitive resin composition having photopatternability. In addition, in the case of imparting the effect of enhancing the sensitivity of the photoreaction, it needs to be more than 10%, so it is more preferably 10 to 90%, and more preferably 30 to 70%. In addition, the acid value of the alkali-soluble resin represented by the general formula (12) used is more preferably 20 to 180, and more preferably 30 to 120.

[0209] The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin represented by the general formula (12) of the present invention measured by colloid permeation chromatography (GPC) (HLC-8220GPC, manufactured by TOSOH Co., Ltd.) is usually 1,000 to 100,000, and more preferably 2,000 to 20,000. When the weight average molecular weight is 1,000 or more, the decrease in pattern adhesion during alkaline development can be suppressed. In addition, when the weight average molecular weight is less than 100,000, it is easy to adjust the solution viscosity of the photosensitive resin composition suitable for coating, and it is not necessary to spend too much time on alkaline development.

[0210] Next, a photosensitive resin composition using an alkali-soluble resin represented by the general formula (2) and / or an alkali-soluble resin represented by the general formula (31) of the present invention and a photosensitive resin composition using an alkali-soluble resin represented by the general formula (12) of the present invention are described. The preferred ratio of components of the photosensitive resin composition is different when the dispersion medium (E) is contained or not contained, and the case where the dispersion medium (E) is not contained will be described first.

[0211] First, the photosensitive resin composition using the alkali-soluble resin represented by the general formula (2) and / or the alkali-soluble resin represented by the general formula (31) of the present invention will be described.

[0212] The photosensitive resin composition is obtained by adding (B) a photopolymerization initiator to (A) an alkali-soluble resin represented by the general formula (2) and / or (31) to obtain a solution viscosity suitable for forming a coating film using a solvent.

[0213] In the above-mentioned photosensitive resin composition, in the solid content of the photosensitive resin composition, the component (A) is 1 to 55% by mass, the component (C) is 0 to 100 parts by mass relative to 100 parts by mass of the component (A), the component (B) is 0.1 to 40 parts by mass relative to 100 parts by mass of the total amount of the component (A) and the component (C), and the component (E) is 1 to 95% by mass.

[0214] In addition, the above-mentioned component (A) contains: an alkali-soluble resin containing a polymerizable unsaturated group represented by the general formula (2), and a resin represented by the general formula (15); the mass m of the alkali-soluble resin containing a polymerizable unsaturated group represented by the formula (2) is A-1 The mass m of the resin represented by general formula (15) A-2 The ratio is m A-1 / m A-2 =75 / 25 to 25 / 75.

[0215]

[0216] (In formula (2), R1 independently represents a hydrocarbon group having 2 to 4 carbon atoms, R2 independently represents a hydrocarbon group having 1 to 3 carbon atoms, R3 represents a hydrogen atom or a methyl group, X represents a divalent organic group having 1 to 20 carbon atoms which may contain a heteroelement, -CO-, -SO2-, -Si(CH3)2-, -O-, or a single bond, Y represents a tetravalent carboxylic acid residue, Z represents a hydrogen atom or a substituent represented by general formula (3), but at least one of Z represents a substituent represented by general formula (3), G represents a hydrogen atom or a substituent represented by general formula (4), a independently represents a number having an average value of 0 to 10, b independently represents a number having an average value of 0 to 4, and n represents a number having an average value of 1 to 20.)

[0217]

[0218] (In formula (3) and (4), R4 represents a hydrogen atom or a methyl group, R5 independently represents a hydrocarbon group having 2 to 4 carbon atoms, L represents a divalent or trivalent carboxylic acid residue, c represents a number of 0 or 1, d and e represent a number of 0, 1 or 2, and d+e represents a number of 1 or 2.)

[0219]

[0220] (In formula (15), R6, R7, R8, and R9 independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group, and R 10 represents a hydrocarbon group having 2 to 4 carbon atoms, R 11 represents a hydrogen atom or a methyl group. In addition, M is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-diyl or a direct bond, Y is a tetravalent carboxylic acid residue, and Z is a hydrogen atom or a substituent represented by the general formula (3). However, at least one of Z represents a substituent represented by the general formula (3), and G represents a hydrogen atom or a substituent represented by the general formula (4). d independently represents a number with an average value of 0 to 10, and m represents a number with an average value of 1 to 20. )

[0221] Next, the photosensitive resin composition using the alkali-soluble resin represented by the general formula (12) of the present invention will be described.

[0222] A photosensitive resin composition is obtained by adding (B) a photopolymerization initiator to (A) an alkali-soluble resin represented by the general formula (12) to obtain a solution viscosity suitable for forming a coating film using a solvent.

[0223] In the above-mentioned photosensitive resin composition, in the solid content of the photosensitive resin composition, the component (A) is 1 to 55% by mass, the component (C) is 0 to 100 parts by mass relative to 100 parts by mass of the component (A), the component (B) is 0.1 to 40 parts by mass relative to 100 parts by mass of the total amount of the component (A) and the component (C), and the component (E) is 1 to 95% by mass.

[0224] Examples of the photopolymerization initiator (B) in the photosensitive resin composition of the present invention include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminoacetophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone; diphenyl ketones such as phenyl ketone, 2-chlorophenyl ketone, and p,p'-bisdimethylaminophenyl ketone; benzoin ethers such as dibenzoyl (benzil), benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)- 4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole and other biimidazole compounds; 2-trichloromethyl-5-phenylvinyl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanophenylvinyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxyphenylvinyl)-1,3,4-oxadiazole and other halomethyldiazole compounds; 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)- Halomethyl-s-triazine compounds such as 1,2-dione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyl oxime), 1-(4-phenylthiophenyl)-butane-1,2-dione-2-oxime- O-acyl oxime compounds such as O-benzoate, 1-(4-methylthiophenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylthiophenyl)butane-1-one oxime-O-acetate; sulfur compounds such as benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, isopropylbenzene peroxide; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole; tertiary amines such as triethanolamine and triethylamine, etc. In addition, these photopolymerization initiators can be used alone or in combination of two or more.

[0225] In particular, when a photosensitive resin composition containing a colorant is prepared, it is more preferred to use O-acyl oxime compounds (including ketoxime). Specific compound groups include O-acyl oxime photopolymerization initiators represented by general formula (38) or general formula (39). Among these, it is more preferred to use an O-acyl oxime photopolymerization initiator having a molar absorption coefficient of 10,000 L / mol·cm or more at 365 nm when using a colorant with a high pigment concentration and when forming a light-shielding film pattern. In addition, the meaning of "photopolymerization initiator" used in the present invention includes sensitizers.

[0226]

[0227] (In formula (38), R 19 , R 20 Each independently represents a C1 to C15 alkyl group, a C6 to C18 aryl group, a C7 to C20 arylalkyl group or a C4 to C12 heterocyclic group, and R 21 represents C1 to C15 alkyl, C6 to C18 aryl, C7 to C20 arylalkyl. Here, the alkyl and aryl groups may be substituted by C1 to C10 alkyl, C1 to C10 alkoxy, C1 to C10 alkanoyl, or halogen, and the alkylene portion may also include an unsaturated bond, an ether bond, a thioether bond, or an ester bond. In addition, the alkyl group may be any of a linear, branched, or cyclic alkyl group.)

[0228]

[0229] (In formula (39), R 22 and R 23 R is independently a linear or branched alkyl group having 1 to 10 carbon atoms; a cycloalkyl group, a cycloalkylalkyl group or an alkylcycloalkyl group having 4 to 10 carbon atoms; or a phenyl group which may be substituted by an alkyl group having 1 to 6 carbon atoms. 24 R independently represents a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, and a portion of the -CH2- groups in the alkyl or alkenyl group may be substituted with an -O- group. 22 To R 24 A part of the hydrogen atoms in the group may be substituted by halogen atoms.

[0230] The photosensitive resin composition of the present invention may contain a solvent. Examples of the solvent include: alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α-terpineol and β-terpineol; acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone (Methyl pyrrolidone) and other ketones; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellulose, methyl cellulose, ethyl cellulose, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; acetates such as ethyl acetate, butyl acetate, cellulose acetate, ethyl cellulose acetate, butyl cellulose acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. These can be used alone or in combination of two or more, dissolved or mixed, to prepare a uniform solution composition. The amount of the solvent varies depending on the target viscosity, but is preferably in the range of 60 to 90% by mass in the photosensitive resin composition solution.

[0231] In the photosensitive resin composition of the present invention, in addition to the above-mentioned (A) alkali-soluble resin of a specific structure and (B) photopolymerization initiator, (C) a photopolymerizable monomer having at least one ethylenically unsaturated bond, and (D) an epoxy compound or epoxy resin containing two or more epoxy groups may be optionally added, and these components (C) and (D) may be used in combination.

[0232] Examples of the (C) photopolymerizable monomer in the photosensitive resin composition of the present invention include: (meth)acrylates having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol (Meth)acrylates such as di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol (meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene oxirane-modified hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and dendrimer-type multifunctional acrylate. These photopolymerizable monomers may be used alone or in combination of two or more.

[0233] In addition, as for the photopolymerizable monomer having at least one ethylenically unsaturated bond, it is more preferred to use molecules of an alkali-soluble resin having two or more photopolymerizable groups and containing an unsaturated group to crosslink each other. In addition, (C) the photopolymerizable monomer having at least one ethylenically unsaturated bond does not have a free carboxyl group.

[0234] Examples of the epoxy resin or epoxy compound (D) having two or more epoxy groups in the photosensitive resin composition of the present invention include: 3,3',5,5'-tetramethyl-4,4'-biphenol type epoxy resin, bisphenol A type epoxy resin, bisphenol fluorene type epoxy resin, phenol novolac type epoxy resin, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexene carboxylate, 1,2-epoxy-4-(2-oxirane)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, epoxy polysilicone resin, etc. These compounds may be used alone or in combination of a plurality of them.

[0235] In a photosensitive resin composition not containing component (E), the preferred blending ratio of the case where component (C) and / or component (D) is used is 0 to 100 parts by mass relative to 100 parts by mass of component (A); in the case where component (D) is used, component (D) is preferably 5 to 30 parts by mass compared to 100 parts by mass of the total amount of component (A) and component (C). The purpose of using component (C) is to improve the sensitivity of the photocuring reaction of the photosensitive resin composition, and the sensitivity will increase if the amount added increases. However, if more component (D) than component (A) is added, the alkali solubility of the photosensitive resin composition is insufficient and the developability will decrease. On the other hand, the purpose of adding component (D) is to improve the physical properties of the photopatterned film by thermal curing in succession to the photocuring reaction and alkaline development, especially when using an epoxy compound having more than two epoxy groups, the surface hardness can be improved by cross-linking the resin component. However, if the amount relative to the photocuring component is too much, it will have an adverse effect on the photopatterning property.

[0236] The photosensitive resin composition may be a photosensitive resin composition to which a dispersion medium (E) is added. When a photosensitive resin composition to which a dispersion medium is added is used, a more preferred blending ratio is that in the solid content containing the component cured by light curing, the content of the component (A) is 1 to 55% by mass, the component (C) is 0 to 100 parts by mass relative to 100 parts by mass of the component (A), the component (B) is 0.1 to 40 parts by mass relative to 100 parts by mass of the total amount of the components (A) and (C), and the component (E) is 1 to 95% by mass in the solid content. When the component (D) is used, the component (D) is more preferably 5 to 30 parts by mass relative to 100 parts by mass of the total amount of the components (A) and (C).

[0237] The (E) dispersion medium that can be used in the present invention can be any known dispersion medium used for conventional photosensitive resin compositions without particular limitation as long as it is a dispersion medium that disperses particles with an average particle size of 1 to 1000 nm (average particle size measured by a laser diffraction / scattering particle size distribution analyzer or a dynamic light scattering particle size distribution analyzer).

[0238] Here, examples of black pigments include perylene black, cyanine black, aniline black, carbon black, titanium black, etc. Examples of mixed color organic pigments include pigments of at least two colors selected from organic pigments such as azo pigments, condensed azo pigments, methine azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindolinone pigments, dioxazine pigments, threne pigments, perylene pigments, peroxycyclic ketone pigments, quinolinone pigments, diketopyrrolopyrrole pigments, and thioindigo pigments. Examples of white pigments include titanium oxide pigments, composite oxide pigments; inorganic fillers such as calcium silicate, magnesium carbonate, calcium carbonate, calcium sulfate, and barium sulfate. These (E) components may be used alone or in combination of two or more, depending on the function of the intended photosensitive resin composition.

[0239] In addition, the above-mentioned (E) dispersion medium can be used alone or in combination according to the function of the photosensitive resin composition of the purpose. For example, the following dispersion media can be appropriately selected and used: the light-shielding photoresist used in the manufacture of the black matrix of the color filter can use carbon black, titanium black, black organic pigments, etc.; the coloring photoresist used to manufacture the pixels (pixel) of the color filter can use red, orange, yellow, green, blue, purple organic pigments, etc.; the solder resist used in the manufacture of the insulating film of the printed wiring board can use organic pigments, inorganic pigments, inorganic fillers, etc.; the decorative photoresist that can be used in the design of the front glass of the touch panel can use carbon black, titanium black, black organic pigments, white pigments, etc.; as a transparent photoresist with high hardness and high durability, a transparent filler such as silica can be used.

[0240] In addition, examples of the organic pigment that can be used as the component (E) include organic pigments with the following color material index names, but are not limited to these.

[0241] Pigment Red: 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279, etc.

[0242] Pigment orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.;

[0243] Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc.;

[0244] Pigment Green 7, 36, 58, etc.;

[0245] Pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc.;

[0246] Pigment Violet 19, 23, 37, etc.

[0247] The blending ratio of the coloring agent as the component (E) can be arbitrarily determined according to the desired light-shielding degree, but is more preferably 1 to 80% by mass based on the solid content in the photosensitive resin composition.

[0248] The above-mentioned (E) component is generally mixed with other blending components as a dispersion dispersed in a solvent (a colorant dispersion in the case of a colorant), and a dispersant (component E') may be added at this time. The dispersant may be a known compound used for dispersing pigments (colorants) (compounds sold on the market under the names of dispersants, dispersing wetting agents, dispersion accelerators, etc.) without particular limitation.

[0249] Examples of dispersants include: cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, pigment derivative dispersants (dispersing aids). In particular, with respect to the adsorption of the colorant, the dispersant is preferably a cationic polymer dispersant having a cationic functional group such as an imidazole group, a pyrrolyl group, a pyridine group, a primary amine group, a secondary amine group or a tertiary amine group, and an amine value of 1 to 100 mgKOH / g and a number average molecular weight of 1,000 to 100,000. Relative to the colorant, the blending amount of this dispersant is preferably 1 to 35% by mass, more preferably 2 to 25% by mass. In addition, high-viscosity substances such as resins generally have the effect of stabilizing dispersion, but high-viscosity substances that do not have the ability to promote dispersion are not used as dispersants. However, it is not limited to using high-viscosity substances for the purpose of stabilizing dispersion.

[0250] As described above, the photosensitive resin composition of the present invention may be used as a photosensitive resin composition to which various (E) dispersion media are added, and may be used, for example, for applications requiring light resistance.

[0251] In addition, in the present invention, other resin components that are polymerized or cured by light or heat may be optionally used in combination. Examples of other resin components include alkali-soluble resins obtained by reacting novolac epoxy resins derived from novolacs such as phenol novolac and cresol novolac with (meth)acrylic acid and anhydride, and alkali-soluble resins obtained by reacting carboxyl groups in copolymers of (meth)acrylic acid and (meth)acrylates with (meth)acrylates containing epoxy groups.

[0252] The photosensitive resin composition of the present invention may also be optionally blended with resins other than component (A) such as epoxy resin, hardeners, hardening accelerators, thermal polymerization inhibitors and antioxidants, plasticizers, fillers, leveling agents, defoamers, surfactants, coupling agents and other additives. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, benzyltriol, tert-butylcatechol, phenothiazine, hindered phenol compounds, etc. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. Examples of fillers include glass fiber, silica, mica, aluminum oxide, etc. Examples of defoamers or leveling agents include silicone, fluorine, and acrylic compounds. Examples of surfactants include fluorine surfactants, silicone surfactants, etc. Examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, and the like.

[0253] The cured film of the present invention is formed by photolithography using the photosensitive resin composition of the present invention. The manufacturing steps include the following method: first, a photosensitive resin composition solution is applied to the surface of a substrate, and then the solvent is dried (prebaked), and then a photomask is placed on the film thus obtained, and ultraviolet rays are irradiated to cure the exposed part, and then an alkaline aqueous solution is used to dissolve the unexposed part, develop it to form a pattern, and then post-bake it as a post-hardening. Here, the substrate on which the photosensitive resin composition solution is applied can use glass, a transparent film (such as polycarbonate, polyethylene terephthalate, polyether sulfone, etc.), etc.

[0254] As for the method of applying the photosensitive resin composition solution to the substrate, in addition to the known solution dipping method and spraying method, any method using a roller coater, a land coater, a slit coater and a spinner can be used. After coating to the desired thickness by these methods, the solvent is removed (pre-baked) to form a film. Pre-baking is carried out by heating with an oven, a heating plate, etc. The heating temperature and heating time of pre-baking can be appropriately selected according to the solvent used, for example, preferably at 80 to 120°C for 1 to 10 minutes.

[0255] As for the radiation used for exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc. can be used, and the wavelength range of the radiation is preferably 250 to 450 nm. In addition, the developer suitable for this alkaline development can use, for example, aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. These developers can be appropriately selected in accordance with the characteristics of the resin layer, but it is also effective to add a surfactant optionally. The development temperature is preferably 20 to 35°C, and a commercially available developer, ultrasonic washing machine, etc. can be used to accurately form a fine image. In addition, water washing is usually performed after alkaline development. The development treatment method can apply: shower development method, spray development method, dipping development method, puddle development method, etc.

[0256] The alkaline development after exposure is performed for the purpose of removing the unexposed portion of the photosensitive resin composition, and the desired pattern is formed by this development. The developer suitable for this alkaline development includes, for example, an aqueous solution of carbonates of alkali metals and alkaline earth metals, an aqueous solution of hydroxides of alkali metals, etc. However, it is particularly preferable to use a weakly alkaline aqueous solution containing 0.03 to 1% by weight of carbonates such as sodium carbonate and potassium carbonate, and to perform development at a temperature of 23 to 27° C., and a commercially available developer and ultrasonic washing machine can be used to accurately form a fine image.

[0257] After development in this manner, heat treatment (post-baking) is performed at 180 to 250°C for 20 to 100 minutes. However, when the heat resistance of the film-forming substrate is low, the composition can be designed so that it can be post-baked at 80 to 180°C for 30 to 100 minutes. The purpose of this post-baking is to improve the adhesion between the patterned coating and the substrate. This post-baking can be performed by heating with an oven, a heating plate, etc. in the same way as pre-baking. The patterned cured film of the present invention is formed by the above steps of the photoetching method.

[0258] (Example)

[0259] Hereinafter, the embodiments of the present invention will be specifically described based on the examples and comparative examples, but the present invention is not limited to these embodiments. In addition, in the following Examples 1 and 2, unless otherwise specified, various measurements and evaluations are performed in the following manner. Regarding various measuring machines, when the same machine model is used, the manufacturer name of the machine is omitted from the second time. In addition, in Examples 1 and 2, the glass substrates used to make the hardened films for measurement all use glass substrates that have been subjected to the same treatment.

[0260] [Example 1]

[0261] First, a synthesis example of the polymerizable unsaturated group-containing alkali-soluble resin having the structure represented by the general formula (2) and the general formula (15) will be described.

[0262] [Solid content]

[0263] 1 g of the resin solution, photosensitive resin composition, etc. obtained in the synthesis example and the comparative synthesis example is impregnated in a glass filter [mass: W0 (g)] and weighed [W1 (g)]. The mass [W2 (g)] after heating at 160°C for 2 hours is calculated using the following formula (1).

[0264] Solid content (mass %) = 100 × (W2-W0) / (W1-W0) (1)

[0265] [Acid value]

[0266] The resin solution was dissolved in tetrahydrofuran and titrated with a 1 / 10 N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.), and the amount of KOH required per 1 g of solid content was taken as the acid value.

[0267] [Molecular weight]

[0268] The colloid permeation chromatography (GPC) was performed using HLC-8220GPC (produced by TOSOH Co., Ltd., solvent: tetrahydrofuran, column: TSKgel Super H-2000 (2

[0269] 1pc)+TSKgelSuperH-3000(1pc)+TSKgelSuperH-4000(1pc)

[0270] The molecular weight was measured by using 1 tube of TSKgel Super H-5000 (1 tube) (manufactured by TOSOH Co., Ltd.), temperature: 40°C, speed: 0.6 ml / min), and the weight average molecular weight (Mw) was calculated using the converted value of standard polystyrene (PS-Oligomer Kit, manufactured by TOSOH Co., Ltd.).

[0271] In addition, the abbreviations used in the synthesis examples and comparative synthesis examples are as follows.

[0272] HBPA-EA1: a reaction product of hydrogenated bisphenol A epoxy resin (epoxy equivalent 201 g / eq) (having a skeleton of the general formula (1)) and acrylic acid (equivalent reaction product of epoxy group and carboxyl group).

[0273] HBPA-EA2: a reaction product of hydrogenated bisphenol A epoxy resin (epoxy equivalent 265 g / eq) (having a skeleton of the general formula (1)) and acrylic acid (equivalent reaction product of epoxy group and carboxyl group).

[0274] BPA-EA: a reaction product of bisphenol A epoxy resin (epoxy equivalent 189 g / eq) (having a skeleton of the general formula (33)) and acrylic acid (equivalent reaction product of epoxy group and carboxyl group).

[0275] BPF-EA: a reaction product of a bisphenol fluorene epoxy resin (epoxy equivalent 250 g / eq) (having a skeleton of the general formula (33)) and acrylic acid (equivalent reaction product of epoxy groups and carboxyl groups).

[0276] BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride.

[0277] HPMDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride.

[0278] THPA: 1,2,3,6-Tetrahydrophthalic anhydride.

[0279] TEAB: tetraethylammonium bromide.

[0280] PGMEA: propylene glycol monomethyl ether acetate.

[0281] (Synthesis example 1)

[0282] In a 1000 ml four-necked flask with a reflux cooler, 50% PGMEA solution of HBPA-EA1 (329.1 g), BPDA (44.1 g), THPA (22.8 g), TEAB (0.43 g), and PGMEA (8.5 g) were added, and the mixture was stirred at 120 to 125° C. for 6 hours to obtain an alkali-soluble resin (i)-1 (solid content concentration: 61.2% by mass, weight average molecular weight (Mw): 3210, acid value (converted to solid content): 123.1 mgKOH / g).

[0283] (Synthesis example 2)

[0284] In a 1000 ml four-necked flask with a reflux cooler, 50% PGMEA solution of HBPA-EA1 (340.0 g), HPMDA (34.7 g), THPA (23.6 g), TEAB (0.43 g), and PGMEA (8.5 g) were added, and stirred at 120 to 125° C. for 6 hours to obtain an alkali-soluble resin (i)-2 (solid content concentration: 61.1% by mass, weight average molecular weight (Mw): 3230, acid value (converted to solid content): 120.4 mgKOH / g).

[0285] (Synthesis example 3)

[0286] In a 1000 ml four-necked flask with a reflux cooler, 50% PGMEA solution of HBPA-EA2 (338.2 g), BPDA (36.8 g), THPA (19.0 g), TEAB (0.43 g), and PGMEA (8.5 g) were added, and stirred at 120 to 125° C. for 6 hours to obtain an alkali-soluble resin (i)-3 (solid content concentration: 73.8% by mass, weight average molecular weight (Mw): 4980, acid value (converted to solid content): 93.0 mgKOH / g).

[0287] (Synthesis Example 4)

[0288] In a 1000 ml four-necked flask with a reflux cooler, 50% PGMEA solution of HBPA-EA2 (338.2 g), HPMDA (28.0 g), THPA (19.0 g), TEAB (0.43 g), and PGMEA (8.5 g) were added, and stirred at 120 to 125° C. for 6 hours to obtain an alkali-soluble resin (i)-4 (solid content concentration: 64.2% by mass, weight average molecular weight (Mw): 3960, acid value (converted to solid content): 100.8 mgKOH / g).

[0289] (Comparative Synthesis Example 1)

[0290] In a 1000 ml four-necked flask with a reflux cooler, a 50% PGMEA solution of BPA-EA (325.1 g), BPDA (45.6 g), THPA (23.6 g), TEAB (0.43 g), and PGMEA (8.5 g) were added, and the mixture was stirred at 120 to 125° C. for 6 hours to obtain an alkali-soluble resin (i)-5 (solid content concentration: 68.5% by mass, weight average molecular weight (Mw): 2080, acid value (converted to solid content): 113.0 mgKOH / g).

[0291] (Comparative Synthesis Example 2)

[0292] In a 1000 ml four-necked flask with a reflux cooler, 50% PGMEA solution of BPA-EA (335.6 g), HPMDA (35.9 g), THPA (24.3 g), TEAB (0.43 g), and PGMEA (8.5 g) were added, and stirred at 120 to 125° C. for 6 hours to obtain an alkali-soluble resin (i)-6 (solid content concentration: 69.5% by mass, weight average molecular weight (Mw): 2630, acid value (converted to solid content): 116.5 mgKOH / g).

[0293] (Comparative Synthesis Example 3)

[0294] In a 1000ml four-necked flask with a reflux cooler, 50% PGMEA solution of BPF-EA (313.7g), BPDA (47.1g), THPA (24.3g), TEAB (0.43g), and PGMEA (8.5g) were added, and stirred at 120 to 125°C for 6 hours to obtain alkali-soluble resin (i)-7 (solid content concentration: 56.55% by mass, weight average molecular weight (Mw): 3600, acid value (solid content conversion): 103.0mgKOH / g).

[0295] Next, the present invention will be specifically described based on examples and comparative examples of the photosensitive resin composition and the cured film, but the present invention is not limited to these examples. The raw materials and abbreviations used in the examples and comparative examples described below are as follows.

[0296] (i)-1: Alkali-soluble resin obtained in Synthesis Example 1.

[0297] (i)-2: Alkali-soluble resin obtained in Synthesis Example 2.

[0298] (i)-3: Alkali-soluble resin obtained in Synthesis Example 3.

[0299] (i)-4: Alkali-soluble resin obtained in Synthesis Example 4.

[0300] (i)-5: Alkali-soluble resin obtained in Comparative Synthesis Example 1.

[0301] (i)-6: Alkali-soluble resin obtained in Comparative Synthesis Example 2.

[0302] (i)-7: Alkali-soluble resin obtained in Comparative Synthesis Example 3.

[0303] (ii): Dipentaerythritol hexaacrylate.

[0304] (iii): Omnirad 184 (manufactured by IGM Resins BV) (former Irgacure 184 (manufactured by BASF Corporation; “Irgacure” is a registered trademark of BASF Corporation).

[0305] (iv): A PGMEA dispersion containing 20.0% by mass of carbon black and 5.0% by mass of a polymer dispersant (solid content: 25.0%, average secondary particle size of carbon black: 162 nm).

[0306] (v): Propylene glycol monomethyl ether acetate.

[0307] [Evaluation of photosensitive resin composition]

[0308] Table 1 shows the content of each component of the photosensitive resin composition solutions of Synthesis Examples 1 to 4, Comparative Examples 1 and 2 (unit: mass %).

[0309]

Table 1

[0310]

[0311]

[0312] (Production of hardened film for measuring light transmittance and refractive index)

[0313] The irradiance was 1000 mJ / cm2 using a low-pressure mercury lamp with a wavelength of 254 nm. 2 On a 125 mm×125 mm glass substrate "#1737" (manufactured by Corning Incorporated) (hereinafter referred to as the "glass substrate"), the photosensitive resin composition solutions of Examples 1 to 4, Comparative Examples 1 and 2 were applied using a spin coater to a dry film thickness of 1.5 μm and dried, and then irradiated with a 500 W high pressure mercury lamp without a photomask at a wavelength of 365 nm and an illumination of 10 mW / cm 2 The glass substrate was exposed to ultraviolet rays. Then, a developer was treated with a 0.4% sodium carbonate aqueous solution at 23°C for 60 seconds at a pressure of 0.1 MPa. Thereafter, a heat curing treatment was performed at 230°C for 30 minutes using a hot air dryer to obtain a cured film (a glass substrate on which a cured film is formed).

[0314] The light transmittance and refractive index of the cured film were evaluated. The results are shown in Table 2.

[0315] (Measurement method of light transmittance)

[0316] The light transmittance at 400 nm was measured using an ultraviolet / visible / near infrared (UV-Vis-NIR) spectrophotometer "UH4150" (manufactured by Hitachi-Hightech Co., Ltd.).

[0317] (Evaluation Criteria)

[0318] ○: The light transmittance is 85% or more.

[0319] ×: The light transmittance is less than 85%.

[0320] (Method for measuring refractive index)

[0321] Using prism coupler film thickness / refractometer "Model 2010 / M"

[0322] The refractive index of light of 633 nm was measured by using a 100 nm reflectometer (manufactured by Metricon). Table 2 shows the results of the measurement of light transmittance and refractive index.

[0323]

Table 2

[0324]

[0325]

[0326] The results of Examples 1 to 4 and Comparative Examples 1 and 2 show that a cured film having high light transmittance and low refractive index can be obtained by using the photosensitive resin composition containing the alkali-soluble resin (i)-1 to (i)-4 having a skeleton of the general formula (1) of the present invention.

[0327] [Evaluation of Colored Photosensitive Resin Composition]

[0328] Table 3 shows the content of each component of the colored photosensitive resin composition solutions of Synthesis Examples 5 to 8, Comparative Examples 3 and 4 (unit: mass %).

[0329]

Table 3

[0330] Element Example 5 Example 6 Example 7 Example 8 Comparative Example 3 Comparative Example 4 (i)-1 3.92 (i)-2 3.93 (i)-3 3.25 (i)-4 3.74 (i)-5 3.50 (i)-6 3.45 (i)-7 9.91 9.91 9.91 9.91 9.91 9.91 (ii) 2.67 2.67 2.67 2.67 2.67 2.67 (iii) 0.75 0.75 0.75 0.75 0.75 0.75 (iv) 37.3 37.3 37.3 37.3 37.3 37.3 (v) 45.45 34.44 46.12 45.63 45.87 45.92

[0331] (Preparation of Colored Cured Film for Reflectivity Measurement)

[0332] The colored photosensitive resin composition solutions of Examples 5 to 8 and Comparative Examples 3 and 4 were applied to a glass substrate using a spin coater to a dry film thickness of 1.5 μm and dried. The glass substrate was then irradiated with a 500 W high pressure mercury lamp at a wavelength of 365 nm and an illumination of 10 mW / cm2 without a photomask. 2 The glass substrate was exposed to ultraviolet rays. Then, a developer solution was treated with a 0.4% sodium carbonate aqueous solution at 23°C for 60 seconds at a pressure of 0.1 MPa. Thereafter, a heat curing treatment was performed at 230°C for 30 minutes using a hot air dryer to obtain a colored cured film (a glass substrate having a colored cured film formed thereon).

[0333] The reflectance (Y) of the glass substrate on which the colored cured film was formed was measured. The results are shown in Table 4.

[0334] (Measurement method of reflectance (Y))

[0335] Reflectance (Y) was measured using a UV-Vis-NIR spectrophotometer

[0336] "UH4150". In addition, the appearance of the surface of the colored cured film was visually confirmed.

[0337] (Evaluation Criteria)

[0338] ◎: No color unevenness was observed at all.

[0339] ○: Color unevenness was observed in an area less than 1 / 4 of the surface.

[0340] △: Color unevenness was observed in an area less than 1 / 3 of the surface.

[0341] ×: Color unevenness is observed overall.

[0342]

Table 4

[0343] Example 5 Example 6 Example 7 Example 8 Comparative Example 3 Comparative Example 4 Y 6.87 6.82 6.96 6.80 7.00 6.96 Appearance ◎ ◎ ◎ ◎ × ×

[0344] (Preparation of Colored Cured Film for Evaluation of Alkali Developability and Adhesion)

[0345] The colored photosensitive resin composition solutions of Examples 5 to 8, Comparative Examples 3 and 4 were applied to a glass substrate using a spin coater to a dry film thickness of 1.5 μm and dried, and then irradiated with a 500 W high pressure mercury lamp at a wavelength of 365 nm and an illumination of 10 mW / cm2 through a pattern forming mask. 2 The glass substrate was exposed to ultraviolet rays of 200° C. Then, a developer was treated using a 0.15% sodium carbonate aqueous solution at 23° C. Thereafter, a heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer to obtain a colored cured film (a glass substrate having a colored cured film formed thereon).

[0346] The alkali developability and adhesion were evaluated about the glass substrate on which the colored cured film was formed. The results are shown in Table 5.

[0347] [Evaluation of alkali developability]

[0348] (Evaluation Method)

[0349] During development, it is visually confirmed whether the thin film of the dried colored photosensitive resin composition is dissolved in the developer.

[0350] (Evaluation Criteria)

[0351] ○: During development, the region not irradiated with ultraviolet rays is dissolved in the developer.

[0352] ×: During development, the region not irradiated with ultraviolet rays was not dissolved in the developer, or was broken into pieces and peeled off.

[0353] [Fitness evaluation]

[0354] (Evaluation Method)

[0355] The formation of fine lines of the photoresist film pattern was confirmed using an optical microscope "ECLIPSE LV100" (manufactured by Nikon Corporation).

[0356] (Evaluation Criteria)

[0357] ○: A pattern having an L / S (line width / space width) of 20 μm / 20 μm or more was formed without any residue.

[0358] ×: A pattern with an L / S (line width / space width) of 20 μm / less than 20 μm was not formed, or tailing and residue of the pattern were noticeable.

[0359]

Table 5

[0360] Example 5 Example 6 Example 7 Example 8 Comparative Example 3 Comparative Example 4 Development 〇 〇 〇 〇 × × Adhesion 〇 〇 〇 〇 × ×

[0361] From the results of Examples 5 to 8, Comparative Examples 3 and 4, it can be seen that by using the photosensitive resin composition of the present invention comprising the alkali-soluble resins (i)-1 to (i)-4 having a skeleton of the general formula (1), a colored film with lower reflection, no color unevenness, and fine pattern can be formed compared to the case of using a resin containing a larger aromatic skeleton such as the general formula (1).

[0362] [Example 2]

[0363] Next, a synthesis example of an alkali-soluble resin containing a polymerizable unsaturated group having a structure represented by general formula (12) is described. In the following Example 2, unless otherwise specified, various measurements and evaluations are performed as described below. In addition, the measurements of solid content concentration, acid value, and molecular weight are the same as those in the above-mentioned Example 1, so they are omitted.

[0364] [Determination of epoxy equivalent]

[0365] A potentiometric titrator "COM-1600" was used. Methyl ethyl ketone was used as the solvent. Tetraethylammonium bromide acetic acid solution was added. The potentiometric titrator was used to measure using a 0.1 mol / L perchloric acid-acetic acid solution.

[0366] [Method for measuring refractive index]

[0367] The refractive index of the cured film was measured in a 633 nm light beam using a prism-coupled film thickness / refractometer "Model 2010 / M".

[0368] [Measurement of yellowness index (YI)]

[0369] The yellowness (YI) was measured using an ultraviolet-visible-near-infrared spectrophotometer "UH4150".

[0370] In addition, the abbreviations used in the synthesis examples and comparative synthesis examples are as follows.

[0371] BPEF: bisphenol fluorene epoxy resin represented by the general formula (40) (epoxy equivalent: 254 g / eq, weight average molecular weight (Mw): 508).

[0372]

[0373] (In formula (39), n represents a number greater than or equal to 0.)

[0374] BPF-EA: The reactant of BPEF and acrylic acid (equivalent reactant of epoxy group and carboxyl group).

[0375] BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride.

[0376] HPMDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride.

[0377] THPA: 1,2,3,6-Tetrahydrophthalic anhydride.

[0378] TEAB: tetraethylammonium bromide.

[0379] PGMEA: propylene glycol monomethyl ether acetate.

[0380] TPP: triphenylphosphine.

[0381] BHT: 2,6-di-tert-butyl-p-cresol.

[0382] [Synthesis of hydrogenated compounds]

[0383] (Synthesis Example 5)

[0384] In an autoclave with a stirring device and an internal volume of 1 L, 50 g of BPEF, 450 g of PGMEA as a solvent, and 5% Rh / C as a hydrogenation catalyst in an amount of 5.0 wt% relative to BPEF were added, and the mixture was reacted at 100° C. for 5 hours at a gauge pressure of 4.5 MPa under a hydrogen atmosphere, and then at 120° C. for further 5 hours. The catalyst was removed to obtain a hydrogenated compound 1.

[0385] [Calculation of hydrogenation rate]

[0386] (Hydrogenated compound 1 13 C-NMR measurement)

[0387] The hydrogenation rate of the hydrogenated compound 1 was calculated by the following procedure. First, about 50 mg of the hydrogenated compound 1 was dissolved in 600 μl of heavy chloroform (CDCl3) to prepare a sample for measurement. The sample was subjected to FT-NMR analysis at room temperature using a "JNMECA400" (manufactured by JEOL Ltd.). 13 C-NMR determination.

[0388] (Calculation method of hydrogenation rate)

[0389] In addition, when calculating the hydrogenation rate of hydrogenated compound 1, the model compound represented by the following general formula (41) is used as a reference, and each carbon atom is numbered from C1 to C14. Assuming that the model compound does not decompose due to the hydrogenation reaction, the integral value of the central quaternary carbon (C8) before and after the reaction is fixed. Therefore, using 13 The quantitative measurement results of C-NMR are used, and the presence rates of phenol residues and fluorene residues are obtained respectively based on the above C8, and the presence rates of the respective hydrogenated forms are calculated. The phenol residue presence rate is calculated by using the integral value of the quaternary carbon (C4). In addition, the fluorene residue presence rate is calculated by subtracting the calculated integral value of the phenol residue from the integral value of the entire aromatic region. In addition, the presence rate of the epoxy ring-opening form is also calculated based on the above C8 and the integral value of the -CH3 group (C1) in the ring-opening epoxy group.

[0390]

[0391] Hydrogenated compound 1 13In C-NMR, the presence ratios of hydrogenated phenylene and fluorene groups were determined based on the integral value (W: 0.208) of the quaternary carbon (C8) at the center of bisphenol fluorene found at 57 to 67 ppm, and the hydrogenation ratio was calculated. The presence ratio of phenylene was calculated using the integral value (X: 0.209) of the quaternary carbon (C4) found at 156 ppm. These values ​​were used to calculate the presence ratio of hydrogenated phenylene using the following formulas (2) and (3).

[0392] The presence ratio of phenylene groups [mol %] = X / (2×W)×100 (2)

[0393] The presence ratio of hydrogenated phenylene groups [mol %] = 100 - (the presence ratio of phenylene groups) (3)

[0394] The abundance of fluorenyl groups was calculated by subtracting the integrated value of phenylene groups from the integrated value of the entire aromatic region observed at 110 to 160 ppm (Y: 2.925). The abundance of fluorenyl groups and the abundance of hydrogenated fluorenyl groups were calculated using these values ​​using the following formulas (4) and (5).

[0395] The existence ratio of fluorene group [mol%] = (Y-6×X) / (12×W)×100 (4)

[0396] The presence ratio of hydrogenated fluorenyl groups [mol%] = 100 - (the presence ratio of fluorenyl groups) (5)

[0397] The presence rate of the ring-opened epoxy group is calculated based on the integral value (W) of the quaternary carbon (C8) and the integral value (Z: 0.0366) derived from the CH3 group observed at 18 to 20 ppm, and the presence rates of the ring-opened epoxy group and the epoxy group are calculated using the following formula (6) and formula (7).

[0398] The existence ratio of ring-opening epoxy groups [mol %] = Z / (2×W)×100 (6)

[0399] The presence ratio of epoxy groups [mol%] = 100 - (the presence ratio of ring-opening epoxy groups) (7)

[0400] (Synthesis Example 6)

[0401] A hydrogenated compound 2 was obtained in the same manner as in Synthesis Example 5 except that the reaction temperature was changed from 100°C to 150°C.

[0402] In addition, for the hydrogenated compound 2 obtained in Synthesis Example 6, the existence ratio of the hydrogenated phenylene group, the existence ratio of the hydrogenated fluorenyl group, and the existence ratio of the ring-opening epoxy group were calculated in the same manner as for the hydrogenated compound 1 obtained in Synthesis Example 5.

[0403] Table 6 shows the abundance ratios of the hydrogenated compound 1 and the hydrogenated compound 2 obtained in the above-mentioned Synthesis Examples 5 and 6.

[0404]

Table 6

[0405]

[0406] Table 7 shows the abundance ratios of the following general formulas (8) and (10) relative to the total of A1, A2, A3, and A4 of hydrogenated compound 1 and hydrogenated compound 2.

[0407]

[0408]

[0409] (In formula (10), * indicates the bonding position of the five-membered ring.)

[0410]

Table 7

[0411] Existence ratio of formula (8) and formula (10) [mol %] Hydrogenated compound 1 42 Hydrogenated compound 2 52

[0412] From the calculation results of the abundance ratios of hydrogenated phenylene groups in hydrogenated compounds 1 and 2 obtained in Synthesis Examples 5 and 6, it was found that hydrogenated compounds having the structure represented by the general formula (5) of the present invention were obtained.

[0413] [Synthesis of alkali-soluble resin]

[0414] (Synthesis Example 7)

[0415] In a 1000 ml four-necked flask with a reflux cooler, 150.0 g of a 40% PGMEA solution in which the hydrogenated compound 1 was dissolved, 15.0 g of acrylic acid, 1.1 g of TPP, and 0.2 g of BHT were added, and stirred at 100 to 105° C. for 8 hours to obtain the hydrogenated compound 1 containing an acrylate group (solid concentration; 44.1% by mass, weight average molecular weight: 780). Subsequently, 50.0 g of the hydrogenated compound 1 containing an acrylate group, 4.5 g of BPDA, and 2.3 g of THPA were added, and stirred at 120 to 125° C. for 10 hours to obtain an alkali-soluble resin (i)-8 (solid concentration: 60.1% by mass, weight average molecular weight (Mw): 1990, acid value (solid conversion): 82.7 mgKOH / g).

[0416] (Synthesis Example 8)

[0417] In a 1000 ml four-necked flask with a reflux cooler, 50.1 g of a hydrogenated compound 1 containing an acrylate group, 3.4 g of HPMDA and 2.4 g of THPA were added, and the mixture was stirred at 120 to 125° C. for 10 hours to obtain an alkali-soluble resin (i)-9 (solid content concentration: 61.3% by mass, weight average molecular weight (Mw): 2520, acid value (converted to solid content): 86.0 mgKOH / g).

[0418] (Synthesis Example 9)

[0419] In a 1000 ml four-necked flask with a reflux cooler, 150.0 g of a 40% PGMEA solution of the hydrogenated compound 2, 13.7 g of acrylic acid, 1.0 g of TPP, and 0.2 g of BHT were added, and stirred at 100 to 105° C. for 8 hours to obtain the hydrogenated compound 2 containing an acrylate group (solid concentration; 45.2% by mass, weight average molecular weight; 510). Subsequently, 50.0 g of the hydrogenated compound 2 containing an acrylate group, 4.3 g of BPDA, and 2.2 g of THPA were added, and stirred at 120 to 125° C. for 10 hours to obtain an alkali-soluble resin (i)-10 (solid concentration: 63.8% by mass, weight average molecular weight (Mw): 1900, acid value (solid conversion): 85.5 mgKOH / g).

[0420] (Synthesis Example 10)

[0421] In a 1000 ml four-necked flask with a reflux cooler, 50.0 g of a hydrogenated compound 2 containing an acrylate group, 3.3 g of HPMDA and 2.2 g of THPA were added, and the mixture was stirred at 120 to 125° C. for 10 hours to obtain an alkali-soluble resin (i)-11 (solid content concentration: 55.2% by mass, weight average molecular weight (Mw): 1480, acid value (converted to solid content): 89.0 mgKOH / g).

[0422] (Comparative Synthesis Example 4)

[0423] In a 1000 ml four-necked flask with a reflux cooler, 313.7 g of a 50% PGMEA solution of BPF-EA, 47.1 g of BPDA, 24.3 g of THPA, 0.43 g of TEAB and 8.5 g of PGMEA were added, and the mixture was stirred at 120 to 125°C for 6 hours to obtain an alkali-soluble resin (i)-12 (solid content concentration: 56.6% by mass, weight average molecular weight (Mw): 3600, acid value (converted to solid content): 89.4 mgKOH / g).

[0424] [Calculation of the number of aromatic rings]

[0425] The number of aromatic rings defined as the number of benzene rings present in the basic skeletons of the alkali-soluble resins (i)-8 to (i)-12 obtained in Synthesis Examples 7 to 10 and Comparative Synthesis Example 4 was calculated from the sum of (the number of benzene rings in each basic skeleton constituent component) × (the amount added (mol)). Table 8 shows the number of aromatic rings calculated from the added mol ratio of each constituent component in Synthesis Examples 7 to 10 and Comparative Synthesis Example 4.

[0426]

Table 8

[0427]

[0428] Next, the present invention will be specifically described based on examples and comparative examples of the photosensitive resin composition and the cured film, but the present invention is not limited to these examples. The raw materials and abbreviations used in the examples and comparative examples described below are as follows.

[0429] (i)-8: The alkali-soluble resin obtained in Synthesis Example 5.

[0430] (i)-9: Alkali-soluble resin obtained in Synthesis Example 6.

[0431] (i)-10: Alkali-soluble resin obtained in Synthesis Example 7.

[0432] (i)-11: Alkali-soluble resin obtained in Synthesis Example 8.

[0433] (i)-12: Alkali-soluble resin obtained in Comparative Synthesis Example 4.

[0434] (ii): Irgacure OXE01 (manufactured by BASF).

[0435] (iii): Megafac F-556 (manufactured by DIC Corporation, "Megafac" is a registered trademark of DIC Corporation).

[0436] (iv): Propylene glycol monomethyl ether acetate.

[0437] [Evaluation of photosensitive resin composition]

[0438] Table 9 shows the content of each component of the photosensitive resin composition solutions of Examples 9 to 12 and Comparative Example 5 (unit: mass %).

[0439]

Table 9

[0440] Element Example 9 Example 10 Embodiment 11 Example 12 Comparative Example 5 (i)-1 32.5 (i)-2 31.8 (i)-3 30.6 (i)-4 35.3 (i)-5 34.5 (ii) 0.4 0.4 0.4 0.4 0.4 (iii) 0.1 0.1 0.1 0.1 0.1 (iv) 67.0 67.7 68.9 64.2 65.0

[0441] (Preparation of Cured Film for Refractive Index Measurement)

[0442] The photosensitive resin composition solutions of Examples 9 to 12 and Comparative Example 5 were applied to a glass substrate using a spin coater to a dry film thickness of 1.5 μm and dried. The substrate was then irradiated with a 500 W high pressure mercury lamp at a wavelength of 365 nm and an illumination of 10 mW / cm2 without using a photomask. 2 Thereafter, a heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer to obtain a cured film (a glass substrate having a cured film formed thereon).

[0443] (Method for measuring refractive index)

[0444] The refractive index hardened film prepared above was measured using a prism-coupled film thickness / refractometer.

[0445] "Model 2010 / M" was used to measure the refractive index of the cured film in 633 nm light. The results are shown in Table 10. Figure 1 It shows the relationship between the number of aromatic rings and the refractive index.

[0446]

Table 10

[0447] Example 9 Example 10 Embodiment 11 Example 12 Comparative Example 5 Refractive Index 1.578 1.556 1.571 1.553 1.616

[0448] [Evaluation of light resistance]

[0449] In order to confirm the light resistance of the cured film composed of the photosensitive resin composition, the cured films of Examples 9 to 12 and Comparative Example 5 on the glass substrate were subjected to a low-pressure mercury lamp at 1200, 2400, and 3500 mJ / cm 2 The yellowing degree (YI) before and after exposure to a low-pressure mercury lamp (ΔYI) was calculated by the following formula (8).

[0450] ΔYI = (YI of the cured film after exposure) - (YI of the cured film before exposure) (8)

[0451] The yellowing degree (ΔYI) at each exposure amount is shown in Table 11. Figure 2 It shows the relationship between the exposure amount and the yellowing degree of the cured film.

[0452]

Table 11

[0453]

[0454] like Figure 1 As shown in Table 10, it is known that the refractive index can be lowered by adjusting the number of aromatic rings remaining in the molecule. That is, by using a photosensitive resin composition containing an alkali-soluble resin ((i)-8 to (i)-11) having a hydrogenated phenyl group and a fluorene group, a cured film having a lower refractive index can be obtained.

[0455] In addition, if Figure 2 As shown in Table 11, it can be seen that by using a photosensitive resin composition containing an alkali-soluble resin ((i)-8 to (i)-11) having a hydrogenated phenyl group and a fluorene group, discoloration of the cured film can be suppressed even when irradiated with ultraviolet light at a high exposure dose. This is considered to be because the number of aromatic rings having conjugated double bonds that easily absorb light in the ultraviolet region in the photosensitive resin composition of the present invention is small, so photolysis is less likely to occur.

[0456] (Industrial Applicability)

[0457] According to the alkali-soluble resin of the present invention, a photosensitive resin composition that can form a fine pattern and can meet the light resistance requirements can be obtained. Therefore, for example, it is used for touch panels, color filters, etc. That is, because the pattern can be formed by photoetching, it has the advantage that it can be formed by the existing photoetching step. In addition, because a thin film can be formed, the structure can be made thinner, which is suitable for the production of touch panels and color filters.

Claims

1. A method for producing an alkali-soluble resin containing a polymerizable unsaturated group, comprising: A reaction product of an epoxy compound (a) having a structure represented by the following general formula (1) and (meth) acrylic acid is reacted with a dicarboxylic acid or a tricarboxylic acid or a monoanhydride of a dicarboxylic acid or a tricarboxylic acid (b) and a tetracarboxylic acid or a dianhydride thereof (c); In formula (1), R1 independently represents a hydrocarbon group having 2 to 4 carbon atoms, R2 independently represents a hydrocarbon group having 1 to 3 carbon atoms, X represents a divalent organic group having 1 to 20 carbon atoms which may contain heteroelements, -CO-, -SO2-, -Si(CH3)2-, -O-, or a single bond, a independently represents a number having an average value of 0 to 10, b independently represents a number having an average value of 0 to 4, The dicarboxylic acid or tricarboxylic acid is at least one selected from succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, phthalic acid, isophthalic acid, and trimellitic acid, The tetracarboxylic acid is at least one selected from butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, pyromelitic acid, diphenyl ketonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ethertetracarboxylic acid, and diphenyl sulfonetetracarboxylic acid.

2. A method for producing an alkali-soluble resin containing a polymerizable unsaturated group, comprising reacting the alkali-soluble resin containing a polymerizable unsaturated group obtained by the production method according to claim 1 with an epoxy compound containing an unsaturated group represented by formula (30), In formula (30), R4 is a hydrogen atom or a methyl group, R5 independently represents a hydrocarbon group having 2 to 4 carbon atoms, and c represents a number of 0 or 1.

3. A method for producing an alkali-soluble resin containing a polymerizable unsaturated group, comprising reacting a hydroxyl group of the alkali-soluble resin containing a polymerizable unsaturated group obtained by the production method according to claim 2 with a dicarboxylic acid or a tricarboxylic acid or a monoanhydride of a dicarboxylic acid or a tricarboxylic acid, wherein: The aforementioned dicarboxylic acid or tricarboxylic acid is at least one selected from succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, phthalic acid, isophthalic acid, and trimellitic acid.

4. An alkali-soluble resin containing a polymerizable unsaturated group, the alkali-soluble resin having a structure represented by the following general formula (2) and obtained by the production method according to any one of claims 1 to 3; In formula (2), R1 independently represents a hydrocarbon group having 2 to 4 carbon atoms, R2 independently represents a hydrocarbon group having 1 to 3 carbon atoms, R3 represents a hydrogen atom or a methyl group, X represents a divalent organic group having 1 to 20 carbon atoms which may contain a heteroelement, -CO-, -SO2-, -Si(CH3)2-, -O- or a single bond, Y represents a tetravalent carboxylic acid residue, Z represents a hydrogen atom or a substituent represented by general formula (3), but at least one of Z represents a substituent represented by general formula (3), G represents a hydrogen atom or a substituent represented by general formula (4), a independently represents a number having an average value of 0 to 10, b independently represents a number having an average value of 0 to 4, and n represents a number having an average value of 1 to 20; In formula (3) and (4), R4 represents a hydrogen atom or a methyl group, R5 independently represents a hydrocarbon group having 2 to 4 carbon atoms, L represents a divalent or trivalent carboxylic acid residue, c represents a number of 0 or 1, d and e represent a number of 0, 1 or 2, and d+e represents a number of 1 or 2.

5. A hydrogenated compound, which is a hydrogenated compound represented by the following general formula (5); In formula (5), R 12 independently represent a hydrocarbon group having 2 to 4 carbon atoms, R 13 independently represent a hydrocarbon group having 1 to 3 carbon atoms, R 14 represents a glycidyl group or the following general formula (6), but R 14 At least one of them represents an epoxypropyl group, a independently represents a number with an average value of 0 to 10, b independently represents a number with an average value of 0 to 4, n represents a number with an average value of 0 to 10, A1 and A2 independently represent the following general formula (7) or general formula (8), A3 and A4 independently represent the following general formula (9) or general formula (10), and the presence rate of the general formula (8) and general formula (10) relative to the total of A1, A2, A3 and A4 is 10 mol% or more and 80 mol% or less; In formula (9), * represents the bonding position of the five-membered ring; In formula (10), * represents the bonding position of the five-membered ring.

6. The hydrogenated compound according to claim 5, wherein In the structure represented by the general formula (5), the presence ratio of the general formula (8) and the general formula (10) is 30 mol% or more and 60 mol% or less relative to the total of A1, A2, A3 and A4.

7. A diol or polyol represented by the following general formula (11); In formula (11), R 12 independently represent a hydrocarbon group having 2 to 4 carbon atoms, R 13 independently represent a hydrocarbon group having 1 to 3 carbon atoms, R 15 represents a hydrogen atom or a methyl group, a independently represents a number with an average value of 0 to 10, b independently represents a number with an average value of 0 to 4, n represents a number with an average value of 0 to 10, A1 and A2 independently represent the following general formula (7) or general formula (8), A3 and A4 independently represent the following general formula (9) or general formula (10), and the presence ratio of the general formula (8) and general formula (10) is 10 mol% or more and 80 mol% or less relative to the total of A1, A2, A3 and A4; In formula (9), * represents the bonding position of the five-membered ring; In formula (10), * represents the bonding position of the five-membered ring.

8. An alkali-soluble resin containing a polymerizable unsaturated group, an alkali-soluble resin represented by the following general formula (12); In formula (12), R 12 independently represent a hydrocarbon group having 2 to 4 carbon atoms, R 13 independently represent a hydrocarbon group having 1 to 3 carbon atoms, R 15 represents a hydrogen atom or a methyl group, R 16 represents a monovalent group obtained by reacting (meth)acrylic acid with a glycidyl group or a monovalent group formed by adding anhydride to the monovalent group, A1 and A2 independently represent the following general formula (7) or general formula (8), A3 and A4 independently represent the following general formula (9) or general formula (10), the presence rate of the general formula (8) and general formula (10) relative to the total of A1, A2, A3 and A4 is 10 mol% or more and 80 mol% or less, Y represents a tetravalent carboxylic acid residue, G represents a hydrogen atom or a substituent represented by general formula (13), a independently represents a number having an average value of 0 to 10, b independently represents a number having an average value of 0 to 4, and m represents a number having an average value of 0 to 10; In formula (9), * represents the bonding position of the five-membered ring; In formula (10), * represents the bonding position of the five-membered ring; In formula (13), R 17 independently represent a hydrogen atom or a methyl group, R 18 Each of them independently represents a hydrocarbon group having 2 to 4 carbon atoms, and c represents 0 or 1.

9. A method for producing a hydrogenated compound, comprising the following steps (i) and (ii), (i) a step of preparing a compound represented by the following general formula (14); and (ii) a step of hydrogenating the phenylene group or fluorenyl group of the aforementioned compound to obtain the hydrogenated compound according to claim 5; In formula (14), R 12 independently represents a hydrocarbon group having 2 to 4 carbon atoms, a independently represents a number having an average value of 0 to 10, and n represents a number having an average value of 0 to 10.

10. A method for producing a hydrogenated compound, comprising the following steps (iii) and (iv); (iii) a step of reacting the hydrogenated compound produced by the method according to claim 9 with (meth)acrylic acid; and (iv) after the above step (iii), a step of reacting a dicarboxylic acid or a tricarboxylic acid, or a monoanhydride of a dicarboxylic acid or a tricarboxylic acid, and a tetracarboxylic acid or a dianhydride thereof with the above hydrogenated compound, wherein: The dicarboxylic acid or tricarboxylic acid is at least one selected from succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, phthalic acid, isophthalic acid, and trimellitic acid, The tetracarboxylic acid is at least one selected from butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, pyromelitic acid, diphenyl ketonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ethertetracarboxylic acid, and diphenyl sulfonetetracarboxylic acid.

11. A photosensitive resin composition comprising: (A) the alkali-soluble resin containing a polymerizable unsaturated group according to claim 4 or claim 8; and (B) Photopolymerization initiator.

12. The photosensitive resin composition according to claim 11, comprising: (C) a photopolymerizable monomer having at least one polymerizable unsaturated group; and (D) The optional component is an epoxy compound or epoxy resin having two or more epoxy groups. 13 . The photosensitive resin composition according to claim 11 , further comprising (E) a dispersion medium.

14. The photosensitive resin composition according to claim 13, wherein The solid content of the component (A) in the photosensitive resin composition is 1 to 55% by mass, the component (C) is 0 to 100 parts by mass based on 100 parts by mass of the component (A), the component (B) is 0.1 to 40 parts by mass based on 100 parts by mass of the total amount of the component (A) and the component (C), and the component (E) is 1 to 95% by mass.

15. The photosensitive resin composition according to claim 11, wherein The aforementioned component (A) contains: An alkali-soluble resin containing a polymerizable unsaturated group represented by the aforementioned general formula (2); and A resin represented by the following general formula (15); The mass m of the polymerizable unsaturated group-containing alkali-soluble resin represented by the general formula (2) is A-1 The mass m of the resin represented by the above general formula (15) A-2 The ratio is m A-1 / m A-2 =75 / 25 to 25 / 75; In formula (15), R6, R7, R8, and R9 independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group, and R 10 independently represent a hydrocarbon group having 2 to 4 carbon atoms, R 11 represents a hydrogen atom or a methyl group; in addition, M represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-diyl or a single bond, Y represents a tetravalent carboxylic acid residue, Z represents a hydrogen atom or a substituent represented by the general formula (3), but at least one of Z represents a substituent represented by the general formula (3), G represents a hydrogen atom or a substituent represented by the general formula (4), d independently represents a number with an average value of 0 to 10, and m represents a number with an average value of 1 to 20; In formula (3) and (4), R4 represents a hydrogen atom or a methyl group, R5 independently represents a hydrocarbon group having 2 to 4 carbon atoms, L represents a divalent or trivalent carboxylic acid residue, c represents a number of 0 or 1, d and e represent a number of 0, 1 or 2, and d+e represents a number of 1 or 2. 16 . A cured film, the cured film being obtained by patterning the photosensitive resin composition according to claim 11 by a photolithography method, and curing the patterned photosensitive resin composition. 17 . A touch panel comprising the cured film according to claim 16 as a constituent component. 18 . A color filter comprising the cured film according to claim 16 as a constituent component.

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