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

文档序号：1137856 发布日期：2020-10-09 浏览：40次中文

阅读说明：本技术 碱可溶性树脂、氢化化合物及其制造方法、树脂组合物及其硬化膜、触控面板及滤光片 (Alkali-soluble resin, hydrogenated compound, method for producing same, resin composition, cured film of resin composition, touch panel, and optical filter ) 是由滑川崇平大嶋寛之清水健博于 2020-03-27 设计创作，主要内容包括：本发明涉及碱可溶性树脂、氢化化合物及其制造方法、树脂组合物及其硬化膜、触控面板及滤光片。具体地,涉及一种含有聚合性不饱和基的碱可溶性树脂的制造方法,该制造方法可得到低折射率且具有耐光性的显影特性优异的感光性树脂组合物。本发明课题的解决手段为一种含有聚合性不饱和基的碱可溶性树脂的制造方法,该方法为：使具有通式(1)所示结构的环氧化合物(a)和含有不饱和基的单羧酸的反应物,与二羧酸或三羧酸或是这些的单酸酐(b)、及四羧酸或其二酸酐(c)反应。<Image he="134" wi="700" file="DDA0002428875380000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention relates to an alkali-soluble resin, a hydrogenated compound, a method for producing the same, a resin composition, a cured film thereof, a touch panel, and an optical filter. More particularly, 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 developing properties with light resistance. The solution of the present invention is a method for producing an alkali-soluble resin containing a polymerizable unsaturated group, the method comprising: a reaction product of an epoxy compound (a) having a structure represented by general formula (1) and a monocarboxylic acid having an unsaturated group is reacted with a dicarboxylic acid or a tricarboxylic acid or a monoanhydride thereof (b) and a tetracarboxylic acid or a dianhydride thereof (c).)

1. A method for producing an alkali-soluble resin containing a polymerizable unsaturated group, comprising:

reacting a reactant of an epoxy compound (a) having a structure represented by the following general formula (1) and a monocarboxylic acid having an unsaturated group with a dicarboxylic acid or tricarboxylic acid or a monoanhydride of the dicarboxylic acid or tricarboxylic acid (b) and a tetracarboxylic acid or a dianhydride thereof (c);

in the formula (1), R₁Independently represents a C2-4 hydrocarbon group, R₂Independently represents a C1-3 hydrocarbon group, X represents a C1-20 2-valent organic group, -CO-, -SO, which may contain a hetero element therein₂-、-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.

2. A method for producing a polymerizable unsaturated group-containing alkali-soluble resin, which comprises reacting the polymerizable unsaturated group-containing alkali-soluble resin obtained by the production method according to claim 1 with a compound having a group capable of reacting with a carboxyl group and a polymerizable unsaturated group.

3. A method for producing a polymerizable unsaturated group-containing alkali-soluble resin, wherein a hydroxyl group of the polymerizable unsaturated group-containing alkali-soluble resin obtained by the production method according to claim 2 is further reacted with a dicarboxylic acid or tricarboxylic acid or a monoanhydride of the dicarboxylic acid or tricarboxylic acid.

4. An alkali-soluble resin containing a polymerizable unsaturated group, which has a structure represented by general formula (2) and is obtained by the production method according to any one of claims 1 to 3;

in the formula (2), R₁Independently represents a C2-4 hydrocarbon group, R₂Independently represents a hydrocarbon group having 1 to 3 carbon atoms, R₃Represents a hydrogen atom or a methyl group, X represents a C1-20 2-valent organic group which may contain a hetero element inside, -CO-, -SO₂-、-Si(CH₃)₂-, -O-or a single bond, Y represents a 4-valent carboxylic acid residue, Z represents a hydrogen atom or a substituent represented by the general formula (3), but at least 1 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), 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 the formulae (3) and (4), R₄Represents a hydrogen atom or a methyl group, R₅Independently represents a hydrocarbon group having 2 to 4 carbon atoms, L represents 2 or 3A 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 represented by the following general formula (5);

in the formula (5), R₁₂Independently represents a C2-4 hydrocarbon group, R₁₃Independently represents a hydrocarbon group having 1 to 3 carbon atoms, R₁₄Represents a glycidyl group or the following general formula (6), except that R₁₄At least 1 of which represents a glycidyl group, 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, n represents a number having an average value of 0 to 10, A₁、A₂Independently represents the following general formula (7) or general formula (8), A₃And A₄Independently represents the following general formula (9) or general formula (10) with respect to A₁、A₂、A₃And A₄The presence ratio of the general formula (8) and the general formula (10) is 1 mol% or more and 100 mol% or less in total;

in the formula (9), denotes the bonding position of the five-membered ring;

in the formula (10), the bond position of the five-membered ring is shown.

6. The hydrogenated compound according to claim 5, wherein in the structure represented by the general formula (5), A is represented by₁、A₂、A₃And A₄The presence ratio of the general formula (8) and the general formula (10) is 10 mol% or more and 80 mol% or less in total.

7. A diol or polyol represented by the following general formula (11);

in the formula (11), R₁₂Independently represents a C2-4 hydrocarbon group, R₁₃Independently represents a hydrocarbon group having 1 to 3 carbon atoms, R₁₅Represents a hydrogen atom or a methyl group, 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, n represents a number having an average value of 0 to 10, A₁、A₂Independently represents the following general formula (7) or general formula (8), A₃And A₄Independently represents the following general formula (9) or general formula (10) with respect to A₁、A₂、A₃And A₄The presence ratio of the general formula (8) and the general formula (10) is 1 mol% or more and 100 mol% or less in total;

in the formula (9), denotes the bonding position of the five-membered ring;

in the formula (10), the bond position of the five-membered ring is shown.

8. An alkali-soluble resin containing a polymerizable unsaturated group, which is represented by the following general formula (12);

in the formula (12), R₁₂Independently represents a C2-4 hydrocarbon group, R₁₃Independently represents a hydrocarbon group having 1 to 3 carbon atoms, R₁₅Represents a hydrogen atom or a methyl group, R₁₆Represents a monovalent group obtained by reacting (meth) acrylic acid with a glycidyl group or a monovalent group obtained by adding a monovalent groupMonovalent radicals formed by anhydride formation, A₁、A₂Independently represents the following general formula (7) or general formula (8), A₃And A₄Independently represents the following general formula (9) or general formula (10) with respect to A₁、A₂、A₃And A₄In which the general formula (8) and the general formula (10) are present in an amount of 1 to 100 mol%, Y represents a 4-valent carboxylic acid residue, G represents a hydrogen atom or a substituent represented by the 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 the formula (9), denotes the bonding position of the five-membered ring;

in the formula (10), denotes the bonding position of the five-membered ring;

in the formula (13), R₁₇Independently represents a hydrogen atom or a methyl group, R₁₈Independently represents a hydrocarbon group having 2 to 4 carbon atoms, and c represents a number of 0 or 1.

9. A process for producing a hydrogenated compound, which comprises 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 Cross phenyl group or fluorenyl group of the aforementioned compound;

in the formula (14), R₁₂Independently represents a hydrocarbon group having 2 to 4 carbon atoms, and a independently represents an average value ofA number from 0 to 10, and n represents a number having an average value of from 0 to 10.

10. A process for producing a hydrogenated compound, which comprises the following steps (iii) and (iv);

(iii) a step of reacting the hydrogenated compound produced by the method according to claim 9 with a monocarboxylic acid having an unsaturated group; and

(iv) (iv) a step of reacting the dicarboxylic acid or tricarboxylic acid or the monoanhydride of the dicarboxylic acid or tricarboxylic acid, and the tetracarboxylic acid or its dianhydride with the hydrogenation compound after the step (iii).

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) a photopolymerization initiator.

12. The photosensitive resin composition according to claim 11, which comprises:

an epoxy compound or an epoxy resin having 2 or more epoxy groups as an optional component (D).

13. The photosensitive resin composition according to claim 11, which contains (E) a dispersion medium.

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

15. The photosensitive resin composition according to claim 11, wherein the component (a) contains:

an alkali-soluble resin containing a polymerizable unsaturated group represented by the 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)_A-1The mass m of the resin represented by the above general formula (15)_A-2Is m_A-1/m_A-275/25 to 25/75;

in the formula (15), R₆、R₇、R₈And R₉Independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R₁₀Independently represents a C2-4 hydrocarbon group, R₁₁Represents 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 4-valent carboxylic acid residue, Z represents a hydrogen atom or a substituent represented by the general formula (3), but at least 1 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 having an average value of 0 to 10, and m represents a number having an average value of 1 to 20;

in the formulae (3) and (4), R₄Represents a hydrogen atom or a methyl group, R₅Independently represents a hydrocarbon group having 2 to 4 carbon atoms, L represents a2 or 3 valent carboxylic acid residue, c represents a number of 0 or 1, d and e represent numbers of 0, 1 or 2, and d + e represents a number of 1 or 2.

16. A cured film obtained by patterning the photosensitive resin composition according to any one of claims 11 to 15 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.

Technical Field

The present invention relates to: a method for producing a polymerizable unsaturated group-containing alkali-soluble resin, a hydrogenated compound and a method for producing the hydrogenated compound, a photosensitive resin composition, a cured film obtained by curing the photosensitive resin composition, and a touch panel and a color filter each containing the cured film as a constituent component.

Background

In recent years, due to the development of portable terminals, display devices such as touch panels and liquid crystal panels used outdoors or in vehicles have increased. In the display device, a light shielding film is provided in the touch panel frame to shield light leakage in the peripheral portion of the rear liquid crystal panel, and a black matrix is provided to suppress light leakage from the screen when the liquid crystal panel displays black and to suppress color mixing between adjacent color resists (color resists).

In a display device or the like, in order to suppress light leakage or the like and improve visual confirmation of a screen of the display device or the like, the concentration of a black pigment in a light-shielding film is increased, and the light-shielding property of the light-shielding film (light transmittance of the light-shielding film is reduced) is sometimes increased. Since the refractive index of the black pigment is higher than the refractive indices of the transparent substrate and the curable resin, if the concentration of the black pigment in the light-shielding film is increased, the reflectance is increased when viewed from the surface of the transparent substrate on which the light-shielding film is formed and the surface opposite to the surface on which the light-shielding film is formed. Therefore, reflection at the interface between the light-shielding film formed on the transparent substrate and the transparent substrate increases, and there occurs a problem that the light-shielding film is reflected or the boundary of the black matrix is conspicuous due to a difference in reflectance and the color filter colored portion. Further, a resin used for a high-quality black matrix forming resist has a high refractive index. Therefore, it is difficult to achieve both light-shielding properties and low reflectance merely by adjusting the black pigment concentration.

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

For example, patent document 1 discloses a resin film containing: at least 2 or more resins, a colorant, and a photoacid generator, wherein in a spectrum plotted with a scattering angle on the horizontal axis and a scattered light intensity on the vertical axis, the half-value width of a peak is a1, and the scattering angle of the maximum light intensity of the peak is a2, the peak has a1/a2 value of more than 0.1 and 2.5 or less in the light scattering measurement of the resin film. The resin film can form a phase separation structure by 2 or more kinds of resins, and thus has excellent low reflectivity.

[ Prior art documents ]

[ patent document ]

Patent document 1: international publication No. 2017/057192.

Disclosure of Invention

[ problems to be solved by the invention ]

However, the present inventors have examined and found that the resin film described in patent document 1 can reduce the reflectance, but may have poor appearance due to reduced surface smoothness or increased diffuse reflection due to the influence of surface irregularities. Therefore, there is an increasing demand for a photosensitive resin composition that can reduce the refractive index of the resin itself to achieve a desired reflectance and that has properties such as development properties required for use in the photosensitive resin composition and heat resistance and adhesion when used as a cured film.

The present invention has been made in view of the above points, and a first object of the present invention is to provide 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 development characteristics with light resistance, and an alkali-soluble resin containing a polymerizable unsaturated group. In addition, a second object is to provide a hydrogenated compound and a method for producing the hydrogenated compound. A third object of the present invention is to provide an alkali-soluble resin containing a polymerizable unsaturated group, a photosensitive resin composition containing the resin, a cured film obtained by curing the photosensitive resin composition, and a touch panel and a color filter containing the cured film as a constituent component.

[ means for solving the problems ]

The method for producing an alkali-soluble resin containing a polymerizable unsaturated group of the present invention comprises:

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

(in the formula (1), R₁Independently represents a C2-4 hydrocarbon group, R₂Independently represents a C1-3 hydrocarbon group, X represents a C1-20 2-valent organic group, -CO-, -SO, which may contain a hetero element therein₂-、-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. )

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

(in the formula (2), R₁Independently represents a C2-4 hydrocarbon group, R₂Independently represents a hydrocarbon group having 1 to 3 carbon atoms, R₃Represents a hydrogen atom or a methyl group, X represents a C1-20 2-valent organic group which may contain a hetero element inside, -CO-, -SO₂-、-Si(CH₃)₂-, -O-or a single bond, Y represents a 4-valent carboxylic acid residue, Z represents a hydrogen atom or a substituent represented by the general formula (3), provided that at least 1 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), 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 an average value of 0 to 4The average is a number from 1 to 20. )

(in the formulae (3) and (4), R₄Represents a hydrogen atom or a methyl group, R₅Independently represents a hydrocarbon group having 2 to 4 carbon atoms, L represents a2 or 3 valent carboxylic acid residue, c represents a number of 0 or 1, d and e represent numbers of 0, 1 or 2, and d + e represents a number of 1 or 2. )

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

(in the formula (5), R₁₂Independently represents a C2-4 hydrocarbon group, R₁₃Independently represents a hydrocarbon group having 1 to 3 carbon atoms, R₁₄Represents a glycidyl group or the following general formula (6), except that R₁₄At least 1 of which represents a glycidyl group, 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, n represents a number having an average value of 0 to 10, A₁、A₂Independently represents the following general formula (7) or general formula (8), A₃And A₄Independently represents the following general formula (9) or general formula (10) with respect to A₁、A₂、A₃And A₄The presence ratio of the general formula (8) and the general formula (10) is 1 mol% or more and 100 mol% or less in total. )

(in the formula (9),. phi.

(in the formula (10),. phi.

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

(in the formula (11), R₁₂Independently represents a C2-4 hydrocarbon group, R₁₃Independently represents a hydrocarbon group having 1 to 3 carbon atoms, R₁₅A represents a hydrogen atom or a methyl group, 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, n represents a number having an average value of 0 to 10, A1 and A2 independently represent the following general formula (7) or general formula (8), A₃And A₄Independently represents the following general formula (9) or general formula (10) with respect to A₁、A₂、A₃And A₄The presence ratio of the general formula (8) and the general formula (10) is 1 mol% or more and 100 mol% or less in total. )

(in the formula (9),. phi.

(in the formula (10),. phi.

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

(in the formula (12), R₁₂Independently represents a C2-4 hydrocarbon group, R₇Independently represents a hydrocarbon group having 1 to 3 carbon atoms, R₁₅Represents a hydrogen atom or a methyl group, R₁₆Represents a monovalent group formed by reacting a glycidyl group with (meth) acrylic acid or a monovalent group formed by adding an acid anhydride to the monovalent group, A₁、A₂Independently represents the following general formula (7) or general formula (8), A₃And A₄Independently represents the following general formula (9) or general formula (10) with respect to A₁、A₂、A₃And A₄In the above general formulae (8) and (10), the ratio of the total. )

(in the formula (9),. phi.

(in the formula (10),. phi.

(in the formula (13), R₁₇Represents a hydrogen atom or a methyl group, R₁₈Independently represents a hydrocarbon group having 2 to 4 carbon atoms, and c represents a number of 0 or 1. )

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

(in the formula (14), R₁₂Independently 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. )

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

(in the formula (2), R₁Independently represents a C2-4 hydrocarbon group, R₂Independently represents a hydrocarbon group having 1 to 3 carbon atoms, R₃Represents a hydrogen atom or a methyl group, X represents a C1-20 2-valent organic group which may contain a hetero element inside, -CO-, -SO₂-、-Si(CH₃)₂-, -O-or a single bond, Y represents a 4-valent carboxylic acid residue, Z represents a hydrogen atom or a substituent represented by the general formula (3), but at least 1 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), 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 the formula (12), R₁₂Independently represents a C2-4 hydrocarbon group, R₁₃Independently represents a hydrocarbon group having 1 to 3 carbon atoms, R₁₅Represents a hydrogen atom or a methyl group, R₁₆Represents a monovalent group formed by reacting a glycidyl group with (meth) acrylic acid or a monovalent group formed by adding an acid anhydride to the monovalent group, A₁、A₂Independently represents the following general formula (7) or general formula (8), A₃And A₄Independently represents the following general formula (9) or general formula (10) with respect to A₁、A₂、A₃And A₄In which the general formula (8) and the general formula (10) are present in an amount of 1 to 100 mol%, Y represents a 4-valent carboxylic acid residue, G represents a hydrogen atom or a substituent represented by the general formula (13), a independently represents a number having an average value of 0 to 10, and b independently represents a group having an average value of 0 to 4And m represents a number having an average value of 0 to 10. )

(in the formula (9),. phi.

(in the formula (10),. phi.

(in the formula (13), R₁₇Represents a hydrogen atom or a methyl group, R₁₈Independently represents a hydrocarbon group having 2 to 4 carbon atoms, and c is 0 or 1. )

The cured film of the present invention is obtained by patterning the photosensitive resin composition by a photolithography (photolithography) method and curing the patterned photosensitive resin composition.

The touch panel of the present invention contains the cured film as a constituent component.

The color filter of the present invention contains the cured film as a constituent.

[ efficacy of the invention ]

The present invention provides a method for producing an alkali-soluble resin containing a polymerizable unsaturated group, which can produce a photosensitive resin composition having a low refractive index and excellent light resistance and developing properties, and an alkali-soluble resin containing a polymerizable unsaturated group. Further, a hydrogenated compound and a method for producing the hydrogenated compound can be provided. Further, an alkali-soluble resin containing a polymerizable unsaturated group, a photosensitive resin composition containing the alkali-soluble resin, a cured film obtained 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.

Drawings

Fig. 1 is a graph showing a relationship between a refractive index and the number of aromatic rings of a cured film according to an embodiment of the present invention.

Fig. 2 is a graph showing the yellowing factor (Δ YI) of the cured film before and after exposure of the cured film according to the embodiment of the present invention.

Description of the symbols

None.

Detailed Description

The following describes embodiments of the present invention, but the present invention is not limited to the following embodiments. In the present invention, when the content of each component is 0 in the first decimal place, the notation below the decimal point is omitted.

The alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in 1 molecule represented by the following general formula (2) of the present invention can be obtained by: a reaction product of an epoxy compound (a) having 2 epoxy groups in 1 molecule and a monocarboxylic acid having an unsaturated group is reacted with a dicarboxylic acid or tricarboxylic acid or a monoanhydride of the dicarboxylic acid or tricarboxylic acid (b) and a tetracarboxylic acid or a dianhydride thereof (c). The polymerizable unsaturated group-containing alkali-soluble resin is an epoxy compound obtained by using an epoxy compound (a-1) as a raw material, wherein the epoxy compound (a-1) has a plurality of oxyalkylene groups and 2 cycloalkyl groups in 1 molecule.

(in the formula (2), R₁Independently represents a C2-4 hydrocarbon group, R₂Independently represents a hydrocarbon group having 1 to 3 carbon atoms, R₃Represents a hydrogen atom or a methyl group, X represents a C1-20 2-valent organic group which may contain a hetero element inside, -CO-, -SO₂-、-Si(CH₃)₂-, -O-or a single bond, Y represents a 4-valent carboxylic acid residue, Z represents a hydrogen atom or a substituent represented by the general formula (3), but at least 1 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), 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. )

The method for producing the alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in 1 molecule represented by the above general formula (2) (hereinafter referred to as "alkali-soluble resin represented by the general formula (2)") will be described in detail.

First, an epoxy compound (a-1) having 2 epoxycycloalkyl groups in 1 molecule represented by the following general formula (1) (hereinafter, also simply referred to as "epoxy compound (a-1) represented by the general formula (1)") is reacted with a monocarboxylic acid having an unsaturated group (e.g., (meth) acrylic acid), thereby obtaining an epoxy (meth) acrylate.

(in the formula (1), R₁Independently represents a C2-4 hydrocarbon group, R₂Independently represents a C1-3 hydrocarbon group, X represents a C1-20 2-valent organic group, -CO-, -SO, which may contain a hetero element therein₂-、-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. )

Examples of the monocarboxylic acid compound having an unsaturated group include acrylic acid and methacrylic acid, and also include compounds obtained by reacting acrylic acid or methacrylic acid with a monoanhydride such as succinic anhydride, maleic anhydride or phthalic anhydride.

The reaction of the epoxy compound (a-1) represented by the above general formula (1) with (meth) acrylic acid can be carried out by a known method. For example, Japanese patent application laid-open No. 4-355450 discloses: the diol compound containing a polymerizable unsaturated group can be obtained by using about 2 moles of (meth) acrylic acid for 1 mole of the epoxy compound having 2 epoxy groups. In the present invention, the compound obtained by the above reaction is a diol (d) represented by the general formula (16).

(in the formula (16), R₁Independently represents a C2-4 hydrocarbon group, R₂Independently represents a hydrocarbon group having 1 to 3 carbon atoms, R₃Represents a hydrogen atom or a methyl group, X represents a C1-20 2-valent organic group which may contain a hetero element inside, -CO-, -SO₂-、-Si(CH₃)₂-, -O-or a single bond. But 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. )

X in the epoxy compound (a-1) represented by the general formula (1) represents a C1-20 2-valent organic group, -CO-, -SO-which may contain a hetero element₂-、-Si(CH₃)₂-, -O-or a single bond. Examples of the 2-valent organic group having 1 to 20 carbon atoms which may contain a hetero element inside include a 2-valent hydrocarbon group, a 2-valent group having a carboxyl group at one or both ends of the hydrocarbon group, and the like. The hydrocarbon group may have an oxygen atom or an ester bond having an ether bond therein.

Examples of the 2-valent hydrocarbon group include: methylene group, vinyl group, propylene group, isopropylidene group(s) ((s))isopropylidene) And a straight-chain or branched hydrocarbon group such as a phenyl group, a secondary butenyl group, a methyl isobutenyl group, a hexenyl group, a decenyl group, or a dodecenyl group. Examples of the 2-valent group having an ester group at the end of the hydrocarbon group include 2-valent organic groups represented by the formulae (17) to (20).

(in the formula (17), g represents an integer of 1 to 20.)

(in the formula (18), h represents an integer of 2 to 20, and i represents an integer of 0 to 10.)

(in the formula (19), j represents an integer of 1 to 20.)

(in the formula (20), k represents an integer of 0 to 18, and l represents an integer of 1 to 10.)

The 2 cyclohexane rings in the above general formula (1) are bonded via X. The cyclohexane ring is bonded to the oxygen atom at the 1-and 2-positions, respectively, and is bonded to X at the 4-or 5-position. The bonding position of X may be either the 4-position or the 5-position, or may be randomly bonded between the 4-position and the 5-position.

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

(in the formula (21), R₁Independently represents a hydrocarbon group having 2 to 4 carbon atoms, and a independently represents a number having an average value of 0 to 10. )

(in the formula (22), R₁Independently represents a hydrocarbon group having 2 to 4 carbon atoms, and a independently represents a number having an average value of 0 to 10. )

(in the formula (23), R₁Independently represents a hydrocarbon group having 2 to 4 carbon atoms, and a independently represents a number having an average value of 0 to 10. )

(in the formula (24), R₁Independently represent a hydrocarbon having 2 to 4 carbon atomsA independently represents a number having an average value of 0 to 10, and g represents an integer of 1 to 20. )

(in the formula (25), R₁Independently 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. )

(in the formula (26), R₁Independently 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. )

(in the formula (27), R₁Independently 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. )

In the production of the polymerizable unsaturated group-containing alkali-soluble resin represented by the general formula (2), the reaction is usually carried out in a solvent optionally using a catalyst. The polymerizable unsaturated group-containing alkali-soluble resin represented by the above formula (2) is produced by synthesizing a diol (d) represented by the general formula (16), and subsequently reacting the synthesized polycarboxylic acid or an anhydride of the polycarboxylic acid with a monofunctional epoxy compound containing a polymerizable unsaturated group reactive with a carboxyl group, or the like.

Examples of the solvent include: cellosolve (cellosolve) solvents such as ethyl cellosolve acetate and butyl cellosolve acetate; high boiling point ether-based or ester-based 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. The reaction conditions of the solvent, catalyst, and the like used are not particularly limited, but for example, it is preferable to use a solvent having no hydroxyl group and a boiling point higher than the reaction temperature as the reaction solvent.

In addition, it is preferable to use a catalyst for the reaction between a carboxyl group and an epoxy group, and JP-A-9-325494 discloses ammonium salts such as tetraethylammonium bromide and benzyltriethylammonium chloride, phosphines such as triphenylphosphine and tris (2, 6-dimethoxyphenyl) phosphine, and the like.

Then, 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 1 molecule (hereinafter referred to as "alkali-soluble resin represented by the general formula (28)").

(in the formula (28), R₁Independently a hydrocarbon group of carbon number 2 to 4, R₂Independently represents a hydrocarbon group having 1 to 3 carbon atoms, R₃Represents a hydrogen atom or a methyl group, X represents a C1-20 2-valent organic group which may contain a hetero element inside, -CO-, -SO₂-、-C(CF₃)₂、-Si(CH₃)₂-, -O-or a single bond, Y represents a 4-valent carboxylic acid residue, and Z' represents a hydrogen atom or a substituent represented by the general formula (29). But 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 the formula (29), L represents a2 or 3-valent carboxylic acid residue, and r represents a number of 1 or 2.)

The acid component used for synthesizing the alkali-soluble resin represented by the general formula (28) is a polybasic acid component capable of reacting 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 tricarboxylic acid or a monoanhydride of a dicarboxylic acid or tricarboxylic acid (b) in combination with a tetracarboxylic acid or a dianhydride thereof (c). The carboxylic acid residue of the acid component may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further, these carboxylic acid residues may include bonds containing hetero elements such as-O-, -S-, and carbonyl groups.

The dicarboxylic acid or tricarboxylic acid or the monoanhydride of the dicarboxylic acid or tricarboxylic acid (b) may be a chain type hydrocarbon dicarboxylic acid or tricarboxylic acid, an alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, an aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid, or a monoanhydride of a dicarboxylic acid or tricarboxylic acid.

Examples of mono-anhydrides of chain hydrocarbon di-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, lateral oxygen glutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid; and mono-anhydrides of dicarboxylic acids or tricarboxylic acids to which an arbitrary substituent is introduced. In addition, examples of the monoanhydride of the alicyclic dicarboxylic acid or tricarboxylic acid include: and monoanhydrides such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, and the like, and monoanhydrides of dicarboxylic acids or tricarboxylic acids into which an arbitrary substituent is introduced. In addition, examples of the monoanhydride of the aromatic dicarboxylic acid or tricarboxylic acid include: monoanhydrides of phthalic acid, isophthalic acid, trimellitic acid, and the like, and monoanhydrides of dicarboxylic acids or tricarboxylic acids into which an arbitrary substituent is introduced.

Among the mono anhydrides of dicarboxylic acids and tricarboxylic acids, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid are more preferable, and succinic acid, itaconic acid, and tetrahydrophthalic acid are more preferable. Further, among the dicarboxylic acids or tricarboxylic acids, the monoanhydrides of the dicarboxylic acids or tricarboxylic acids are preferably used. The above-mentioned mono-anhydrides of the dicarboxylic acids or tricarboxylic acids may be used alone in 1 kind, or 2 or more kinds may be used in combination.

The tetracarboxylic acid or the dianhydride thereof (c) may be a chain hydrocarbon tetracarboxylic acid, an alicyclic hydrocarbon tetracarboxylic acid, an aromatic hydrocarbon tetracarboxylic acid, or a dianhydride thereof.

Examples of the chain hydrocarbon tetracarboxylic acids include: butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and chain hydrocarbon tetracarboxylic acids into which a substituent such as an alicyclic hydrocarbon group or an unsaturated hydrocarbon group has been introduced. Examples of the alicyclic tetracarboxylic acid include: cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornane-tetracarboxylic acid, and alicyclic tetracarboxylic acids into which a substituent such as a chain hydrocarbon group or an unsaturated hydrocarbon group has been introduced. In addition, examples of the aromatic tetracarboxylic acid include: pyromelic acid, diphenylketotetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, and the like.

Among tetracarboxylic acids or their dianhydrides, biphenyltetracarboxylic acid, diphenylketotetracarboxylic acid and diphenylethertetracarboxylic acid are more preferable, and biphenyltetracarboxylic acid and diphenylethertetracarboxylic acid are still more preferable. Among tetracarboxylic acids and dianhydrides thereof, the use of dianhydrides thereof is more preferable. The tetracarboxylic acid or the dianhydride thereof may be used alone in 1 kind, or 2 or more kinds may be used in combination.

The reaction of the diol (d) represented by the general formula (16) with the acid components (b) and (c) is not particularly limited, and a known method can be employed. For example, Japanese patent application laid-open No. 9-325494 discloses a method of reacting an epoxy (meth) acrylate with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140 ℃.

Here, it is preferable that the molar ratio of the diol (d), the dicarboxylic acid or tricarboxylic acid, or the mono-anhydride of the dicarboxylic acid or tricarboxylic acid (b), and the tetracarboxylic dianhydride (c) is (d): (b) the method comprises the following steps (c) 1: 0.01 to 1.0: 0.2 to 1.0, to thereby form a carboxyl group at the terminal of the compound.

For example, when the (b) monoanhydride and the (c) dianhydride are used, the reaction is preferably carried out so that the molar ratio [ (d)/[ (b)/2+ (c) ] of the polymerizable unsaturated group-containing diol (d) to the acid component amount [ (b)/2+ (c) ] becomes 0.5 to 1.0. When the molar ratio is 1.0 or less, the content of unreacted polymerizable unsaturated group-containing diol (d) is not increased, and therefore, the stability of the alkali-soluble resin composition with time can be improved. On the other hand, when the molar ratio exceeds 0.5, the terminal of the alkali-soluble resin represented by the general formula (2) does not become an acid anhydride, so that the increase in the content of unreacted dianhydride can be suppressed, and the stability of the alkali-soluble resin composition over time can be improved. The molar ratio of each component (d), (b) and (c) can be arbitrarily changed within the above range by adjusting the acid value and the molecular weight of the alkali-soluble resin represented by the general formula (2).

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

(in the formula (30), R₄Is a hydrogen atom or a methyl group, R₅Independently represents a hydrocarbon group having 2 to 4 carbon atoms, and c represents a number of 0 or 1. )

The molar ratio of the epoxy group of the unsaturated group-containing epoxy compound 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 (influenced by the magnitude of the polymerizable double bond amount) or the acid value of the alkali-soluble resin represented by the general formula (2). When the number of moles of the general formula (30) is 90% or less based on the total number of moles of the components (b) and (c) which is 2 times the number of moles, alkali developability can be imparted, and the composition can be used for a photosensitive resin composition having a photopatternable property. In addition, in order to provide the effect of improving the photoreaction sensitivity, 10% or more is necessary, and therefore, 10 to 90% is preferable, and 30 to 70% is more preferable. In addition, the acid value of the alkali-soluble resin represented by the general formula (2) to be used is more preferably 20 to 180, and still more preferably 30 to 120.

The weight average molecular weight (Mw) of the alkali-soluble resin represented by the general formula (2) of the present invention as measured by colloid permeation chromatography (GPC) is usually 1000 to 100000, preferably 2000 to 20000, in terms of polystyrene as measured by HLC-8220GPC (TOSOH Co., Ltd.). When the weight average molecular weight is 1000 or more, the decrease in pattern adhesion during alkaline development can be suppressed. When the weight average molecular weight is less than 100000, the solution viscosity of the photosensitive resin composition can be easily adjusted to a viscosity suitable for application without taking too much time for the alkali development. The alkali-soluble resin can be measured by colloid permeation chromatography (GPC) using "HLC-8220 GPC" (TOSOH Co., Ltd.).

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

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

(in the formula (31), Y is 4 valence carboxylic acid residue, Z is hydrogen atom or general formula (3) substituent, but at least 1 of Z is general formula (3) substituent, G represents hydrogen atom or general formula (4) substituent, W and W' represented by the general formula (34) shown later on the 2 valence organic group P and/or the general formula (35) shown later on the 2 valence organic group Q shown in the 2 valence organic group Q2 organic group, but f represents an average value of 1 to 20.)

(in the formulae (3) and (4), R⁴Represents a hydrogen atom or a methyl group, R⁵Independently represents a C2-4 hydrocarbon group, LRepresents a2 or 3 valent 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. )

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

(in the formula (32), R₆、R₇、R₈And R₉Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R₁₀Independently 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 (excluding 0) having an average value of 0 to 10. )

The component (a-2) is an epoxy compound having 2 glycidyl ether groups, which is obtained by reacting a bisphenol with epichlorohydrin. In this reaction, the diglycidyl ether compound is usually oligomerized, and thus, the diglycidyl ether compound is an oligomer represented by the general formula (31), but the m values of the respective molecules are different from each other, and the average value of m is more than 0 and 10 or less, and more preferably 0.05 to 5.

Examples of bisphenols used as the raw material of 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-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2-bis (4-hydroxy-3, 5-dichlorophenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 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-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9-bis (4-hydroxy-3-bromophenyl) fluorene, 9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene, 9-bis (4-hydroxy-3, 5-dichlorophenyl) fluorene, 9-bis (4-hydroxy-3, 5-dibromophenyl) fluorene, 4,4 '-biphenol (4, 4' -biphenol), 3 '-biphenol (3, 3' -biphenol), and derivatives of these bisphenols. Among the above bisphenols, 2-bis (4-hydroxyphenyl) propane is more preferable. The bisphenols used as the raw material of the component (a-2) may be used alone in 1 kind, or 2 or more kinds may be used in combination.

In the first step of producing the compound represented by the general formula (31), the component (a-1) and the component (a-2) are added so that the amount of the component (a-2) is 10 to 100 parts by mass (more preferably 30 to 60 parts by mass) per 100 parts by mass of the component (a-1), and reacted with (meth) acrylic acid 2 times the total molar number of the epoxy compounds (a-1) and (a-2) having 2 epoxy groups to obtain an epoxy (meth) acrylate (d'). As described above, the reaction is preferably carried out using a catalyst in a solvent. The epoxy (meth) acrylate (d') may be obtained by mixing an epoxy acrylate obtained by reacting 1 mole of (a-1) with 2 moles of (meth) acrylic acid and an epoxy acrylate obtained by reacting 1 mole of (a-2) with 2 moles of (meth) acrylic acid.

In the second step, the epoxy (meth) acrylate (d') obtained in the first step is reacted with a dicarboxylic acid or tricarboxylic acid or a monoanhydride thereof (b) and a tetracarboxylic acid or a dianhydride thereof (c) to obtain an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in 1 molecule of the general formula (33) (hereinafter referred to as "alkali-soluble resin of the general formula (33)").

(in the formula (33), Y represents a 4-valent carboxylic acid residue, Z 'represents a hydrogen atom or a substituent represented by the general formula (29), W and W' represent a 2-valent organic group P represented by the general formula (34) and/or a 2-valent organic group represented by a 2-valent organic group Q represented by the general formula (35), wherein f represents a number having an average value of 1 to 20.)

(in the formula (29), L represents a2 or 3-valent carboxylic acid residue, and r represents a number of 1 or 2.)

Here, when f in 1 molecule of each alkali-soluble resin represented by general formula (34) is an integer and the number of units represented by P and Q in 1 molecule is fP and fQ, respectively, f is fP + fQ. When W' is P, fQ ≠ 0; when W' is Q, fP is not equal to 0; when W' is P, W must contain Q; when W' is Q, W must contain P.

(in the formula (34), R₁Independently represents a C2-4 hydrocarbon group, R₂Independently represents a hydrocarbon group having 1 to 3 carbon atoms, R₃Represents a hydrogen atom or a methyl group, X represents a C1-20 2-valent organic group which may contain a hetero element inside, -CO-, -SO₂-、-Si(CH₃)₂-, -O-or a single bond. But 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. )

(in the formula (35), R₆、R₇、R₈And R₉Independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R₁₀Independently represents a C2-4 hydrocarbon group, R₁₁Is 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-bisA radical or a direct bond. But d independently represents a number having an average value of 0 to 10. )

In the second step, the kind, amount of the acid components (b) and (c) used for producing the alkali-soluble resin of the general formula (33), reaction conditions, and the like are the same as those used for producing the alkali-soluble resin of the general formula (28).

In the third step, an alkali-soluble resin represented by the general formula (33) is reacted with an epoxy compound having an unsaturated group represented by the general formula (30). This reaction is also carried out in the same manner as in the production of the alkali-soluble resin represented by the general formula (2) from the alkali-soluble resin represented by the general formula (28), to obtain the alkali-soluble resin represented by the general formula (31) from the alkali-soluble resin represented by the general formula (33). When the number of moles of the general formula (29) is 90% or less based on 2 times the total number of moles of the component (b) and the number of moles of the component (c), alkali developability can be imparted, and the photosensitive resin composition can be used for a photosensitive resin composition having a photopatternable property. In addition, in order to provide the effect of improving the photoreaction sensitivity, the number of moles of the general formula (29) is preferably 10 to 90%, more preferably 30 to 70%, because it is necessary to be 10% or more.

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

Next, an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in 1 molecule represented by general formula (12) (hereinafter referred to as "alkali-soluble resin represented by general formula (12)") will be described.

(in the formula (9),. phi.

(in the formula (10),. phi.

(in the formula (13), R₁₇Independently represents a hydrogen atom or a methyl group, R₁₈Independently represents a hydrocarbon group having 2 to 4 carbon atoms, and c is 0 or 1. )

First, the hydroxyphenyl 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 2 hydrogenated hydroxyphenyl groups and hydrogenated fluorenyl groups in 1 molecule.

(in the formula (5), R₁₂Independently representing a carbon number of 2 to 4Hydrocarbyl radical, R₁₃Independently represents a hydrocarbon group having 1 to 3 carbon atoms, R₁₄Represents a glycidyl group or the following general formula (6), except that R₁₄At least 1 of which represents a glycidyl group, 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, n represents a number having an average value of 0 to 10, A₁、A₂Independently represents the following general formula (7) or general formula (8), A₃And A₄Independently represents the following general formula (9) or general formula (10) with respect to A₁、A₂、A₃And A₄The presence ratio of the general formula (8) and the general formula (10) is 1 mol% or more and 100 mol% or less in total. )

(in the formula (9),. phi.

(in the formula (10),. phi.

In addition, in the structure represented by the general formula (5), A is the same as A₁、A₂、A₃And A₄The presence ratio of the general formula (8) and the general formula (10) is more preferably 1 mol% or more and less than 100 mol%, more preferably 10 mol% or more and 80 mol% or less, and still more preferably 30 mol% or more and 60 mol% or less. If relative to A₁、A₂、A₃And A₄The presence ratio of the general formula (8) and the general formula (10) in total of (a) and (b) is less than 100 mol%, and the aromatic compound can exhibit its characteristics such as heat resistance. In addition, if it is relative to A₁、A₂、A₃And A₄When the total of the general formulae (8) and (10) is 1 mol% or more, the refractive index of the photosensitive resin composition can be lowered and the photosensitive resin composition can be used as a photosensitive resin composition having excellent light resistanceConstituent components of the resin composition.

In the present embodiment, the epoxy compound (a-3) represented by the general formula (14) has a ratio of hydrogenated and ring-opened epoxy groups to the ratio of unhydrogenated epoxy groups of preferably 10 mol% or less, more preferably 1 mol% or less. When the percentage of epoxy groups hydrogenated and ring-opened 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.

The hydrogenation of the epoxy compound (a-3) represented by the above general formula (14) can be carried out by a known method (for example, Japanese patent application laid-open Nos. 11-217379 and 2002-097251). The hydrogenation ratio of the epoxy compound (a-3) represented by the above general formula (14) can be adjusted by adjusting the reaction time and the reaction temperature.

Then, the epoxy compound (a-3) represented by the above general formula (14) is reacted with a monocarboxylic acid (e.g., (meth) acrylic acid) having an unsaturated group to obtain an epoxy (meth) acrylate.

The reaction of the epoxy compound (a-3) represented by the above general formula (14) with (meth) acrylic acid can be carried out by a known method. For example, Japanese patent application laid-open No. 4-355450 discloses: 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 2 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).

(in the formula (11), R₁₂Independently represents a C2-4 hydrocarbon group, R₁₃Independently represents a hydrocarbon group having 1 to 3 carbon atoms, R₁₅Represents a hydrogen atom or a methyl group, 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, n represents a number having an average value of 0 to 10, A₁、A₂Independently represents the following general formula (7) or general formula (8), A₃And A₄Independently represents the following general formula (9) or general formula (10) with respect to A₁、A₂、A₃And A₄The presence ratio of the general formula (8) and the general formula (10) is 1 mol% or more and 100 mol% or less in total. )

(in the formula (9),. phi.

(in the formula (10),. phi.

The alkali-soluble resin represented by the general formula (12) is produced by synthesizing a diol or a polyol (d) represented by the general formula (11), and optionally reacting the synthesized polycarboxylic acid or an anhydride of the polycarboxylic acid with a monofunctional epoxy compound containing a polymerizable unsaturated group having reactivity with a carboxyl group, followed by addition reaction. In this production, a catalyst is usually used in a solvent to carry out the reaction, optionally.

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

The reaction of the carboxyl group with 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).

Then, the diol or polyol (d)) represented by the general formula (11) obtained by reacting an epoxy compound with (meth) acrylic acid is reacted with a dicarboxylic acid or tricarboxylic acid which is an acid component, or a monoanhydride (b) thereof and a tetracarboxylic acid or a dianhydride thereof (c) to obtain an alkali-soluble resin represented by the general formula (36).

(in the formula (36), R₁₂Independently represent a hydrocarbon having 2 to 4 carbon atomsRadical, R₁₃Independently represents a hydrocarbon group having 1 to 3 carbon atoms, R₁₄Represents a hydrogen atom or a methyl group, A₁、A₂Independently represents formula (7) or formula (8), A₃And A₄Independently represents the following general formula (9) or general formula (10) with respect to A₁、A₂、A₃And A₄In the above general formula (8) and the general formula (10), the total ratio is 1 mol% or more and 100 mol% or less, Y represents a 4-valent carboxylic acid residue, and Z represents a hydrogen atom or a substituent represented by the following general formula (29). But a 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 the formula (9),. phi.

(in the formula (10),. phi.

(in the formula (29), L independently represents a 2-or 3-valent carboxylic acid residue, and r independently represents a number of 1 or 2.)

The acid component used for synthesizing the alkali-soluble resin represented by the general formula (12) is a polybasic acid component capable of reacting with the hydroxyl group in the molecule of the diol or polyol (d) represented by the general formula (11), and it is necessary to use a dicarboxylic acid or tricarboxylic acid or monoanhydride (b) thereof and a tetracarboxylic acid or dianhydride (c) thereof in combination. The carboxylic acid residue of the acid component may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further, these carboxylic acid residues may include bonds containing hetero elements such as-O-, -S-, and carbonyl groups.

The dicarboxylic acid or tricarboxylic acid or the monoanhydride (b) thereof, the tetracarboxylic acid or the dianhydride thereof (c) may be the same compound as that used for producing the alkali-soluble resin represented by the general formula (2).

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 discloses a method of reacting an epoxy (meth) acrylate with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140 ℃.

Here, it is more preferable that the molar ratio of the diol or polyol (d), the dicarboxylic acid or tricarboxylic acid or the monoanhydride (b) thereof, the tetracarboxylic acid or dianhydride thereof (c) is (d): (b) the method comprises the following steps (c) 1: 0.01 to 1.0: 0.2 to 1.0, to thereby form a carboxyl group at the terminal of the compound.

For example, when the monoanhydride (b) and the dianhydride (c) are used, it is preferable to carry out the reaction so that the molar ratio [ (d)/[ (b)/2+ (c) ] of the diol or polyol (d) having a polymerizable unsaturated group to the acid component amount [ (b)/2+ (c) ] becomes 0.5 to 1.0. When the molar ratio is 1.0 or less, the content of unreacted diol or polyol compound having a polymerizable unsaturated group does not increase, and the stability of the alkali-soluble resin composition with time can be improved. On the other hand, when the molar ratio exceeds 0.5, the terminal of the alkali-soluble resin represented by the general formula (36) does not become an acid anhydride, and therefore, the increase in the content of unreacted dianhydride can be suppressed, and the stability of the alkali-soluble resin composition with time can be improved. The molar ratio of each component (d), (b) and (c) can be arbitrarily changed within the above range by adjusting the acid value and the molecular weight of the alkali-soluble resin represented by the general formula (36).

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

(in the formula (37), R₁₇Represents a hydrogen atom or a methyl group, R₁₈Independently represents a hydrocarbon group having 2 to 4 carbon atoms, and c represents a number of 0 or 1. )

The molar ratio of the epoxy group in the unsaturated group-containing epoxy compound represented by the general formula (37) to the carboxyl group represented by the general formula (36) can be arbitrarily changed for the purpose of adjusting the sensitivity of photoreaction (due to the amount of polymerizable double bonds) or the acid value of the alkali-soluble resin represented by the general formula (12). When the number of moles of the general formula (37) is 90% or less based on the total number of moles of the components (b) and (c) which is 2 times the number of moles, alkali developability can be imparted, and the composition can be used for a photosensitive resin composition having a photopatternable property. In addition, in the case where the effect of improving the photoreaction sensitivity is to be provided, it is required to be 10% or more, and therefore, it is 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) to be used is more preferably 20 to 180, and still more preferably 30 to 120.

The weight average molecular weight (Mw) of the alkali-soluble resin represented by the general formula (12) of the present invention as measured by colloid permeation chromatography (GPC) is usually 1000 to 100000, preferably 2000 to 20000, in terms of polystyrene as measured by HLC-8220GPC (TOSOH Co., Ltd.). When the weight average molecular weight is 1000 or more, the decrease in pattern adhesion during alkaline development can be suppressed. When the weight average molecular weight is less than 100000, the solution viscosity of the photosensitive resin composition suitable for application can be easily adjusted, and it does not take much time for the alkali development.

Next, a 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 and a photosensitive resin composition using the alkali-soluble resin represented by the general formula (12) of the present invention will be described. The ratio of the components of the photosensitive resin composition is different between the case where the dispersion medium (E) is contained and the case where the dispersion medium (E) is not contained, and the case where the dispersion medium (E) is not contained will be described later.

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

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

The photosensitive resin composition contains, in a solid content of the photosensitive resin composition, 1 to 55% by mass of the component (A), 0 to 100 parts by mass of the component (C) per 100 parts by mass of the component (A), 0.1 to 40 parts by mass of the component (B) per 100 parts by mass of the total amount of the components (A) and (C), and 1 to 95% by mass of the component (E).

Further, the 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 polymerizable unsaturated group-containing alkali-soluble resin represented by the formula (2)_A-1With the mass m of the resin represented by the formula (15)_A-2Is m_A-1/m_A-275/25 to 25/75.

(in the formula (2), R₁Independently represents a C2-4 hydrocarbon group, R₂Independently represents a hydrocarbon group having 1 to 3 carbon atoms, R₃Represents a hydrogen atom or a methyl group, X represents a C1-20 2-valent organic group which may contain a hetero element inside, -CO-, -SO₂-、-Si(CH₃)₂-, -O-or a single bond, Y represents a 4-valent carboxylic acid residue, Z represents a hydrogen atom or a substituent represented by the general formula (3), at least 1 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), and a independently represents an averageValues from 0 to 10, b independently represents a number having an average value from 0 to 4, and n represents a number having an average value from 1 to 20. )

(in the formula (15), R₆、R₇、R₈And R₉Independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R₁₀Represents a C2-4 hydrocarbon group, R₁₁Represents 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 4-valent carboxylic acid residue, and Z is a hydrogen atom or a substituent represented by the general formula (3). At least 1 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 having an average value of 0 to 10, and m represents a number having an average value of 1 to 20. )

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

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

Examples of the photopolymerization initiator (B) in the photosensitive resin composition of the present invention include: acetophenones such as acetophenone, 2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone and p-tert-butyl acetophenone; diphenylketones such as diphenylketone, 2-chlorodiphenylketone, and p, p' -bisdimethylaminodiphenylketone; benzoin ethers such as dibenzoyl (benzil), benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; biimidazole compounds such as 2- (o-chlorophenyl) -4, 5-phenylbiimidazole, 2- (o-chlorophenyl) -4, 5-bis (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4, 5-diphenylbiimidazole, 2- (o-methoxyphenyl) -4, 5-diphenylbiimidazole, and 2,4, 5-triarylbiimidazole; halomethyl oxadiazole compounds such as 2-trichloromethyl-5-styryl-1, 3, 4-oxadiazole, 2-trichloromethyl-5- (p-cyanobenzyl) -1,3, 4-oxadiazole, and 2-trichloromethyl-5- (p-methoxystyryl) -1,3, 4-oxadiazole; 2,4, 6-Ginseng (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) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxystyryl) -4, 6-bis (trichloromethyl) -1, halomethyl-s-triazine compounds such as 3, 5-triazine, 2- (3,4, 5-trimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, and 2- (4-methylthiostyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine; o-acyloxime-based compounds such as 1, 2-octanedione, 1- [4- (phenylthio) phenyl ] -,2- (O-benzoyloxime), 1- (4-phenylthiophenyl) butane-1, 2-dione-2-oxime-O-benzoate, 1- (4-methylthiophenyl) butane-1, 2-dione-2-oxime-O-acetate, and 1- (4-methylthiophenyl) butane-1-ketoxime-O-acetate; sulfur compounds such as benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2, 4-diethylthioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1, 2-benzoanthraquinone, and 2, 3-diphenylanthraquinone; organic peroxides such as azobisisobutylonitrile, benzoyl peroxide, cumene peroxide and the like; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole; and tertiary amines such as triethanolamine and triethylamine. These photopolymerization initiators may be used alone in 1 kind or in combination of 2 or more kinds.

In particular, when a photosensitive resin composition containing a colorant is prepared, it is preferable to use O-acyloxime compounds (including ketoximes). Specific examples of the compound group include O-acyloxime photopolymerization initiators represented by the general formula (38) or (39). Of these, the O-acyloxime-based photopolymerization initiator having a molar absorption coefficient of 10000L/mol cm or more for 365nm is more preferable when the colorant is used at a high pigment concentration and when the light-shielding film pattern is formed. The term "photopolymerization initiator" used in the present invention includes a sensitizer.

(in the formula (38), R₁₉、R₂₀Each independently represents an alkyl group of C1 to C15, an aryl group of C6 to C18, an arylalkyl group of C7 to C20, or a heterocyclic group of C4 to C12, R₂₁Represents an alkyl group of C1 to C15, an aryl group of C6 to C18, an arylalkyl group of C7 to C20. Here, the alkyl group and the aryl group may be substituted with an alkyl group of C1 to C10, an alkoxy group of C1 to C10, an alkanoyl group of C1 to C10, and a halogen, and the alkylene portion may also include an unsaturated bond, an ether bond, a thioether bond, and an ester bond. The alkyl group may be any of linear, branched, and cyclic alkyl groups. )

(in the formula (39), R₂₂And R₂₃Each independently a linear or branched alkyl group having 1 to 10 carbon atoms; or cycloalkyl, cycloalkylalkyl or alkylcycloalkyl of carbon number 4 to 10; or phenyl which may be substituted with an alkyl group having 1 to 6 carbon atoms. R₂₄Independently represents a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, wherein-CH in the alkyl or alkenyl group₂Part of the-groups may be substituted by-O-groups. In addition, these R₂₂To R₂₄A part of the hydrogen atoms in the group (2) may be substituted with a halogen atom. )

The photosensitive resin composition of the present invention may contain a solvent. Examples of the above solvent include: alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α -terpineol and β -terpineol; ketones such as acetone, methylethylketone, cyclohexanone, and N-Methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, ethyl cellosolve, 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, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. These are used alone or in combination with 2 or more kinds of them, and dissolved and mixed, thereby a uniform solution composition can be prepared. 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.

In the photosensitive resin composition of the present invention, (C) a photopolymerizable monomer having at least 1 ethylenically unsaturated bond and (D) an epoxy compound or an epoxy resin having 2 or more epoxy groups may be optionally added in addition to the alkali-soluble resin having the specific structure (a) and the photopolymerization initiator (B) described above, and these (C) component and (D) component may be used in combination.

Examples of the photopolymerizable monomer (C) in the photosensitive resin composition of the invention include: (meth) acrylic acid esters 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 di (meth) acrylate, pentaerythritol tri (meth) acrylate, (meth) acrylates such as pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate or dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, alkylene oxide-modified hexa (meth) acrylate of phosphazene, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like; polyfunctional acrylates of the dendrimer (dendrimer) type. These photopolymerizable monomers may be used alone in 1 kind, or 2 or more kinds may be used in combination.

In addition, the photopolymerizable monomer having at least 1 ethylenically unsaturated bond is preferably crosslinked with each other using molecules of an alkali-soluble resin having 2 or more photopolymerizable groups and containing an unsaturated group. The photopolymerizable monomer (C) having at least 1 ethylenically unsaturated bond does not have a free carboxyl group.

Examples of the epoxy resin or epoxy compound having 2 or more epoxy groups (D) in the photosensitive resin composition of the present invention include: 3,3 ', 5,5 ' -tetramethyl-4, 4 ' -biphenol-type epoxy resin, bisphenol a (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-oxacyclopropane) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol, epoxy silicone resin, and the like. These may be used alone in 1 kind or in combination of plural kinds.

In the photosensitive resin composition not containing the component (E), the blending ratio of the component (C) and/or the component (D) is preferably 0 to 100 parts by mass relative to 100 parts by mass of the component (a); in the case of using the component (D), the amount of the component (D) is preferably 5 to 30 parts by mass based on 100 parts by mass of the total amount of the components (A) and (C). The component (C) is used for the purpose of improving the sensitivity of the photosensitive resin composition to the photo-curing reaction, and the sensitivity is improved when the amount added is increased. However, if the component (D) is added in an amount larger than that of the component (a), the alkali solubility of the photosensitive resin composition becomes insufficient, and the developability is lowered. On the other hand, the component (D) is added for the purpose of improving the physical properties of the photopatterned film by thermal curing following a photo-curing reaction and an alkali development, and particularly when an epoxy compound having 2 or more epoxy groups is used, the surface hardness and the like can be improved by crosslinking the resin component. However, if the amount of the photo-curing component is too large, the photo-patterning property is adversely affected.

The photosensitive resin composition may be a photosensitive resin composition to which the dispersion medium (E) is added. When the photosensitive resin composition containing a dispersion medium is used, the content of the component (a) is preferably 1 to 55% by mass, the component (C) is preferably 0 to 100 parts by mass, and the component (B) is preferably 0.1 to 40 parts by mass, and the component (E) is preferably 1 to 95% by mass, based on 100 parts by mass of the total amount of the components (a) and (C), the component (D) is preferably 5 to 30 parts by mass, based on 100 parts by mass of the total amount of the components (a) and (C), when the component (D) is used, the component (a) is contained in an amount of 1 to 55% by mass, based on 100 parts by mass of the component (a).

The dispersion medium (E) usable in the present invention is a dispersion medium in which the dispersion medium (E) is dispersed with an average particle diameter of 1 to 1000nm (an average particle diameter measured by a particle diameter distribution meter by a laser diffraction/scattering method or a particle diameter distribution meter by a dynamic light scattering method), and a known dispersion medium used for a conventional photosensitive resin composition can be used without particular limitation.

Here, examples of the black pigment include: perylene black, cyanine black, aniline black, carbon black, titanium black, and the like. Examples of color-mixed organic pigments include: a pigment mixed with at least 2 colors selected from organic pigments such as azo pigments, condensed azo pigments, methine azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, vat (threne) pigments, perylene pigments, perinone pigments, quinolinone pigments, diketopyrrolopyrrole pigments, thioindigo pigments, and the like. Examples of the white pigment include: titanium oxide pigments, composite oxide pigments; inorganic fillers such as calcium silicate, magnesium carbonate, calcium sulfate, and barium sulfate. These components (E) may be used alone in 1 kind, or in combination of 2 or more kinds, depending on the intended function of the photosensitive resin composition.

The dispersion medium (E) may be used singly or in combination of two or more kinds depending on the intended function of the photosensitive resin composition. For example, the following dispersion media can be appropriately selected and used: the light-shielding light resistance used for manufacturing the black matrix of the color filter can use carbon black, titanium black, black organic pigment and the like; as the colored resist used for manufacturing pixels (pixels) of the color filter, red, orange, yellow, green, blue, violet organic pigments and the like can be used; as the solder resist used for producing the insulating film of the printed wiring board, organic pigments, inorganic fillers, and the like can be used; the decorative light resistance used in the design of the front glass of the touch panel can use carbon black, titanium black, black organic pigment, white pigment and the like; as the transparent resist having high hardness and high durability, a transparent filler such as silica is used.

Examples of the organic pigment that can be used as the component (E) include, but are not limited to, organic pigments having color material index names shown below.

Pigment Red (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, and the like;

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

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.;

pigment green 7, 36, 58, etc.;

pigment blue 15, 15: 1. 15: 2. 15: 3. 15: 4. 15: 6. 16, 60, 80, etc.;

pigment violet 19, 23, 37, and the like.

(E) The blending ratio of the colorant of the component (b) may be arbitrarily determined depending on the desired light-shielding degree, but is preferably 1 to 80% by mass relative to the solid content in the photosensitive resin composition.

The component (E) is generally mixed with other blending components as a dispersion dispersed in a solvent (colorant dispersion in the case of a colorant), and in this case, a dispersant (component E') may be added. As the dispersant, there can be used, without particular limitation, known compounds (commercially available compounds such as dispersants, dispersion wetting agents, and dispersion promoters) used for dispersing pigments (colorants).

Examples of the dispersant include: a cationic polymer dispersant, an anionic polymer dispersant, a nonionic polymer dispersant, and a pigment derivative type dispersant (dispersing aid). In particular, the dispersant is preferably a cationic polymer dispersant having a cationic functional group such as an imidazole group, a pyrrole group, a pyridine group, a primary amino group, a secondary amino group or a tertiary amino group, an amine value of 1 to 100mgKOH/g, and a number average molecular weight of 1 to 10 ten thousand, in terms of adsorption to the colorant. The amount of the dispersant blended is preferably 1 to 35% by mass, more preferably 2 to 25% by mass, relative to the colorant. In addition, high-viscosity substances such as resins generally have an effect of stabilizing dispersion, but high-viscosity substances having no ability to promote dispersion are not used as a dispersant. However, the use of a high-viscosity material for the purpose of stabilizing dispersion is not limited.

As described above, the photosensitive resin composition of the present invention can be used for applications in which light resistance is required, for example, by using a photosensitive resin composition to which various dispersion media (E) are added.

In addition, other resin components that are polymerized or hardened by light or heat may be optionally used in combination in the present invention. Other resin components may be exemplified by: alkali-soluble resins obtained by reacting novolak epoxy resins derived from novolak resins such as phenol novolak and cresol novolak with (meth) acrylic acid and an acid anhydride, alkali-soluble resins obtained by reacting carboxyl groups in a copolymer of (meth) acrylic acid and (meth) acrylic esters with epoxy group-containing (meth) acrylic esters, and the like.

The photosensitive resin composition of the present invention may optionally contain: a resin other than the component (A) such as an epoxy resin, a curing agent, a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a surfactant, a coupling agent, and the like. Examples of the thermal polymerization inhibitor and the antioxidant include: hydroquinone, hydroquinone monomethyl ether, benzenetriol, t-butyl catechol, phenothiazine, hindered phenol compounds, and the like. Examples of plasticizers include: dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of the filler include: glass fibers, silica, mica, alumina, and the like. Examples of defoaming or leveling agents include: silicone, fluorine, and acrylic compounds. Examples of the surfactant include: fluorine-based surfactants, silicone-based surfactants, and the like. Examples of coupling agents include: 3- (glycidyloxy) propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, etc.

The cured film of the present invention is formed by photolithography using the photosensitive resin composition of the present invention. The production process includes the following steps: first, a photosensitive resin composition solution is applied to a substrate surface, followed by drying of a solvent [ prebake (prebake) ], then a photomask is placed on the thus obtained coating film, ultraviolet rays are irradiated to cure an exposed portion, an unexposed portion is dissolved out using an alkali aqueous solution, and a pattern is formed by development, and further, post-cure is performed (postbake). As the substrate to which the photosensitive resin composition solution is applied, glass, a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, or the like), or the like can be used.

As a method for applying the photosensitive resin composition solution to the substrate, any of methods using a roll coater, a land coater, a slit coater, a spinner (spinner), and the like can be used, in addition to the known solution dipping method and spraying method. After coating to a desired thickness by these methods, the coating film is formed by removing the solvent (prebaking). Prebaking is performed by heating with an oven, a hot plate, or the like. The heating temperature and the heating time of the prebaking may be appropriately selected depending on the solvent used, and are preferably, for example, from 1 to 10 minutes at 80 to 120 ℃.

As the radiation used for exposure, for example: visible rays, ultraviolet rays, far ultraviolet rays, electron rays, X-rays, etc., and the wavelength range of the radiation is preferably 250 to 450 nm. In addition, a developer suitable for this alkali development may use, for example: sodium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, and the like. These developing solutions can be appropriately selected depending on the characteristics of the resin layer, but it is also effective to add a surfactant optionally. The developing temperature is preferably 20 to 35 ℃, and a fine image can be formed precisely using a commercially available developing machine, ultrasonic washing machine, or the like. In addition, the alkali development is usually followed by water washing. The developing treatment method can be applied: a shower development (shower development) method, a spray development method, a dipping development (dipping) method, a liquid coating (puddle) method, and the like.

The alkali development after the exposure is performed for the purpose of removing the photosensitive resin composition in the unexposed portion, and a desired pattern is formed by the development. Suitable developers for this alkaline development are, for example: aqueous solutions of alkali metal and alkaline earth metal carbonates, aqueous solutions of alkali metal hydroxides, and the like. However, it is preferable to use a weakly alkaline aqueous solution containing 0.03 to 1 wt% of a carbonate salt such as sodium carbonate or potassium carbonate and develop the solution at a temperature of 23 to 27 ℃, and a fine image can be formed precisely by using a commercially available developing machine, an ultrasonic washing machine, or the like.

After development in this manner, heat treatment (post-baking) is performed at 180 to 250 ℃ for 20 to 100 minutes. However, when the heat resistance of a substrate or the like to be formed into a film is low, the blending of the composition may be designed so as to be carried out under post-baking conditions of 80 to 180 ℃ for 30 to 100 minutes. The post baking is performed for the purpose of improving adhesion between the patterned coating film and the substrate. The baking thereafter can be performed by heating with an oven, a hot plate, or the like, as in the case of the prebaking. The patterned hard film of the present invention is formed through the above steps by the photolithography method.

(examples)

Hereinafter, embodiments of the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these embodiments. In the following examples 1 and 2, unless otherwise specified, various measurements and evaluations were performed in the following manners. When the same model is used for each measurement device, the manufacturer name of the device is omitted from the second time. In examples 1 and 2, the same treatment was applied to both glass substrates used for producing the cured films for measurement.

[ example 1]

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

[ solid concentration ]

A glass filter was impregnated with 1g of the resin solution and the photosensitive resin composition obtained in each of the synthesis examples and comparative synthesis examples (mass: w₀(g) In (c), and weighing [ W ]₁(g) The mass [ W ] after heating at 160 ℃ for 2 hours was determined by the following equation (1)₂(g)〕。

The solid concentration (mass%) is 100 × (W)₂-W₀)/(W₁-W₀)(1)

[ acid value ]

The resin solution was dissolved in tetrahydrofuran, and the solution was titrated with 1/10N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Pongan industries Co., Ltd.) so that the amount of KOH required per 1g of solid content was used as the acid value.

[ molecular weight ]

The weight average molecular weight (Mw) was determined by Gel Permeation Chromatography (GPC) using "HLC-8220 GPC" (manufactured by TOSOH Co., Ltd., solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2X) + TSKgelSuperH-3000 (1X) + TSKgelSuperH-4000 (1X) + TSKgelSuperH-5000 (1X) (manufactured by TOSOH Co., Ltd.), temperature: 40 ℃ and rate: 0.6 ml/min) and converted to standard polystyrene (PS-Oligomer Kit, manufactured by TOSOH Co., Ltd.).

The abbreviations used in the synthesis examples and comparative synthesis examples are as follows.

HBPA-EA 1: a reactant of hydrogenated bisphenol a epoxy resin (epoxy equivalent 201g/eq) (having a skeleton of general formula (1)) and acrylic acid (equivalent reactant of epoxy group and carboxyl group).

HBPA-EA 2: a reactant of hydrogenated bisphenol a epoxy resin (epoxy equivalent 265g/eq) (having a skeleton of general formula (1)) and acrylic acid (equivalent reactant of epoxy group and carboxyl group).

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

BPF-EA: a reactant of bisphenol fluorene type epoxy resin (epoxy equivalent 250g/eq) (having a skeleton of general formula (33)) and acrylic acid (equivalent reactant of epoxy group and carboxyl group).

BPDA: 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride.

HPMDA: 1,2,4, 5-cyclohexanetetracarboxylic dianhydride.

THPA: 1,2,3, 6-tetrahydrophthalic anhydride.

TEAB: tetraethylammonium bromide.

PGMEA: propylene glycol monomethyl ether acetate.

(Synthesis example 1)

A50% PGMEA solution (329.1g) of HBPA-EA1, BPDA (44.1g), THPA (22.8g), TEAB (0.43g) and PGMEA (8.5g) were charged into a 1000ml four-necked flask equipped with a reflux condenser, and the mixture was stirred at 120 to 125 ℃ for 6 hours to obtain alkali-soluble resin (i) -1 (solid content: 61.2 mass%, weight average molecular weight (Mw) 3210, acid value (in terms of solid content): 123.1 mgKOH/g).

(Synthesis example 2)

A50% PGMEA solution (340.0g) of HBPA-EA1, HPMDA (34.7g), THPA (23.6g), TEAB (0.43g) and PGMEA (8.5g) were put in a 1000ml four-necked flask equipped with a reflux condenser, and stirred at 120 to 125 ℃ for 6 hours to obtain alkali-soluble resin (i) -2 (solid content concentration: 61.1 mass%, weight average molecular weight (Mw): 3230, acid value (solid content conversion): 120.4 mgKOH/g).

(Synthesis example 3)

A50% PGMEA solution (338.2g) of HBPA-EA2, BPDA (36.8g), THPA (19.0g), TEAB (0.43g) and PGMEA (8.5g) were charged into a 1000ml four-necked flask equipped with a reflux condenser, and stirred at 120 to 125 ℃ for 6 hours to obtain alkali-soluble resin (i) -3 (solid content: 73.8 mass%, weight average molecular weight (Mw): 4980, acid value (solid content conversion): 93.0 mgKOH/g).

(Synthesis example 4)

A50% PGMEA solution (338.2g) of HBPA-EA2, HPMDA (28.0g), THPA (19.0g), TEAB (0.43g) and PGMEA (8.5g) were put in a 1000ml four-necked flask equipped with a reflux condenser, and stirred at 120 to 125 ℃ for 6 hours to obtain alkali-soluble resin (i) -4 (solid content concentration: 64.2 mass%, weight average molecular weight (Mw): 3960, and acid value (solid content conversion): 100.8 mgKOH/g).

(comparative Synthesis example 1)

A50% PGMEA solution (325.1g) of BPA-EA, BPDA (45.6g), THPA (23.6g), TEAB (0.43g) and PGMEA (8.5g) were charged into a 1000ml four-necked flask equipped with a reflux condenser, and the mixture was stirred at 120 to 125 ℃ for 6 hours to obtain alkali-soluble resin (i) -5 (solid content concentration: 68.5 mass%, weight average molecular weight (Mw) 2080 and acid value (solid content conversion): 113.0 mgKOH/g).

(comparative Synthesis example 2)

A50% PGMEA solution (335.6g), HPMDA (35.9g), THPA (24.3g), TEAB (0.43g) and PGMEA (8.5g) of BPA-EA were charged into a 1000ml four-necked flask equipped with a reflux condenser, and stirred at 120 to 125 ℃ for 6 hours to obtain alkali-soluble resin (i) -6 (solid content concentration: 69.5 mass%, weight average molecular weight (Mw): 2630, acid value (in terms of solid content): 116.5 mgKOH/g).

(comparative Synthesis example 3)

A50% PGMEA solution (313.7g), BPDA (47.1g), THPA (24.3g), TEAB (0.43g) and PGMEA (8.5g) of BPF-EA were charged into a 1000ml four-necked flask equipped with a reflux condenser, and stirred at 120 to 125 ℃ for 6 hours to obtain alkali-soluble resin (i) -7 (solid content: 56.55 mass%, weight average molecular weight (Mw): 3600, acid value (in terms of solid content): 103.0 mgKOH/g).

The present invention will be specifically described with reference to examples and comparative examples of a photosensitive resin composition and a cured film, but the present invention is not limited to these examples. The raw materials used in the examples and comparative examples described below and their abbreviations are as follows.

(i) -1: the alkali-soluble resin obtained in example 1 was synthesized.

(i) -2: the alkali-soluble resin obtained in example 2 was synthesized.

(i) -3: the alkali-soluble resin obtained in Synthesis example 3 was synthesized.

(i) -4: the alkali-soluble resin obtained in Synthesis example 4 was synthesized.

(i) -5: the alkali-soluble resins obtained in Synthesis example 1 were compared.

(i) -6: the alkali-soluble resins obtained in Synthesis example 2 were compared.

(i) -7: the alkali-soluble resins obtained in Synthesis example 3 were compared.

(ii) The method comprises the following steps Dipentaerythritol hexaacrylate.

(iii) The method comprises the following steps Omnirad184 (manufactured by IGM Resins b.v.) (former Irgacure184 (the "Irgacure" manufactured by BASF is a registered trademark of BASF).

(iv) The method comprises the following steps 20.0% by mass of carbon black, and 5.0% by mass of a polymer dispersant (25.0% by mass of solid content, average secondary particle diameter of carbon black: 162 nm).

(v) The method comprises the following steps Propylene glycol monomethyl ether acetate.

[ evaluation of photosensitive resin composition ]

Table 1 shows the content (unit is mass%) of each component of the photosensitive resin composition solutions of synthesis examples 1 to 4, comparative example 1, and comparative example 2.

[ TABLE 1]

Composition (I)	Example 1	Example 2	Example 3	Example 4	Comparative example 1	Comparative example 2
							(i)-1	31.8
(i)-2		31.9
							(i)-3			26.4
(i)-4				30.4
							(i)-5					28.5
(i)-6						28.1
							(iii)	0.4	0.4	0.4	0.4	0.4	0.4
(v)	67.8	67.7	73.2	69.2	71.1	71.5

(preparation of a cured film for measuring light transmittance and refractive index)

The illuminance at 254nm for a low-pressure mercury lamp was 1000mJ/cm²The photosensitive resin composition solutions of examples 1 to 4, comparative example 1 and comparative example 2 were applied and dried under the condition that the dry film thickness was 1.5 μm by using a spin coater on a 125mm × 125mm glass substrate (manufactured by Corning Corp.) (hereinafter referred to as "glass substrate") whose surface was cleaned by ultraviolet irradiation, and then irradiated with an illuminance of 10mW/cm at a wavelength of 365nm using a 500W high-pressure mercury lamp without using a photomask²And exposure is performed. Then, a 0.4% sodium carbonate aqueous solution at 23 ℃ was used at 0.1MPa for 60 secondsThe developer treatment is performed under the pressure of (1). Thereafter, a heat curing treatment was performed at 230 ℃ for 30 minutes using a hot air dryer, and a cured film (a cured film-formed glass substrate) was obtained.

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

(method of measuring light transmittance)

The light transmittance at 400nm was measured using an ultraviolet/visible/near infrared (UV-Vis-NIR) spectrophotometer "UH 4150" (manufactured by hitachi-rightech Co., Ltd.).

(evaluation Standard)

O: the light transmittance is 85% or more.

X: the light transmittance is less than 85%.

(method of measuring refractive index)

The refractive index of light at 633nm was measured using a prism coupler (prism coupler) film thickness/refractometer Model 2010/M (manufactured by Metricon). Table 2 shows the measurement results of the light transmittance and the refractive index.

[ TABLE 2]

From the results of examples 1 to 4 and comparative examples 1 and 2, it is understood that a cured film having high light transmittance and low refractive index can be obtained by using the photosensitive resin composition of the present invention containing the alkali-soluble resins (i) -1 to (i) -4 having a skeleton of the general formula (1).

[ evaluation of colored photosensitive resin composition ]

Table 3 shows the content (unit is mass%) of each component in the colored photosensitive resin composition solutions of synthesis examples 5 to 8, comparative example 3, and comparative example 4.

[ TABLE 3 ]

Composition (I)	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

(preparation of colored cured film for reflectance measurement)

The colored photosensitive resin composition solutions of examples 5 to 8, comparative examples 3 and comparative example 4 were coated on a glass substrate using a spin coater under a condition that the dry film thickness was 1.5. mu.m, and then dried, and then irradiated with a 500W high-pressure mercury lamp without a mask at an illuminance of 10mW/cm at a wavelength of 365nm²And exposing to ultraviolet light. Then, the developer treatment was performed at a pressure of 0.1MPa for 60 seconds using a 0.4% sodium carbonate aqueous solution at 23 ℃. Thereafter, a heat curing treatment was performed at 230 ℃ for 30 minutes using a hot air dryer, thereby obtaining a color cured film (a glass substrate on which the color cured film was formed).

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

(method of measuring reflectance (Y))

The reflectance (Y) was measured using an ultraviolet-visible near-infrared spectrophotometer "UH 4150". In addition, the appearance of the surface of the colored cured film was visually confirmed.

(evaluation Standard)

Very good: no color unevenness was confirmed at all.

Good: color non-uniformity was observed in the area below 1/4 of the surface.

And (delta): color non-uniformity was observed in the area below 1/3 of the surface.

X: color unevenness was observed as a whole.

[ TABLE 4 ]

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