JP2015214684A - Alkali-soluble resin, photosensitive resin composition comprising the same, cured product using the same, and touch panel and color filter including said cured product as constituent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkali-soluble resin capable of providing a photosensitive resin composition which has excellent development characteristics as well as sufficient photodiscoloration resistance; and the photosensitive resin composition.SOLUTION: A reaction product of an unsaturated group-containing monocarboxylic acid and an epoxy compound (a-1) having two epoxycycloalkyl groups in each molecule is reacted with a dicarboxylic acid or tricarboxylic acid or an acid monoanhydride thereof (b) and a tetracarboxylic acid or an acid dianhydride thereof (c); thereby obtaining an alkali-soluble resin of the general formula (1). Also provided is a photosensitive resin composition comprising the same.

Description

  The present invention relates to an alkali-soluble resin suitable for a photosensitive resin composition capable of forming a desired pattern and having excellent light discoloration resistance, a photosensitive resin composition using the same, and a cured product thereof. The present invention relates to a touch panel and a color filter containing the cured product as a constituent component. In particular, the photosensitive resin composition according to the present invention can be used as a white photosensitive resin composition for forming a white cured product having a large influence of light discoloration resistance. Suitable as a material. Other than that, the photosensitive resin composition of the present invention can be applied to transparent cured films, light-shielding films, etc. that require light resistance as components of display devices such as color filters and touch panels. It is also useful as a resin composition, a black photosensitive resin composition, and the like.

  In recent years, with the trend toward diversification of information equipment and the reduction in size and weight of mobile terminals, input displays that have been integrated with flat displays such as liquid crystal display panels, such as mobile phones, mobile information terminals, car navigation systems, etc. Integrated touch panel flat displays have become popular in the market. There are various types of touch panels such as a resistance film type and a capacitance type depending on the structure and detection method. Among these, the capacitive touch panel has a translucent conductive film (translucent electrode) on a single substrate, and has a capacitance formed by contact (touch) with a finger or a pen. The position to be touched is specified by detecting a change in the amount of weak current flowing through it, and the liquid crystal display device or the like is driven by receiving the instructed content as an input signal. The capacitive touch panel has an advantage that higher transmittance can be obtained as compared with the resistive touch panel.

  In any of the touch panels, a transparent protective plate such as a cover glass is usually used on the upper surface for detecting an input signal or protecting the screen. Therefore, a transparent protective plate is provided on the upper surface of the touch panel, or the transparent protective plate itself constitutes the touch panel. Some transparent protective plates include functional films such as a low reflection film, an antiglare film, a hard coat film, and an electromagnetic shield film.

  In recent years, with the trend toward electronic devices, decorations such as LCD (liquid crystal display) wiring shielding are generally applied by various printing methods on transparent protective plates of mobile terminal devices such as mobile phones. It is. For example, Patent Document 1 and Patent Document 2 include a protective panel in which a decorative film in which a window forming layer having a transparent window portion is formed in advance on the back surface of a hard coat film is attached to the transparent protective plate surface in a laminated state. The transparent protective plate is bonded to the movable electrode film at a peripheral portion so as to form an air layer between the movable electrode film laminated with a decorative film and the movable electrode film. An electronic device configured by a touch panel including the fixed electrode plate is disclosed. Conventionally, as described above, the decorated transparent protective plate and the touch panel are generally formed separately and combined in a later step. However, in recent years, there is a strong need for thinning mobile phones, and the number of processes can be reduced by forming a touch panel directly on the decorative transparent protective plate. A method using a photosensitive resin is attracting attention. A touch panel manufacturing method using this method is described in Patent Document 3. Black is generally used as the color of the decorative portion of the decorative transparent protective plate for touch panels, but with the trend toward electronic fashion, white decoration is required.

  However, particularly in the case of a white photosensitive resin, discoloration may occur due to heat applied when the coating film is heated and cured or in the process of manufacturing the touch panel, and the light reflectance may be reduced. Moreover, when light resistance is insufficient, it will color while using a touch panel, or a light reflectance will fall. In the case of a white photosensitive resin for a touch panel, since discoloration and a decrease in reflectance are particularly conspicuous, there is a possibility that the commercial value may be lowered, and a solution is required.

JP 2007-279756 A JP 2007-323092 A JP 2013-8272 A

  Accordingly, an object of the present invention is to solve the above-mentioned problems in the prior art and to obtain a white photosensitive resin composition excellent in development characteristics while having sufficient light discoloration resistance, an alkali-soluble resin, The object is to provide a white photosensitive resin composition, a cured product using the same, and a touch panel having the cured product as a constituent component. Further, in a photosensitive resin composition that does not contain a colorant or a photosensitive resin composition that contains a colorant other than white, the use of a polymerizable unsaturated group-containing alkali-soluble resin having a specific structure enables light resistance requirements. Therefore, a cured product to which this technology is applied can be applied to an overcoat, an insulating film, and a colored pixel with good light resistance. That is, the present invention can be applied to other than the white photosensitive resin composition, and can be used as, for example, a constituent element of a touch panel or a color filter having good light resistance.

  As a result of diligent research to solve the above problems, the present inventors have used an alkali-soluble resin (A) having a carboxyl group and a polymerizable unsaturated group in one molecule having a specific structure. The present inventors have found that a photosensitive resin composition that can satisfy the light resistance requirement can be obtained. That is, in addition to the component (A), it is a photosensitive resin composition containing a photopolymerization initiator (B) as an essential component, and is also a photopolymerizable monomer (C) and / or an epoxy compound or an epoxy resin (D ) Is further added to the photosensitive resin composition, and the photosensitive resin composition is further added with the dispersoid (E). Among these, it is suitable as a white photosensitive resin composition containing a white light-shielding material as a dispersoid (E), pattern formation by light is possible, and a cured product having excellent light discoloration resistance can be obtained. For example, it has been found useful for decorating touch panels.

（但し、Ｒ₁は水素原子またはメチル基を示す。Ｘは単結合又は内部にヘテロ元素を含んでいてもよい炭素数１〜２０の２価の有機基を示し、Ｙは４価のカルボン酸残基を示し、Ｚは水素原子又は下記一般式（２）で示される置換基を示し、Ｇは水素原子または下記一般式（３）で示される置換基を示す。ｎは１〜２０の平均値を示す。）

（但し、Ｒ₁は一般式（１）に示したものと同義であり、Ｒ₂は炭素数２〜１０の２価の炭化水素基を示し、Ｌは２または３価のカルボン酸残基を示し、ｍは０又は１である。ｐ及びｑは０又は１又は２であり、ｐ＋ｑが１又は２である。） The gist of the present invention is as follows.
(1) The present invention relates to a reaction product of an epoxy compound (a) having two epoxy groups in one molecule and an unsaturated group-containing monocarboxylic acid, a dicarboxylic acid or tricarboxylic acid or an acid monoanhydride thereof. In an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule obtained by reacting (b) and tetracarboxylic acid or its acid dianhydride (c), one molecule as an epoxy compound (a) It is represented by the following general formula (1) by using an epoxy compound (a-1) having two epoxycycloalkyl groups in it, and has a carboxyl group and a polymerizable unsaturated group in one molecule. It is a characteristic alkali-soluble resin.

(However, R ₁ represents a hydrogen atom or a methyl group. X represents a single bond or a divalent organic group having 1 to 20 carbon atoms which may contain a hetero element therein, and Y represents a tetravalent carboxylic acid. Represents a residue, Z represents a hydrogen atom or a substituent represented by the following general formula (2), G represents a hydrogen atom or a substituent represented by the following general formula (3), n is an average of 1 to 20 Indicates the value.)

(Wherein, R ₁ is the same meaning as in general formula (1), R ₂ represents a divalent hydrocarbon group having 2 to 10 carbon atoms, L is a divalent or trivalent carboxylic acid residue M is 0 or 1. p and q are 0, 1 or 2, and p + q is 1 or 2.)

（但し、Ｒ₁、Ｘ、Ｙ、ｎは一般式（１）に示したものと同義であり、Ｚ’は水素原子又は一般式（６）で示される置換基を示す。）

（但し、Ｌは一般式（２）に示したものと同義であり、ｒは１または２である。）

（但し、Ｒ₁、Ｒ₂、ｍは一般式（１）、（２）及び（３）に示したものと同義である。） (2) The present invention is also a reaction product of an epoxy compound (a-1) represented by the following general formula (4) having two epoxycycloalkyl groups in one molecule and an unsaturated group-containing monocarboxylic acid. A polymerizable unsaturated group of the following general formula (5) obtained by reacting dicarboxylic acid or tricarboxylic acid or acid monoanhydride (b) thereof with tetracarboxylic acid or acid dianhydride (c) thereof The alkali-soluble resin according to item (1), wherein the unsaturated group-containing epoxy compound represented by the following general formula (7) is further reacted with the carboxyl group of the alkali-soluble resin. .

(However, R ₁ , X, Y, and n are as defined in formula (1), and Z ′ represents a hydrogen atom or a substituent represented by formula (6).)

(However, L is synonymous with what was shown in General formula (2), and r is 1 or 2.)

(However, R ₁ , R ₂ and m are synonymous with those shown in the general formulas (1), (2) and (3).)

〔但し、Ｒ₃、Ｒ₄、Ｒ₅、及びＲ₆は、独立に水素原子、炭素数１〜５のアルキル基、ハロゲン原子又はフェニル基を示す。また、Ｍは-CO-、-SO₂-、-C(CF₃)₂-、-Si(CH₃)₂-、-CH₂-、-C(CH₃)₂-、-O-、フルオレン-9,9-ジイル基又は単結合を示し、ｅは０〜１０の平均値（但し０は含まず）を表す。〕

〔但し、Ｗ及びＷ'は、下記一般式（１０）で表される２価の有機基Ｐ、及び／又は下記一般式（１１）で表される２価の有機基Ｑで表される２価の有機基を示し、Ｙは４価のカルボン酸残基を示し、Ｚは水素原子又は下記一般式（２）で示される置換基を示し、Ｇは水素原子または下記一般式（３）で示される置換基を示す。

（但し、Ｒ₁は水素原子またはメチル基を示し、Ｒ₂は炭素数２〜１０の２価の炭化水素基を示し、Ｌは２又は３価のカルボン酸残基を示し、ｍは０又は１である。ｐ及びｑは、０又は１又は２であり、ｐ＋ｑが１又は２である）、ｆは１〜２０の平均値を表す。ここで、一般式（９）で表されるアルカリ可溶性樹脂の個々の１分子内においてｆは整数であり、当該１分子内における有機基Ｐ及びＱで表されるユニット数をそれぞれｆ_P及びｆ_Qとした場合にｆ＝ｆ_P＋ｆ_Qである。なお、Ｗ'＝Ｐである場合はｆ_Q≠０（ｆ_Qはゼロではない）であり、Ｗ'＝Ｑである場合はｆ_P≠０（ｆ_Pはゼロではない）である。

（但し、Ｒ₁は一般式（２）に示したものと同義、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｍ、ｅは一般式（８）に示したものと同義である。）〕 (3) The present invention also relates to a reaction product of an epoxy compound (a) having two epoxy groups in one molecule and an unsaturated group-containing monocarboxylic acid, a dicarboxylic acid or a tricarboxylic acid or an acid monoanhydride thereof. In an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule obtained by reacting the product (b) and tetracarboxylic acid or its acid dianhydride (c), 1 as an epoxy compound (a) An epoxy compound having two epoxy groups in one molecule derived from a bisphenol represented by the following general formula (8) together with an epoxy compound (a-1) having two epoxycycloalkyl groups in the molecule By using (a-2) in combination, it is represented by the following general formula (9) and has a carboxyl group and a polymerizable unsaturated group in one molecule. It is a sexual resin.

_{[However, R 3, R 4, R} 5, and R ₆ represents independently a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, a halogen atom or a phenyl group. M is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, fluorene -9,9-diyl group or a single bond, e represents an average value of 0 to 10 (however, 0 is not included). ]

[W 2 and W ′ are represented by a divalent organic group P represented by the following general formula (10) and / or a divalent organic group Q represented by the following general formula (11). Y represents a tetravalent carboxylic acid residue, Z represents a hydrogen atom or a substituent represented by the following general formula (2), and G represents a hydrogen atom or the following general formula (3). The substituents shown are shown.

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a divalent hydrocarbon group having 2 to 10 carbon atoms, L represents a divalent or trivalent carboxylic acid residue, and m represents 0 or 1. p and q are 0, 1 or 2, and p + q is 1 or 2. f represents an average value of 1-20. Here, f is an integer in each molecule of the alkali-soluble resin represented by the general formula (9), and the number of units represented by the organic groups P and Q in the molecule is represented by f _P and f, respectively. _{When Q is} assumed, f = f _P + f _Q. When W ′ = P, f _Q ≠ 0 (f _Q is not zero), and when W ′ = Q, f _P ≠ 0 (f _P is not zero).

(However, R ₁ has the same meaning as that shown in the general formula (2), and R ₃ , R ₄ , R ₅ , R ₆ , M, and e have the same meanings as those shown in the general formula (8).)]

(4) The present invention also provides (A) an alkali-soluble resin of the general formula (1) described in the above item (1) or an alkali-soluble resin of the general formula (9) described in the above item (3). Either one or both,
(B) a photopolymerization initiator;
It is a photosensitive resin composition characterized by containing.

(5) In addition to the components (A) and (B), the present invention also includes (C) a photopolymerizable monomer having at least one polymerizable unsaturated group and / or (D) two epoxy groups. It is the photosensitive resin composition as described in said (4) term containing the epoxy compound or epoxy resin contained above.
(6) The present invention is also a photosensitive resin composition characterized by further containing (E) a dispersoid in the photosensitive resin composition described in the above item (4) or (5).
(7) The present invention also provides the white photosensitive resin composition according to (6), wherein (E) the dispersoid is (E-1) a white pigment.
(8) The present invention also provides the white photosensitive resin composition of the above item (7), wherein in the solid content, the component (A) is 1 to 55% by mass, the component (C) is 100 parts by mass of the component (A). In contrast, 0 to 100 parts by mass, (B) component is 0.1 to 40 parts by mass, and (E) component is 1 to 95 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (C). % White photosensitive resin composition characterized by containing.
(9) The present invention is also a cured product obtained by patterning the photosensitive resin composition according to any one of the above items (4) to (8) by a photolithography method and then thermally curing it.
(10) The present invention is also a touch panel having the cured product of item (9).
(11) The present invention is also a color filter having the cured product of item (9).

（但し、Ｒ₁は水素原子またはメチル基を示す。Ｘは単結合又は内部にヘテロ元素を含んでいてもよい炭素数１〜２０の２価の有機基を示し、Ｙは４価のカルボン酸残基を示し、Ｚは水素原子又は一般式（２）で示される置換基を示し、Ｇは水素原子又は一般式（３）で示される置換基を示す。ｎは１〜２０の平均値を表す。）

（但し、Ｒ₁は水素原子またはメチル基を示し、Ｒ₂は炭素数２〜１０の２価の炭化水素基を示し、Ｌは２又は３価のカルボン酸残基を示し、ｍは０又は１である。ｐ及びｑは、０又は１又は２であり、ｐ＋ｑが１又は２である。） The present invention is described in detail below.
The alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule of the present invention is a reaction product of an epoxy compound (a) having two epoxy groups in one molecule and an unsaturated group-containing monocarboxylic acid. Is obtained by reacting dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (b), and tetracarboxylic acid or its acid dianhydride (c), and as an epoxy compound, two epoxies in one molecule. An epoxy compound (a-1) having a cycloalkyl group is used, and an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule represented by the following general formula (1).

(However, R ₁ represents a hydrogen atom or a methyl group. X represents a single bond or a divalent organic group having 1 to 20 carbon atoms which may contain a hetero element therein, and Y represents a tetravalent carboxylic acid. Z represents a hydrogen atom or a substituent represented by the general formula (2), G represents a hydrogen atom or a substituent represented by the general formula (3), and n represents an average value of 1 to 20. Represents.)

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a divalent hydrocarbon group having 2 to 10 carbon atoms, L represents a divalent or trivalent carboxylic acid residue, and m represents 0 or 1 and p and q are 0, 1 or 2, and p + q is 1 or 2.)

（但し、Ｘは一般式（１）に示したものと同義である。） A method for producing an alkali-soluble resin represented by the general formula (1) and having a carboxyl group and a polymerizable unsaturated group in one molecule (hereinafter referred to as “alkali-soluble resin of the general formula (1)”) in detail. explain.
First, an unsaturated group-containing monocarboxylic acid is reacted with an epoxy compound (a-1) having two epoxycycloalkyl groups in one molecule represented by the general formula (4), preferably (meth) acrylic. An acid is reacted to obtain an epoxy (meth) acrylate compound. Examples of the unsaturated group-containing monocarboxylic acid compound include, in addition to acrylic acid and methacrylic acid, compounds obtained by reacting acrylic acid or methacrylic acid with acid monoanhydrides such as succinic anhydride, maleic anhydride, and phthalic anhydride. It is done.

(However, X is synonymous with what was shown in General formula (1).)

（但し、Ｒ₁、Ｘは一般式（１）に示したものと同義である。） For the reaction of such an epoxy compound with (meth) acrylic acid, a known method can be used. For example, about 2 mol of (meth) acrylic acid is added to 1 mol of an epoxy compound having two epoxy groups. Use to do. The reaction product obtained by this reaction is described, for example, in JP-A-4-355450. The reaction product obtained by this reaction is a diol compound containing a polymerizable unsaturated group, and is an epoxy (meth) acrylate compound (d) represented by the following general formula (12).

(However, R ₁ and X are synonymous with those shown in the general formula (1).)

（但し、ｇは１〜２０の整数を表し、ｈは２〜２０の整数を表し、ｉは０〜１０の整数を表し、ｊは１〜２０の整数を表し、ｋは０〜１８の整数を表し、ｌは１〜１０の整数を表す。） X of the epoxy compound (a-1) having two epoxycycloalkyl groups in the molecule represented by the general formula (4) has 1 to 20 carbon atoms which may contain a single bond or a hetero element inside. These are divalent organic groups. Examples of the divalent organic group having 1 to 20 carbon atoms that may contain a hetero element therein include a divalent hydrocarbon group and a divalent hydrocarbon group having a carboxyl group at one or two ends of the hydrocarbon group. Groups, etc., and the hydrocarbon group herein may have an etheric oxygen atom or ester bond therein. Examples of such divalent hydrocarbon groups include methylene groups, ethylene groups, propylene groups, isopropylidene groups, sec-butylene groups, methylisobutylene groups, hexylene groups, decylene groups, and dodecylene groups. Is mentioned. Examples of the divalent group having a carboxyl group at the end of the hydrocarbon group include divalent organic groups represented by the following general formulas (13) to (16). In general formula (13), g is 1, h is 5 and i is 1 in general formula (14), j is 2 in general formula (15), and k in general formula (16). Is preferably 4 and l is 1.

(However, g represents the integer of 1-20, h represents the integer of 2-20, i represents the integer of 0-10, j represents the integer of 1-20, k represents the integer of 0-18. And l represents an integer of 1 to 10.)

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

（但し、ｇ〜ｌは一般式（１３）〜（１６）で示したものと同義である。） Specific examples of the epoxy compound (a-1) having two epoxycycloalkyl groups in the molecule represented by the general formula (4) include epoxy compounds represented by the following general formulas (17) to (23). 2 or more may be used in combination. Preferably, it is an epoxy compound represented by the general formula (20) or (21) from the viewpoint of availability and physical properties of the cured product, and it is preferable that g is 1, h is 5 and i is 1.

(However, g ~ l is synonymous with what was shown by General formula (13)-(16).)

  Synthesis of epoxy (meth) acrylate compound (d) as represented by the above general formula (12), and subsequent addition reaction of polyvalent carboxylic acid or anhydride thereof, and further polymerizability having reactivity with carboxyl group In the production of an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in the molecule represented by the general formula (1) by reacting with a monofunctional epoxy compound having an unsaturated group, it is usually necessary in a solvent. Depending on the reaction, the reaction is carried out using a catalyst. Here, the reaction conditions such as the solvent and catalyst used are not particularly limited. For example, a solvent having no hydroxyl group and having a boiling point higher than the reaction temperature is preferably used as the reaction solvent. For example, cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high boiling point ether or ester solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, cyclohexanone, diisobutyl ketone It is preferable to use a ketone solvent such as A catalyst is preferably used in the reaction between the carboxyl group and the epoxy group. Examples of the catalyst used include ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, triphenylphosphine, and tris (2, 6- Known phosphines such as dimethoxyphenyl) phosphine can be used. These are described in detail in JP-A-9-325494.

（但し、Ｒ₁、Ｘ、Ｙ、ｎは一般式（１）に示したものと同義であり、Ｚ’は水素原子又は一般式（６）で示される置換基を示す。）

（但し、Ｌは一般式（２）に示したものと同義であり、ｒは１または２である。） As the second reaction, the epoxy (meth) acrylate compound (d) obtained by the reaction of the epoxy compound and (meth) acrylic acid is reacted with the acid components (b) and (c) to obtain the general formula (5). An alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule represented by (hereinafter referred to as “alkali-soluble resin of the general formula (5)”) can be obtained.

(However, R ₁ , X, Y, and n are as defined in formula (1), and Z ′ represents a hydrogen atom or a substituent represented by formula (6).)

(However, L is synonymous with what was shown in General formula (2), and r is 1 or 2.)

  The acid component used for synthesizing the alkali-soluble resin of the general formula (5) is a polyvalent acid component capable of reacting with a hydroxyl group in the epoxy (meth) acrylate compound molecule, and is a dicarboxylic acid or tricarboxylic acid or It is necessary to use the acid monoanhydride (b) and the tetracarboxylic acid or the acid dianhydride (c) in combination. The carboxylic acid residue of this acid component may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group, and these carboxylic acid residues are bonds containing heteroelements such as —O—, —S—, and carbonyl groups. May be included. Among these, as dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (b), chain hydrocarbon dicarboxylic acid or tricarboxylic acid, alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid Or acid monoanhydrides thereof or the like can be used. Moreover, as tetracarboxylic acid or its acid dianhydride (c), chain | strand-type hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, aromatic hydrocarbon tetracarboxylic acid, or those acid dianhydrides, etc. Can be used. In view of reactivity and reaction control, it is advantageous to use acid monoanhydride for (b) and acid dianhydride for (c).

Specific examples of the acid component to be used are shown below.
First, it shows about dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (b). Although the example of dicarboxylic acid or tricarboxylic acid is shown below, it is preferable to use the acid monoanhydride, and it can also use 2 or more types together.
Examples of the saturated chain hydrocarbon dicarboxylic acid or tricarboxylic acid include succinic acid, acetyl succinic acid, adipic acid, azelaic acid, citrate malic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacin An acid, suberic acid, diglycolic acid etc. can be mentioned. Further, it may be a saturated chain hydrocarbon dicarboxylic acid or tricarboxylic acid having a substituent such as an alicyclic hydrocarbon group or an unsaturated hydrocarbon group. Next, examples of the alicyclic hydrocarbon dicarboxylic acid and tricarboxylic acid include hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, hexahydrotrimellitic acid, and the like. Furthermore, alicyclic dicarboxylic acids and tricarboxylic acids with substituents such as chain hydrocarbons and unsaturated hydrocarbon groups may be used. Examples of the unsaturated dicarboxylic acid and tricarboxylic acid include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, and trimellitic acid. Furthermore, unsaturated dicarboxylic acids and tricarboxylic acids with substituents such as saturated chain hydrocarbon groups, alicyclic hydrocarbon groups, and unsaturated hydrocarbon groups may be used. Of these, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid and trimellitic acid are preferred, and succinic acid, itaconic acid and tetrahydrophthalic acid are more preferred.

Next, it shows about tetracarboxylic acid or its acid dianhydride (c). Although the example of tetracarboxylic acid is shown below, it is preferable to use the acid dianhydride, and it can also use 2 or more types together.
Examples of the chain hydrocarbon tetracarboxylic acid include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid and the like, and further substitution of alicyclic hydrocarbon group, unsaturated hydrocarbon group, etc. It may be a chain hydrocarbon tetracarboxylic acid with a group attached.

  Examples of the alicyclic tetracarboxylic acid include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, and chain carbonization. It may be an alicyclic tetracarboxylic acid with a substituent such as a hydrogen group or an unsaturated hydrocarbon group. Examples of the aromatic tetracarboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, and diphenyl sulfone tetracarboxylic acid. Of these, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, and diphenyl ether tetracarboxylic acid are preferable, and biphenyl tetracarboxylic acid and diphenyl ether tetracarboxylic acid are more preferable.

  The method for reacting the epoxy (meth) acrylate compound (d) with the acid components (b) and (c) is not particularly limited, and is described, for example, in JP-A-9-325494. Thus, a well-known method which makes an epoxy (meth) acrylate compound and tetracarboxylic dianhydride react with reaction temperature 90-140 degreeC is employable. Preferably, the epoxy (meth) acrylate compound (d), dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (b), tetracarboxylic dianhydride (c) is used so that the terminal of the compound is a carboxyl group. It is desirable to carry out the reaction so that the molar ratio is (d) :( b) :( c) = 1: 0.01 to 1.0: 0.2 to 1.0. Here, (b) acid monoanhydride and (c) acid dianhydride are used as an example for quantitative explanation. A diol compound containing a polymerizable unsaturated group (epoxy (meth) acrylate compound) The reaction is performed so that the molar ratio [(d) / [(b) / 2 + (c)]] of the amount [(b) / 2 + (c)] of the acid component to (d) is 0.5 to 1.0. It is desirable to make it. When the molar ratio exceeds 1.0, the content of the diol compound containing an unreacted polymerizable unsaturated group increases, and there is a concern that the stability over time of the alkali-soluble resin composition may be reduced. On the other hand, when the molar ratio is less than 0.5, the terminal of the alkali-soluble resin represented by the general formula (1) becomes an acid anhydride, and the content of unreacted acid dianhydride increases to be alkali-soluble. There is a concern that the stability of the resin composition will deteriorate over time. The molar ratio of each component of (d), (b) and (c) can be arbitrarily changed within the above range for the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin represented by the general formula (1). .

  In the alkali-soluble resin obtained by the reaction of the diol compound (d) containing the polymerizable unsaturated group and the acid components (b) and (c), G in the general formula (1) is all hydrogen atoms. Yes, having the structure of the above general formula (5). In this invention, the unsaturated group containing epoxy compound represented by the said General formula (7) is made to react with the carboxyl group of the said General formula (5). For the reaction of the unsaturated group-containing epoxy compound represented by the general formula (5) and the general formula (7), a known method can be used, for example, as represented by the general formula (12). The manufacturing method of an epoxy (meth) acrylate compound can be used.

  The molar ratio of the epoxy group of the unsaturated group-containing epoxy compound represented by the general formula (7) to the carboxyl group of the general formula (5) is the photoreaction of the alkali-soluble resin represented by the general formula (1). It can be arbitrarily changed for the purpose of adjusting sensitivity (depending on the amount of polymerizable double bond) and acid value. When the number of moles of the general formula (7) is 90% or less with respect to the total number of moles of the component (b) and twice the number of moles of the component (c), alkali developability can be imparted. Yes, it can be used for a photosensitive resin composition having photo-patterning properties. Moreover, since it is necessary to make it 10% or more when providing the sensitivity improvement effect of photoreaction, it is preferable that it is 10 to 90%. Furthermore, it is more preferable that it is 30 to 70%. The acid value of the alkali-soluble resin of the general formula (1) used is preferably 20 to 180, and more preferably 30 to 120.

  The weight average molecular weight (Mw) in terms of polystyrene as measured by gel permeation chromatography (GPC) of the alkali-soluble resin of the general formula (1) of the present invention is usually 1000 to 100,000, and 2000 to 20000. Is preferred. If the weight average molecular weight is less than 1000, the adhesion of the pattern during alkali development may be reduced. When the weight average molecular weight exceeds 100,000, it is difficult to obtain a solution viscosity of the photosensitive resin composition suitable for coating, or it takes too much time for alkali development, which is not preferable.

Next, the unsaturated group-containing alkali-soluble resin of the general formula (9) (hereinafter referred to as “alkali-soluble resin of the general formula (9)”) will be described.
The method for producing the alkali-soluble resin of the general formula (9) can be carried out by the method for producing the alkali-soluble resin of the general formula (1), but the epoxy having two epoxy groups in one molecule of the first step. When the compound (a) is reacted with an unsaturated group-containing monocarboxylic acid, it is derived from the epoxy compound (a-1) having two epoxycycloalkyl groups in one molecule as the component (a) and bisphenols. It is characterized by using an epoxy resin (a-2) in combination.

ここで、Ｒ₃、Ｒ₄、Ｒ₅、及びＲ₆は、独立に水素原子、炭素数１〜５のアルキル基、ハロゲン原子又はフェニル基を示す。また、Ｍは-CO-、-SO₂-、-C(CF₃)₂-、-Si(CH₃)₂-、-CH₂-、-C(CH₃)₂-、-O-、フルオレン-9,9-ジイル基又は単結合を示し、ｅは０〜１０の平均値(但し０は含まず)を表す。 The epoxy resin (a-2) derived from bisphenols is represented by the general formula (8).

_{Here, R 3, R 4, R} 5, and R ₆ represents independently a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, a halogen atom or a phenyl group. M is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, fluorene It represents a -9,9-diyl group or a single bond, and e represents an average value of 0 to 10 (excluding 0).

  The component (a-2) is an epoxy compound having two glycidyl ether groups by reacting bisphenols and epichlorohydrin. The reaction generally involves oligomerization of a diglycidyl ether compound, resulting in an oligomer as shown in the general formula (8), but each molecule has a different e value, and the average value of e as described above. Is more than 0 and 10 or less, preferably 0.05 or more and 5 or less.

  Examples of the bisphenols used as the raw material for the component (a-2) include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, and 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) dimethyl Silane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5- Dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5) -Dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4 -Hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichloropheny) ) Ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9 , 9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) Fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, 4,4′-biphenol, 3,3 ′ -Biphenol and the like and derivatives thereof. Among these, 2,2-bis (4-hydroxyphenyl) propane is preferably used. Two or more bisphenols can also be used as a raw material for the component (a-2).

  In the first step of the production of the compound of the general formula (9), the component (a-1) and the component (a-2) are mixed with 10 parts of (a-2) with respect to 100 parts by mass of the component (a-1). 100 parts by mass, preferably 30 to 60 parts by mass, added twice the total number of moles of the epoxy compounds (a-1) and (a-2) having two epoxy groups (meth) Acrylic acid is reacted to obtain an epoxy (meth) acrylate compound (d ′). As described above, this reaction is preferably carried out using a catalyst in a solvent. In addition, 2 mol mol (meth) acryl with respect to 1 mol of (a-2) and the epoxy acrylate which reacted 2 mol mol (meth) acrylic acid with respect to 1 mol of (a-1) separately. An epoxy (meth) acrylate compound (d ′) may be obtained by mixing with an epoxy acrylate reacted with an acid.

In the second step, the epoxy (meth) acrylate compound (d ′) obtained in the first step is added to a dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (b) and a tetracarboxylic acid or its acid dianhydride (c). To obtain an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule of the general formula (24) (hereinafter referred to as “alkali-soluble resin of the general formula (24)”).

（但し、Ｒ₁は一般式（１）に示したものと同義、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｍ、ｅは一般式（８）に示したものと同義である。） Here, W and W ′ are 2 represented by a divalent organic group P represented by the following general formula (10) and / or a divalent organic group Q represented by the following general formula (11). Y and Z ′ are synonymous with those shown in the general formula (5). f represents an average value of 1 to 20. Here, f is an integer in each molecule of the alkali-soluble resin represented by the general formula (24), and the number of units represented by P and Q in the molecule is represented by f _P and f _Q , respectively. In this case, f = f _P + f _Q. When W ′ = P, f _Q ≠ 0, when W ′ = Q, f _P ≠ 0, and when W ′ is P, W always includes Q, and W ′ is Q In the case of W, W always includes P.

(Wherein, R ₁ is the general formula (1) in the indicated ones _{synonymous, R 3, R 4, R} 5, R 6, M, e has the same meaning as in formula (8).)

  When the alkali-soluble resin of the general formula (24) is produced in the second step, the types and addition amounts of the acid components (b) and (c) to be used, the reaction conditions, etc., the alkali of the general formula (5) This is the same as the case of producing a soluble resin.

  In the third step, the unsaturated group-containing epoxy compound represented by the general formula (7) is reacted with the alkali-soluble resin of the general formula (24). For this reaction, the alkali of the general formula (9) is converted from the alkali-soluble resin of the general formula (24) in the same manner as in the case of producing the alkali-soluble resin of the general formula (1) from the alkali-soluble resin of the general formula (5). A soluble resin is obtained. When the number of moles of the general formula (7) is 90% or less with respect to the total number of moles of the component (b) and twice the number of moles of the component (c), alkali developability can be imparted. Yes, it can be used for a photosensitive resin composition having photo-patterning properties. Moreover, since it is necessary to make it 10% or more when providing the sensitivity improvement effect of photoreaction, it is preferable that it is 10 to 90%. Furthermore, it is more preferable that it is 30 to 70%.

  The weight average molecular weight of the alkali-soluble resin of the general formula (9) is preferably 1000 to 100,000, and preferably 2000 to 30000. The acid value of the alkali-soluble resin of the general formula (9) is preferably 20 to 180, and preferably 30 to 120.

Next, the photosensitive resin composition using the alkali-soluble resin of the general formula (1) and / or the alkali-soluble resin of the general formula (9) of the present invention will be described.
(E) Although the component ratio of the preferable photosensitive resin composition differs by the case where a dispersoid is included and the case where it does not include, first, the case where (E) a dispersoid is not included is demonstrated.
(A) To the alkali-soluble resin of the general formula (1) and / or the general formula (9), (B) a photopolymerization initiator is added, and the solution viscosity is suitable for forming a coating film using a solvent. By doing so, a photosensitive resin composition is obtained. As the photosensitive resin composition of the present invention, the component (A) of the present invention is 50 to 95 mass% in the solid content including the component that becomes solid after photocuring, and the component (B) is 100 mass of the component (A). When there is a component solidified by the photocuring reaction in addition to the component ((A) component), it is preferable to contain 0.1 to 40 parts by mass with respect to the component amount (mass part).

  Examples of the (B) photopolymerization initiator in the photosensitive resin composition of the present invention include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, Acetophenones such as p-tert-butylacetophenone, benzophenone, 2-chlorobenzophenone, benzophenones such as p, p'-bisdimethylaminobenzophenone, benzoin such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether Ethers, 2- (o-chlorophenyl) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole, Biimidazole compounds such as-(o-fluorophenyl) -4,5-diphenylbiimidazole, 2- (o-methoxyphenyl) -4,5-diphenylbiimidazole and 2,4,5-triarylbiimidazole 2-trichloromethyl-5-styryl-1,3,4-oxadiazol, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -Halomethyldiazole compounds such as (p-methoxystyryl) -1,3,4-oxadiazole, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- 4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -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) -1,3 5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylthiostyryl) -4,6-bis Halomethyl-s-triazine compounds such as (trichloromethyl) -1,3,5-triazine, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime) ), 1- (4-phenylsulfanylphenyl) butane-1,2-dione-2-oxime-O-benzoate, 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime- O-acyl oxime compounds such as O-acetate, 1- (4-methylsulfanylphenyl) butan-1-one oxime-O-acetate, benzyldimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethyl Sulfur compounds such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobis Isobutyl nitrile, benzoyl peroxide , Organic peroxides such as cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, thiol compounds such as 2-mercaptobenzothiazole, triethanolamine, etc. tertiary amines such as triethylamine and the like. Among these, it is preferable to use O-acyloxime compounds from the viewpoint of easily obtaining a highly sensitive photosensitive resin composition. Two or more of these photopolymerization initiators can also be used. In addition, the photoinitiator as used in the field of this invention is used by the meaning containing a sensitizer.

  Examples of the solvent contained in the photosensitive resin composition include alcohols such as methanol, ethanol, N-propanol, isopropanol, ethylene glycol, and propylene glycol, terpenes such as α- or β-terpineol, acetone, Ketones such as methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, Butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene Glycol ethers such as glycol monomethyl ether and triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether Examples thereof include acetates such as acetate, propylene glycol monoethyl ether acetate, and 3-methoxy-3-methylbutyl acetate, and these can be dissolved and mixed to form a uniform solution composition. it can. Although the quantity of a solvent changes with target viscosity, the range of 60-90 mass% in the photosensitive resin composition solution is preferable.

  In addition to (A) the alkali-soluble resin having a specific structure and (B) the photopolymerization initiator, the photosensitive resin composition of the present invention includes (C) at least one ethylenic resin as necessary. A photopolymerizable monomer having an unsaturated bond, (D) an epoxy compound or epoxy resin containing two or more epoxy groups can be added, and these (C) component and (D) component are used in combination. Can do.

  Examples of (C) photopolymerizable monomers include (meth) acrylic acid esters having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. , 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, pentaerythritol tetra (meth) acryl , Dipentaerythritol tetra (meth) acrylate, glycerol (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate , (Meth) acrylic acid esters such as phosphazene alkylene oxide-modified hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and dendrimer type polyfunctional acrylates. One or two of these The above can be used. The photopolymerizable monomer having at least one ethylenically unsaturated bond is one having two or more photopolymerizable groups and capable of crosslinking molecules of the unsaturated group-containing alkali-soluble resin. It is preferable. Note that (C) the photopolymerizable monomer having at least one ethylenically unsaturated bond does not have a free carboxyl group.

  (D) Epoxy compounds or compounds used as epoxy resins include phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, glycidyl methacrylate and other epoxy compounds, bisphenol A Type epoxy resin, bisphenol F type epoxy resin, 3,3 ', 5,5'-tetramethyl-4,4'-biphenol type epoxy resin, bisphenol type epoxy resin such as bisphenol fluorene type epoxy resin, phenol novolac type epoxy Resin, novolak epoxy resins such as cresol novolac epoxy resin, glycidyl ether of polyhydric alcohol, glycidyl ester of polycarboxylic acid, 3,4-epoxycyclohexenylmethyl-3 Cycloaliphatic epoxy compounds such as', 4'-epoxycyclohexenecarboxylate, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, epoxy silicone Examples thereof include epoxy resins having a silicone skeleton such as a resin. Preferably, it is an epoxy compound or epoxy resin having two or more epoxy groups.

  In the photosensitive resin composition not containing the component (E) of the present invention, the preferred blending ratio when the component (C) and / or the component (D) is used is such that the component (C) is 100 parts by weight of the component (A). When using 0-100 mass parts and (D) component with respect to (A) component, it is good to set it as 5-30 mass parts with respect to 100 mass parts of total amounts of (A) component and (C) component. The purpose of using the component (C) is to improve the sensitivity of the photocuring reaction of the photosensitive resin composition, and the sensitivity increases as the amount added is increased. However, if it is added in a larger amount than the component (A), the alkali solubility of the photosensitive resin composition is insufficient and the developability is lowered. On the other hand, the purpose of adding the component (D) is to improve the physical properties of the photo-patterned film by thermal curing following the photo-curing reaction and alkali development. In particular, an epoxy compound having two or more epoxy groups is sold. When used, surface hardness and the like can be improved by crosslinking the resin component. However, when there is too much quantity with respect to a photocuring component, it will have a bad influence on optical patterning property.

  The above-mentioned photosensitive resin composition can also be used as a photosensitive resin composition to which (E) a dispersoid is further added. A preferable blending ratio when used as a photosensitive resin composition containing a dispersoid is such that the content of the component (A) is 1 to 55% by mass in the solid content including the component solidified by photocuring, and the component (C). Is 0 to 100 parts by mass with respect to 100 parts by mass of the component (A), the component (B) is 0.1 to 40 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (C), E) is 1 to 95% by mass in the solid content, and when component (D) is used, it should be 5 to 30 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (C). .

  The (E) dispersoid that can be used in the present invention is dispersed with an average particle diameter of 1 to 1000 nm (average particle diameter measured by a laser diffraction / scattering particle size distribution meter or a dynamic light scattering particle size distribution meter). If it is a thing, the well-known dispersoid conventionally used for the photosensitive resin composition can be especially used without a restriction | limiting. For example, azo pigment, condensed azo pigment, azomethine pigment, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, isoindoline pigment, dioxazine pigment, selenium pigment, perylene pigment, perinone pigment, quinophthalone pigment, diketopyrrolopyrrole pigment, thioindigo pigment, etc. Organic pigments, inorganic pigments such as titanium oxide pigments and composite oxide pigments, and pigments such as carbon black pigments (colorants that do not substantially dissolve in the medium) can be preferably used. Organic fillers such as acrylic polymer particles and urethane polymer particles, and inorganic fillers such as silica, talc, mica, glass fiber, carbon fiber, calcium silicate, magnesium carbonate, calcium carbonate, calcium sulfate, and barium sulfate are also used. be able to. Furthermore, metal or metal oxide nanoparticles can also be exemplified.

  These (E) dispersoids are used singly or in combination depending on the function of the desired photosensitive resin composition. For example, as a light-shielding resist used in the production of a black matrix of a color filter, carbon black, titanium Black, black organic pigments, etc. can be used, and the colored resist used in the manufacture of color filter pixels can be red, orange, yellow, green, blue, purple organic pigments, etc. As the solder resist used in the production of the insulating film, organic pigments, inorganic pigments, inorganic fillers, etc. can be used, and as the decorative resist used in the design of the front glass of the touch panel, carbon black, titanium black, black Organic pigments, white pigments, etc. are used as transparent resists with high hardness and high durability. Can be used for transparent filler, each can be used in properly selected.

  In addition, as an organic pigment which can be used as the component (E), pigment red 2, 3, 3, 4, 5, 9, 12, 14, 22, 23, 31 as color index names 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, 264, 266, 272, 279, Pigment Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68 71, 72, 73, 74, 81, Pigment Yellow 1, 3, 12, 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, 191, 194, 199, 213, 214, Pigment Green 7, 36, 58, Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16 and 16 60, 80, Pigment Violet 19, 3, can be exemplified by the same 37, and the like.

  As described above, the photosensitive resin composition of the present invention can be used as a photosensitive resin composition to which various dispersoids (E) are added, for example, for applications requiring light resistance. As an embodiment, a white photosensitive resin composition for applications requiring light resistance with a white cured product that has been photo-patterned may be mentioned.

  That is, the white photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin represented by the general formula (1) and / or the general formula (9), (B) a photopolymerization initiator, and (E) a dispersoid ( E-1) A white pigment is included as an essential component, and (C) a photopolymerizable monomer and / or (D) an epoxy compound or an epoxy resin, depending on the required characteristics of the process such as photopatterning and the physical properties of the cured product Can be added. Details of the components (A) to (D) are as described above.

  Examples of the white pigment (E-1) in the white photosensitive resin composition of the present invention include a white organic pigment and a white inorganic pigment. Examples of white organic pigments include organic compound salts of the general formula An-n [B] disclosed in JP-A No. 11-129613 (A is a substituted stilbene fluorescent whitening agent having an anionic group and a sulfonic acid group, substituted coumarin. Fluorescent brightener components such as fluorescent brighteners and substituted thiophene fluorescent brighteners, B is an organic cation such as ammonium or pyridinium having 15 or more carbon atoms, and n is an integer of 1 to 9) White organic pigments such as alkylene bismelamine derivatives such as ethylene bismelamine and N, N′-dicyclohexylethylene bismelamine disclosed in JP-A-6-122673 (commercially available products include Shigenox OWP, Shigenox OWPL (manufactured by Hackol Chemical Co., Ltd.) )), Hollow particles using a thermoplastic resin described in JP-A-2008-1072, for example, styrene-acrylic And the like, and hollow particles made of a cross-linked styrene-acrylic copolymer (commercially available products are SX866 and SX8782 (manufactured by JSR)).

  Examples of white inorganic pigments include chromium oxide, iron oxide, titanium oxide, titanium white, titanium oxynitride, and titanium nitride. These light shielding materials, including white organic pigments and white inorganic pigments, can be used alone or in appropriate selection of two or more, and in particular, titanium white has light shielding properties, surface smoothness, The dispersion stability and the affinity with the resin are preferable. Moreover, the average particle diameter (volume average particle diameter measured by a laser diffraction / scattering particle diameter measuring apparatus) of the white organic white pigment or organic inorganic pigment used is preferably 20 to 1000 nm, more preferably 50 to 700 nm. preferable.

  In addition, the white photosensitive resin composition of the present invention may be used in combination with a colored ink or a colored inorganic pigment without particular limitation in order to change the color to gray, pink, etc. according to the use or to adjust the light shielding property. Can do. Examples of the colored inorganic pigment used in combination include carbon black, chromium oxide, iron oxide, titanium oxide, titanium black, titanium oxynitride, and titanium nitride. In addition, when forming for the purpose of concealing a wiring layer like the decoration layer of a touch panel, etc., it can also be set as a black light shielding layer and a two-layer structure for the purpose of adjusting light-shielding property. In the case of a two-layer structure, for example, a white cured film layer can be formed on a glass plate for surface protection, and a light-shielding layer can be formed thereon using a black photosensitive resin composition.

  The color inks (black, cyan, magenta and yellow inks) used in combination are not particularly limited, and any known water-soluble dye or oil-soluble dye can be used as long as it can achieve a hue and color density suitable for the intended use of the ink. And pigments can be appropriately selected and used. Among these, it is preferable to use oil-soluble dyes and pigments that are easily dispersed and dissolved in a water-insoluble liquid. When using an oil-soluble dye, the content of the dye is preferably in the range of 0.05 to 20% by mass in terms of solid content of the white photosensitive resin composition. However, this content shall be added in the range which does not exceed content of (E) component.

  About the component ratio of each component of (A)-(C) and (E-1) component in white photosensitive resin composition, content of (A) component in solid content of white photosensitive resin is 1-. It is good that it is 55 mass%, and 3-50 mass% is preferable. When there is little content of (A) component in solid content, the intensity | strength of hardened | cured material will fall. On the other hand, if the amount is too large, the proportion of the white light shielding material of the component (E) in the photosensitive resin composition of the present invention is reduced, and the light shielding performance is lowered. (A) With respect to 100 parts by mass, (C) is 0 to 100 parts by mass, and (B) is 0.1 to 40 parts by mass with respect to 100 parts by mass of the total amount of (A) and (C). is there. (E-1) is 1-95 mass% in solid content (including the monomer component which becomes solid content by photocuring reaction). Preferably (A) is 30 to 50 parts by mass with respect to 100 parts by mass, and (B) is 3 to 30 parts by mass with respect to 100 parts by mass of the total amount of (A) and (C). Yes, (E-1) is 40-90 mass% in solid content. Furthermore, when using (D) component, it is preferable that it is 5-30 mass parts with respect to 100 mass parts of total amounts of (A) component and (C) component. Solid content here contains the component which becomes solid by photocuring, in other words, it is components other than the solvent contained in a white photosensitive resin composition.

  (A) When (C) exceeds 100 parts by mass with respect to 100 parts by mass, the solubility of the coating film in the developer becomes too low, and the photolithography performance is deteriorated.

  When (B) is less than 0.1 parts by mass with respect to 100 parts by mass of the total amount of (A) and (C), the coating film is not cured, and when it exceeds 40 parts by mass, an area larger than the mask opening area is obtained. Since it hardens | cures, photolithography performance falls.

  When (E-1) is less than 1% by mass in the solid content, the coloring power is remarkably reduced, and when it is more than 95% by mass, the viscosity of the ink is increased and the coating of the film becomes difficult.

  The white photosensitive resin composition of this invention contains the said (A), (B), (E-1) component as a main component, and may contain (C) and (D) component as needed. it can. In this white photosensitive resin composition, the total amount of the components (A) to (D) and (E-1) is 70% by mass or more in the solid content (including the monomer component that becomes a solid content after photocuring), Preferably it is 80 mass%, More preferably, it is 90 mass% or more.

  In the white photosensitive resin composition of this invention, it is preferable to adjust a viscosity using a solvent other than said (A)-(D) and (E-1). The solvent to be used is as exemplified above.

  In the present invention, if necessary, other resin components that are polymerized or cured by light or heat may be used in combination. Other resin components include, for example, alkali-soluble resins obtained by reacting (meth) acrylic acid and acid anhydrides with novolak epoxy resins derived from novolaks such as phenol novolak and cresol novolak, (meth) acrylic acid And an alkali-soluble resin obtained by reacting an epoxy group-containing (meth) acrylate with a carboxyl group in a copolymer of (meth) acrylic acid esters.

  Further, the white photosensitive resin composition of the present invention includes a curing accelerator, an antioxidant, a thermal polymerization inhibitor, a plasticizer, a leveling agent, an antifoaming agent, a coupling agent, a surfactant and the like as necessary. Additives can be blended. Examples of thermal polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, etc., and examples of antioxidants include hindered phenol antioxidants and phosphorus processing heat stabilizers. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate, and examples of the antifoaming agent and leveling agent include silicone, fluorine, and acrylic compounds. Examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant. Examples of the silane coupling agent include 3- (glycidyloxy) propyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane. , 3-ureidopropyltriethoxysilane and the like.

Next, an embodiment for obtaining a cured product including a white cured product using the photosensitive resin composition of the present invention will be described.
The cured product of the present invention is formed by a photolithography method using the photosensitive resin composition of the present invention. As the manufacturing process, first, a photosensitive resin composition solution is applied to the substrate surface, and then the solvent is dried (pre-baked). Then, a photomask is applied on the coating film thus obtained, and ultraviolet rays are applied. There is a method in which an exposed portion is cured by irradiation, a pattern is formed by performing development that elutes an unexposed portion using an alkaline aqueous solution, and post-baking is further performed as post-curing. Here, as a substrate to which the photosensitive resin composition solution is applied, glass, a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, or the like) is used.

  As a method for applying the photosensitive resin composition solution to the substrate, any method such as a method using a roller coater machine, a land coater machine, a slit coater machine or a spinner machine in addition to a known solution dipping method and spray method can be used. Can be adopted. After applying to a desired thickness by these methods, the film is formed by removing the solvent (pre-baking). Pre-baking is performed by heating with an oven, a hot plate or the like. The heating temperature and heating time in the pre-baking are appropriately selected according to the solvent to be used, and are performed, for example, at a temperature of 60 to 110 ° C. for 1 to 3 minutes.

  The exposure performed after pre-baking is performed by an exposure machine, and only the photosensitive resin composition corresponding to the pattern is exposed by exposure through a photomask. The exposure machine and the exposure irradiation conditions are appropriately selected, and exposure is performed using a light source such as an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, or a deep ultraviolet lamp, and the photosensitive resin composition in the coating film is photocured.

  The alkali development after exposure is performed for the purpose of removing the photosensitive resin composition in the unexposed portions, and a desired pattern is formed by this development. Examples of the developer suitable for the alkali development include an aqueous solution of an alkali metal or alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like. It is good to develop at a temperature of 23 to 27 ° C. using a weakly alkaline aqueous solution containing 0.03 to 1% by weight of carbonate, and a fine image is precisely obtained using a commercially available developing machine or ultrasonic cleaner. Can be formed.

  After the development as described above, a thermosetting treatment (post-bake) is performed at a temperature of 200 to 240 ° C. for 20 to 60 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned film and the substrate. This is performed by heating with an oven, a hot plate or the like, as in the pre-baking. The patterned cured product of the present invention is formed through each step by the above photolithography method.

  The alkali-soluble resins of the general formula (1) and the general formula (9) of the present invention are both suitable for light-resistant photosensitive resin compositions, and the photosensitive resin compositions can be patterned by photolithography. In particular, a cured product having excellent development characteristics and light resistance can be obtained. For example, it can be suitably used to obtain a white cured film having excellent light discoloration resistance.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

  Hereinafter, the present invention will be described in more detail based on examples of synthesis of alkali-soluble resins of the general formula (1) and the general formula (9) as the component (A). The scope of the present invention is not limited by these examples. Moreover, evaluation of resin in the following synthesis examples was performed as follows unless otherwise noted.

[Solid content]
1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: w ₀ (g)], weighed [w ₁ (g)], and heated at 160 ° C. for 2 hours [w ₂ ( g)] from the following equation.
Solid content concentration (% by weight) = 100 × (w ₂ −w ₀ ) / (w ₁ −w ₀ )

[Acid value]
Dissolve the resin solution in dioxane, titrate with 1 / 10N-KOH aqueous solution using potentiometric titrator (trade name COM-1600 manufactured by Hiranuma Sangyo Co., Ltd.), and the amount of KOH required per gram of solid content Was the acid value.

[Molecular weight]
Gel permeation chromatography (GPC) (HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuper-H5000 ( 1) (manufactured by Tosoh Corporation), temperature: 40 ° C., speed: 0.6 ml / min), and weight average molecular weight (Mw) as standard polystyrene (Tosoh Corporation PS-oligomer kit) conversion value Is the value obtained.

The abbreviations used in the examples of alkali-soluble resin synthesis and comparative examples are as follows.
EP (a-1-1): 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate
Epoxy compound in which g is 1 in general formula (20)
EP (a-1-2): 6-[(3,4-epoxy) cyclohexylcarbonyloxy] hexanoic acid (3,4-epoxy) cyclohexyl methyl ester
An epoxy compound in which h is 5 and i is 1 in the general formula (21)
EP (a-2-1): Bisphenol A type epoxy resin (epoxy equivalent = 480)
In general formula (8), R ₃ , R ₄ , R ₅ and R ₆ are hydrogen, M is —C (CH ₃ ) ₂ —, and e (average value) = 2.3.

AA: Acrylic acid
MAA: Methacrylic acid
MMA: Methyl methacrylate
CHMA: cyclohexyl methacrylate
BPFL-DGE: 9,9-bis [4- (2-epoxypropyl) phenyl] -9H-fluorene
BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride
BuTDA: 1,2,3,4-butanetetracarboxylic dianhydride
THPA: 1,2,3,6-tetrahydrophthalic anhydride
GMA: Glycidyl methacrylate
TEAB: Tetraethylammonium bromide
AIBN: Azobisisobutyronitrile
PGMEA: Propylene glycol monomethyl ether acetate
DMDG: Diethylene glycol dimethyl ether

[Example 1]
EP (a-1-1) 0.34mol, AA 0.68mol, PGMEA 139.0g and TEAB 2.15g were charged in a 500ml four-neck flask with a reflux condenser, and the reaction was stirred for 20 hours while heating at 100 to 105 ° C. I let you. Next, BPDA 0.12 mol and THPA 0.27 mol were charged into the flask, and the reaction was carried out with stirring at 120 to 125 ° C. for 8 hours. Further, 0.28 mol of GMA was added, and the mixture was stirred at 100 to 105 ° C. for 8 hours with heating to obtain an alkali-soluble resin (A) -1. The obtained resin solution had a solid content concentration of 66.7 wt%, an acid value (converted to a solid content) of 55 mg KOH / g, and Mw by GPC analysis of 4200. The average value of n in the general formula (1) calculated from Mw by GPC analysis was 3.9.

[Example 2]
EP (a-1-1) 0.34mol, AA 0.68mol, PGMEA 139.0g and TEAB 2.14g were charged in a 500ml four-necked flask equipped with a reflux condenser, and the reaction was stirred for 20 hours while heating at 100 to 105 ° C. I let you. Subsequently, 0.12 mol of BuTDA and 0.27 mol of THPA were charged in the flask, and the reaction was carried out by stirring at 120 to 125 ° C. for 8 hours while heating. Further, 0.28 mol of GMA was added, and the mixture was stirred at 100 to 105 ° C. for 8 hours with heating to obtain an alkali-soluble resin (A) -2. The obtained resin solution had a solid content concentration of 65.6 wt%, an acid value (in terms of solid content) of 58 mgKOH / g, and Mw by GPC analysis of 4500. The average value of n in the general formula (1) calculated from Mw by GPC analysis was 4.9.

[Example 3]
EP (a-1-2) 0.28mol, AA 0.56mol, PGMEA 147.0g and TEAB 1.77g were charged in a 500ml four-neck flask with a reflux condenser and stirred at 100 to 105 ° C for 20 hours while heating for reaction. I let you. Next, BPDA (0.10 mol) and THPA (0.22 mol) were charged into the flask, and the reaction was carried out with stirring at 120 to 125 ° C. for 6 hours. Further, 0.23 mol of GMA was added, and the mixture was stirred at 100 to 105 ° C. for 8 hours with heating to obtain an alkali-soluble resin (A) -3. The obtained resin solution had a solid content concentration of 64.3 wt%, an acid value (in terms of solid content) of 48 mg KOH / g, and Mw by GPC analysis of 6600. The average value of n in the general formula (1) calculated from Mw by GPC analysis was 5.9.

[Example 4]
EP (a-1-2) 0.28mol, AA 0.56mol, PGMEA 147.0g and TEAB 1.77g were charged in a 500ml four-neck flask with a reflux condenser and stirred at 100 to 105 ° C for 20 hours while heating for reaction. I let you. Next, BuTDA (0.10 mol) and THPA (0.22 mol) were charged into the flask, and the mixture was reacted at 12 to 125 ° C. with heating for 8 hours. Further, 0.23 mol of GMA was added, and the mixture was stirred at 100 to 105 ° C. for 8 hours with heating to obtain an alkali-soluble resin (A) -4. The obtained resin solution had a solid content concentration of 63.5 wt%, an acid value (in terms of solid content) of 50 mg KOH / g, and Mw by GPC analysis of 6900. The average value of n in the general formula (1) calculated from Mw by GPC analysis was 6.9.

[Example 5]
EP (a-1-1) 0.175 mol, EP (a-2-1) 0.075 mol, AA 0.50 mol, PGMEA 154.0 g and TEAB 1.58 g were charged into a 500 ml four-necked flask equipped with a reflux condenser. The reaction was carried out by stirring at 105 ° C. for 20 hours under heating. Next, 0.09 mol of BPDA and 0.20 mol of THPA were charged in the flask, and the reaction was carried out by stirring at 120 to 125 ° C. for 8 hours while heating. Further, 0.20 mol of GMA was added, and the mixture was stirred at 100 to 105 ° C. for 8 hours with heating to obtain an alkali-soluble resin (A) -5. The obtained resin solution had a solid content concentration of 62.9 wt%, an acid value (in terms of solid content) of 44 mgKOH / g, and Mw by GPC analysis of 7200. The average value of f in the general formula (9) calculated from Mw by GPC analysis was 5.8.

[Synthesis Example 1]
BPFL-DGE 0.23 mol, AA 0.46 mol, PGMEA 161.0 g and TEAB 0.48 g were charged into a 500 ml four-necked flask equipped with a reflux condenser, and stirred at 100 to 105 ° C. for 20 hours with stirring for reaction. Next, 0.12 mol of BPDA and 0.12 mol of THPA were charged into the flask, and stirred at 120 to 125 ° C. for 6 hours with heating to obtain an alkali-soluble resin (A) -6. The obtained resin solution had a solid content concentration of 55.6 wt%, an acid value (converted to a solid content) of 103 mg KOH / g, and Mw by GPC analysis of 3600.

[Synthesis Example 2]
MAA 51.65 g (0.60 mol), MMA 38.44 g (0.38 mol), CHMA 36.33 g (0.22 mol), AIBN 5.91 g, and DMDG 368 g were charged into a 1000 ml four-necked flask equipped with a nitrogen inlet tube and a reflux tube, and 80 to 85 Polymerization was carried out by stirring for 8 hours under nitrogen flow at ℃. Further, 39.23 g (0.28 mol) of GMA, 1.44 g of TPP, and 0.055 g of DTBC were charged into the flask and stirred at 80 to 85 ° C. for 16 hours to obtain a polymerizable unsaturated group-containing (meth) acrylate resin (A) -7. It was. The obtained resin solution had a solid content concentration of 32% by mass, an acid value (converted to a solid content) of 110 mgKOH / g, and Mw by GPC analysis of 18080.

(Preparation of white photosensitive resin composition solution)
The white photosensitive resin composition solutions of Examples 6 to 13 and Comparative Example 1 were prepared by blending according to the composition shown in Table 1. Each component used for the blending is as follows. In addition, the numerical value in Table 1 represents mass%.
(A) Polymerizable unsaturated group-containing alkali-soluble resin solution:
(A) -1 Resin Solution (A) -2 of Example 1 Resin Solution (A) -3 of Example 2 Resin Solution (A) -4 of Example 3-4 Resin Solution (A) -5 of Example 4 Resin solution (A) -6 in Example 5 Resin solution (A) -7 in Synthesis example 1 Resin solution (B) in Synthesis example 2 Photopolymerization initiator: 1,2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)] (trade name Irgacure OXE01 manufactured by BASF)
(C) Photopolymerizable monomer: Dipentaerythritol hexaacrylate (trade name DPHA manufactured by Nippon Kayaku Co., Ltd.)
(E) -1 white light-shielding material: titanium white (average particle size 270 nm) concentration 73 mass%, titanium white dispersion of propylene glycol monomethyl ether acetate solvent (F) solvent:
(F) -1: Propylene glycol monomethyl ether acetate (PGMEA)
(F) -2: 3-methoxy-3-methylbutyl acetate (G) surfactant (1% propylene glycol monomethyl ether acetate solution)
(H) Silane coupling agent

(Evaluation of white photosensitive resin composition: developability)
The white photosensitive resin composition solutions of Examples 6 to 13 and Comparative Example 1 were applied and dried on a degreased and washed 1.2 mm thick glass plate using a spin coater under conditions that resulted in a dry film thickness of 10 μm. Thereafter, a photomask was brought into close contact, and irradiation with ultraviolet rays having a wavelength of 365 nm and an illuminance of 10 mW / cm ² was performed for 10 seconds using a 500 W high-pressure mercury lamp lamp. After the exposure, development was performed with a 0.4% aqueous sodium carbonate solution at 23 ° C. for 60 seconds at a pressure of 0.1 MPa to remove the unexposed portion of the coating film, and then using a hot air dryer at 230 ° C. for 30 minutes. A heat curing treatment was performed to obtain a white film pattern (cured product). And the white film | membrane pattern formed on the glass plate was confirmed with the microscope, and the evaluation regarding pattern formation was performed according to the following. The results are shown in Table 2.
・ Pattern formation ○: Pattern can be formed (5 μm to 30 μm line & space pattern remains)
×: Not dissolved in developer or pattern peeling

(Evaluation of white photosensitive resin composition: light discoloration resistance)
The white photosensitive resin composition solutions of Examples 6 to 13 and Comparative Example 1 were coated on a 1.2 mm thick glass plate that had been degreased and washed using a spin coater under conditions that resulted in a dry film thickness of 10 μm. After drying, the entire surface of the same white film-formed glass plate as described above was irradiated with ultraviolet light having a wavelength of 365 nm and an illuminance of 10 mW / cm ² for 10 seconds without using a photomask. After the exposure, a developer treatment was performed using a 0.4% aqueous sodium carbonate solution at 23 ° C. for 60 seconds at a pressure of 0.1 MPa. Thereafter, a heat curing treatment was performed at 230 ° C. for 30 minutes using a hot air dryer. In order to confirm the light discoloration resistance, an ultraviolet ray having an illuminance of 130 W / cm ² having a wavelength of 254 nm was further irradiated for 2 hours using a low-pressure mercury lamp, and a b ^* value was measured with a spectrophotometer. The results are shown in Table 2.

As is clear from the results of Examples 6 to 13 and Comparative Example 1 shown above, the alkali-soluble resins (A) -1 to (A) -5 of the general formula (1) or general formula (9) of the present invention. And a white photosensitive resin composition in which a part of the component (A) is replaced with a polymerizable unsaturated group-containing alkali-soluble resin which is an acrylic copolymer such as (A) -7 According to the product, it was found that a pattern can be formed and a good white cured product can be obtained with respect to the b ^* value. Note that when the b ^* value exceeds 1.5, yellowing becomes noticeable, which is inappropriate as a white color, and the light discoloration resistance is not sufficient.

  Next, the Example regarding the transparent photosensitive resin composition using the polymerizable unsaturated group containing alkali-soluble resin of this invention is shown.

(Preparation of transparent photosensitive resin composition solution)
Blending was carried out according to the composition shown in Table 3, and transparent photosensitive resin composition solutions of Examples 14 to 22 and Comparative Example 2 were prepared. Each component used for the blending is as follows. In addition, the numerical value of Table 3 represents the mass%.
(A) Polymerizable unsaturated group-containing alkali-soluble resin solution:
(A) -1 Resin solution of Example 1 (A) -6 Resin solution of Synthesis Example 1 (A) -7 Resin solution of Synthesis Example 2 (B) Photopolymerization initiator: 1,2-octanedione, 1- [4- (Phenylthio)-, 2- (O-benzoyloxime)] (trade name Irgacure OXE01 manufactured by BASF)
(C) Photopolymerizable monomer: Dipentaerythritol hexaacrylate (trade name DPHA manufactured by Nippon Kayaku Co., Ltd.)
(D) Epoxy compound: phenol novolac type epoxy resin (JER154 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 178)
(E) Dispersoid dispersion:
(E) -2 (for refractive index adjustment): Titanium oxide dispersion of PGMEA solvent having a titanium oxide concentration of 19.6% by mass and a dispersant of 9.3% by mass (dynamic viscoelasticity measurement (Otsuka Electronics particle size analyzer FPAR -1000) average particle size of cumulant titanium oxide 62nm)
(E) -3 (for shrinkage adjustment): Silica dispersion of PGMEA solvent having a silica sol concentration of 20% by mass (YA010C manufactured by Admatechs) (dynamic viscoelasticity measurement (particle size analyzer FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.)) Silica average particle size of 65nm)
(E) -4 (for coloring): Carbon black dispersion (F) solvent of PGMEA solvent having a carbon black concentration of 25% by mass and a polymer dispersant of 7.5% by mass:
(F) -1: PGMEA
(F) -3: Diethylene glycol methyl ethyl ether (G) Surfactant: Polyether-modified polydimethylsiloxane (BYK302 manufactured by Big Chemie Japan) (1% PGMEA solution)
(H) Silane coupling agent: 3-glycidoxypropyltrimethoxysilane

(Evaluation of transparent photosensitive resin composition: transmittance)
The transparent photosensitive resin composition solutions of Examples 14 to 22 and Comparative Example 2 were degreased and washed on a glass substrate having a thickness of 1.2 mm and a size of 125 mm × 125 mm, and a dry film thickness of 1.0 μm using a spin coater. After coating and drying under the conditions described above, ultraviolet rays with an illuminance of 10 mW / cm ² having a wavelength of 365 nm were irradiated for 10 seconds using a 500 W high-pressure mercury lamp without using a photomask. After the exposure, development was performed using a 0.4% aqueous sodium carbonate solution at 23 ° C. for 60 seconds at a pressure of 0.1 MPa, and then heat curing treatment was performed at 230 ° C. for 30 minutes using a hot air dryer. About the glass substrate in which this cured film was formed, transparency was evaluated based on the transmittance | permeability as follows. The light transmittance was measured at 400 nm using a spectrophotometer (device: Nippon Denshoku SD5000). The results are shown in Table 4.
・ Transparency ○: Transmittance 85% or more ×: Transmittance less than 85%

(Evaluation of transparent photosensitive resin composition: developability)
The transparent photosensitive resin composition solutions of Examples 14 to 22 and Comparative Example 2 were coated on a 1.2 mm thick glass plate that had been degreased and washed using a spin coater under the conditions that resulted in a dry film thickness of 1.5 μm. After drying, a photomask was brought into close contact, and irradiated with ultraviolet rays having a wavelength of 365 nm and an illuminance of 10 mW / cm ² for 10 seconds using a 500 W high pressure mercury lamp lamp. After the exposure, development was performed with a 0.4% aqueous sodium carbonate solution at 23 ° C. for 60 seconds at a pressure of 0.1 MPa to remove the unexposed portion of the coating film, and then using a hot air dryer at 230 ° C. for 30 minutes. A heat curing treatment was performed to obtain a transparent film pattern (cured product). And the transparent film pattern formed on the glass plate was confirmed with the microscope, and the evaluation regarding pattern formation was performed according to the following. The results are shown in Table 4.
・ Developability ○: Pattern can be formed (5 μm to 30 μm line & space pattern remains)
×: Not dissolved in developer or pattern peeling

(Evaluation of transparent photosensitive resin composition: light-resistant adhesion)
The transparent photosensitive resin composition solutions of Examples 14 to 22 and Comparative Example 2 were dried on a glass substrate having a thickness of 1.2 mm and a size of 125 mm × 125 mm using a spin coater and a dry film thickness of 1.5 μm. After coating and drying under the conditions as described above, ultraviolet rays with an illuminance of 10 mW / cm ² having a wavelength of 365 nm were irradiated for 10 seconds using a 500 W high-pressure mercury lamp without using a photomask. After the exposure, development was performed using a 0.4% aqueous sodium carbonate solution at 23 ° C. for 60 seconds at a pressure of 0.1 MPa, and then heat curing treatment was performed at 230 ° C. for 30 minutes using a hot air dryer. The glass substrate on which this cured film was formed was evaluated for light resistance adhesion. In the UV cleaning, the surface of the glass substrate is cleaned by irradiating with UV light having a wavelength of 254 nm and an illuminance of 1000 mJ / cm ² with a low-pressure mercury lamp.

A xenon (Xe) lamp (irradiated surface illuminance of 250 W / m ² ) was irradiated from the glass surface side of the glass substrate on which the cured film was formed, and left for 200 hours under conditions of a temperature of 60 ° C. and a humidity of 50%. After that, cut into this cured film so that 100 square squares of 1mm x 1mm were formed using the product name "Super Cutter Guide" manufactured by Dazai Equipment Co., Ltd. A tape peeling test was performed in which cellophane tape (manufactured by Nichiban) was applied and then peeled off, and evaluation was performed according to the following criteria. The results are shown in Table 4.
Light-resistant adhesion ○: The cured product in the cell is not peeled at all Δ: Less than 1/3 of the cured product in the cell is peeled ×: More than 1/3 is peeled off

(Evaluation of transparent photosensitive resin composition: light discoloration resistance)
The transparent photosensitive resin composition solutions of Examples 14 to 22 and Comparative Example 2 were degreased and washed on a glass plate having a thickness of 1.2 mm using a spin coater under the condition that a dry film thickness of 1.5 μm was obtained. After coating and drying, ultraviolet rays having an illuminance of 10 mW / cm ² having a wavelength of 365 nm were irradiated for 10 seconds from the transparent film forming side using a 500 W high-pressure mercury lamp lamp without using a photomask. After the exposure, a developer treatment was performed using a 0.4% aqueous sodium carbonate solution at 23 ° C. for 60 seconds at a pressure of 0.1 MPa. Thereafter, a heat curing treatment was performed at 230 ° C. for 30 minutes using a hot air dryer. About this cured film, b ^* value was measured with the spectrophotometer (apparatus: Nippon Denshoku SD5000). Next, in order to confirm the light discoloration resistance, an ultraviolet ray having an illuminance of 130 W / cm ² having a wavelength of 254 nm was further irradiated for 2 hours using a low-pressure mercury lamp, and b ^{* was} measured with a spectrophotometer (device: Nippon Denshoku SD5000) ^. The value was measured. The results are shown in Table 4 including the value of the difference Δb ^* between the b ^* values before and after further ultraviolet irradiation.

  As is clear from the results of Examples 14 to 22 and Comparative Example 2 shown above, the transparent photosensitive resin composition containing the alkali-soluble resin (A) -1 represented by the general formula (1) can be patterned. Thus, as in Comparative Example 2, it can be confirmed that there is no decrease in adhesion to the glass substrate after the ultraviolet irradiation, and the b * value does not change greatly after the ultraviolet irradiation. Therefore, it turned out that the transparent photosensitive resin composition excellent in light resistance can be provided by this invention. In addition, in Example 17 where the actual epoxy resin was used in combination with the components of Examples 14 to 16, the effect of improving light resistance was obtained, and the epoxy resin was used in combination for improving surface hardness and chemical resistance. You can see that it is possible. Moreover, even if it added metal oxides, such as a titanium oxide and a silica, to the component of Examples 14-16, the improvement effect of light resistance can be maintained like Examples 18-20, and adjustment of refractive index or This shows that it is possible to control the surface hardness and cure shrinkage of the cured product. Example 21 shows that an acrylic copolymer such as (A) -7 may be used in combination with the alkali-soluble resin (A) -1 of the general formula (1) in the configuration to which the metal oxide is added. . As described above, it can be seen that by using the photosensitive resin composition of the present invention, a cured product having excellent light resistance can be obtained while adjusting the physical properties of the cured product depending on the application.

  Next, the Example regarding the black photosensitive resin composition using the polymerizable unsaturated group containing alkali-soluble resin of this invention is shown.

(Preparation of black photosensitive resin composition solution)
Compounding was carried out according to the composition shown in Table 5, and black photosensitive resin composition solutions of Examples 23 to 26 and Comparative Example 3 were prepared. Each component used for the blending is as follows. In addition, the numerical value in Table 5 represents the mass%.
(A) Polymerizable unsaturated group-containing alkali-soluble resin solution:
(A) -1 Resin solution of Example 1 (A) -7 Resin solution of Synthesis Example 2 (B) Photopolymerization initiator: 1- [9-ethyl-6- (2-methylbenzoyl) carbazol-3-yl ] Ethanone = O-acetyloxime (trade name Irgacure OXE02 manufactured by BASF)
(C) Photopolymerizable monomer: Dipentaerythritol hexaacrylate (trade name DPHA manufactured by Nippon Kayaku Co., Ltd.)
(E) Dispersoid dispersion:
(E) -4 (for coloring): Carbon black dispersion (E) -5 (for coloring) of PGMEA solvent having a carbon black concentration of 25% by mass and a polymer dispersant of 7.5% by mass: C.I. I. Pigment Black 31 concentration 15% by mass, polymer dispersant 10% by mass PGMEA solvent black organic pigment dispersion (F) solvent:
(F) -1: PGMEA
(F) -3: Diethylene glycol methyl ethyl ether (G) Surfactant: Polyether-modified polydimethylsiloxane (BYK302 manufactured by Big Chemie Japan) (1% PGMEA solution)
(H) Silane coupling agent: 3-glycidoxypropyltrimethoxysilane

(Evaluation of black photosensitive resin composition: light shielding rate)
A dry film thickness of 1.0 μm using a spin coater on a glass substrate having a thickness of 1.2 mm and a size of 125 mm × 125 mm obtained by degreasing and cleaning the black photosensitive resin composition solutions of Examples 23 to 26 and Comparative Example 3. After coating and drying under the conditions described above, ultraviolet rays with an illuminance of 10 mW / cm ² having a wavelength of 365 nm were irradiated for 10 seconds from the black film side using a 500 W high-pressure mercury lamp without using a photomask. After the exposure, development was performed using a 0.4% aqueous sodium carbonate solution at 23 ° C. for 60 seconds at a pressure of 0.1 MPa, and then heat curing treatment was performed at 230 ° C. for 30 minutes using a hot air dryer. About the glass substrate in which this cured film was formed, the light-shielding rate (OD / micrometer) was measured. OD was measured using a Macbeth transmission densitometer. The results are shown in Table 6.

(Evaluation of black photosensitive resin composition: developability)
The black photosensitive resin composition solutions of Examples 23 to 26 and Comparative Example 3 were coated on a 1.2 mm thick glass plate that had been degreased and washed using a spin coater under the conditions that resulted in a dry film thickness of 1.1 μm. After drying, a photomask was brought into close contact, and irradiated with ultraviolet rays having a wavelength of 365 nm and an illuminance of 10 mW / cm 2 for 10 seconds using a 500 W high pressure mercury lamp lamp. After the exposure, development was performed with a 0.4% aqueous sodium carbonate solution at 23 ° C. for 60 seconds at a pressure of 0.1 MPa to remove the unexposed portion of the coating film, and then using a hot air dryer at 230 ° C. for 30 minutes. A heat curing treatment was performed to obtain a black film pattern (cured product). And the black film pattern formed on the glass plate was confirmed with the microscope, and the evaluation regarding pattern formation was performed according to the following. The results are shown in Table 6.
・ Developability ○: Pattern can be formed (5 μm to 30 μm line & space pattern remains)
×: Not dissolved in developer or pattern peeling

(Evaluation of black photosensitive resin composition: light-resistant adhesion)
The black photosensitive resin composition solutions of Examples 23 to 26 and Comparative Example 3 were dried on a glass substrate having a thickness of 1.2 mm and a size of 125 mm × 125 mm using a spin coater and a dry film thickness of 1.5 μm. After coating and drying under the conditions described above, ultraviolet rays with an illuminance of 10 mW / cm ² having a wavelength of 365 nm were irradiated for 10 seconds from the black film side using a 500 W high-pressure mercury lamp without using a photomask. After the exposure, development was performed using a 0.4% aqueous sodium carbonate solution at 23 ° C. for 60 seconds at a pressure of 0.1 MPa, and then heat curing treatment was performed at 230 ° C. for 30 minutes using a hot air dryer. The glass substrate on which this cured film was formed was evaluated for light resistance adhesion. In the UV cleaning, the surface of the glass substrate is cleaned by irradiating with UV light having a wavelength of 254 nm and an illuminance of 1000 mJ / cm ² with a low-pressure mercury lamp.

A xenon (Xe) lamp (irradiated surface illuminance of 250 W / m ² ) was irradiated from the glass surface side of the glass substrate on which the cured film was formed, and left for 200 hours under conditions of a temperature of 60 ° C. and a humidity of 50%. After that, cut into this cured film so that 100 square squares of 1mm x 1mm were formed using the product name "Super Cutter Guide" manufactured by Dazai Equipment Co., Ltd. A tape peeling test was performed in which cellophane tape (manufactured by Nichiban) was applied and then peeled off, and evaluation was performed according to the following criteria. The results are shown in Table 6.
Light-resistant adhesion ○: The cured product in the cell is not peeled at all Δ: Less than 1/3 of the cured product in the cell is peeled ×: More than 1/3 is peeled off

(Evaluation of black photosensitive resin composition: reflectivity change by ultraviolet irradiation)
The black photosensitive resin composition solutions of Examples 23 to 26 and Comparative Example 3 were degreased and washed on a glass plate having a thickness of 1.2 mm using a spin coater under the condition that a dry film thickness of 1.5 μm was obtained. After coating and drying, ultraviolet rays with an illuminance of 10 mW / cm ² having a wavelength of 365 nm were irradiated for 10 seconds from the black film side using a 500 W high pressure mercury lamp lamp without using a photomask. After the exposure, a developer treatment was performed using a 0.4% aqueous sodium carbonate solution at 23 ° C. for 60 seconds at a pressure of 0.1 MPa. Thereafter, a heat curing treatment was performed at 230 ° C. for 30 minutes using a hot air dryer. The Y value of this cured film was measured with a spectrophotometer (device: Nippon Denshoku SD5000). Next, in order to confirm the change in reflectivity due to UV irradiation, UV light having a wavelength of 254 nm and an illuminance of 130 W / cm ^{2 was} further irradiated for 2 hours using a low-pressure mercury lamp, and a spectrophotometer (device: Nippon Denshoku SD5000) was used. The Y value was measured. The results are shown in Table 6 including the value of the difference ΔY between the Y values before and after further ultraviolet irradiation.

(Evaluation of black photosensitive resin composition: maximum displacement and recovery rate of cured film)
The black photosensitive resin composition solutions of Examples 23 to 26 and Comparative Example 3 were coated on a 1.2 mm thick glass plate that had been degreased and washed under the condition that a dry film thickness of 3 μm was obtained using a spin coater. After drying, ultraviolet rays with a wavelength of 365 nm and an illuminance of 10 mW / cm ² were irradiated for 10 seconds from the black film side using a 500 W high pressure mercury lamp lamp without using a photomask. After the exposure, a developer treatment was performed using a 0.4% aqueous sodium carbonate solution at 23 ° C. for 60 seconds at a pressure of 0.1 MPa. Thereafter, a heat curing treatment was performed at 230 ° C. for 30 minutes using a hot air dryer. About this cured film, the maximum displacement and the elastic recovery rate were measured using the micro compression tester (Brand name: HM2000, Fischer Instruments company make). With a flat indenter of 50μm square, the load speed and unloading speed are both 5mN / sec. After loading up to 50mN, unloading is performed, and the load-deformation curve and the load-deformation curve during unloading. A curve was created. At this time, the deformation amount at a load of 50 mN at the time of loading was defined as the maximum displacement. Further, the elastic recovery rate was calculated by the following formula using the maximum displacement and the deformation amount at the time of unloading.
Elastic recovery rate (%) = (Maximum displacement-Deformation amount at unloading) x 100 / Maximum displacement / Maximum displacement ○: 0.2 micron or more ×: 0.2 micron or less Elastic recovery rate ○: 30% or more x: Less than 30% Table 6 shows the measurement results.

  As is clear from the results of Examples 23 to 26 and Comparative Example 3 described above, according to the black photosensitive resin composition containing the alkali-soluble resin (A) -1 of the general formula (1) of the present invention, Pattern formation is possible, and the adhesiveness with the glass substrate after being irradiated with ultraviolet rays is sufficient, and a pattern with better light-resistant adhesiveness than Comparative Example 3 can be formed. In addition, with respect to the reflectivity indicated as the Y value, ΔY before and after UV irradiation is a numerical value less than 1, and it can be seen that the change in reflectivity before and after UV irradiation is smaller than that of Comparative Example 3, It is shown that the black photosensitive resin composition of the present invention is also useful when it is desired to avoid a decrease in designability due to a change in reflectance due to ultraviolet irradiation. Furthermore, the maximum displacement and recovery rate at the time of pressure loading and unloading are at a level that can be used without any problem as a black column spacer (a component of an LCD that also serves as a photo spacer and a black matrix). As the black column spacer, no particular difference from Comparative Example 3 is observed, but the present invention is an effective technique if an application in which light resistance is a problem is found.

  According to the alkali-soluble resin of the present invention, a photosensitive resin composition capable of forming a pattern and satisfying the light resistance requirement can be obtained. Therefore, in addition to being useful for decorating touch panels, for example, the white photosensitive resin composition using the alkali-soluble resin of the present invention can form a white film excellent in light discoloration resistance. In other words, since it can be formed by photolithography, there is an advantage that it can be formed by an existing photolithography process. Furthermore, since it can be formed by a thin film, it can contribute to thinning of the structure, and white color in the production of touch panels. Suitable for forming a film.

Claims (11)

Dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (b), and tetracarboxylic acid as a reaction product of an epoxy compound (a) having two epoxy groups in one molecule and an unsaturated group-containing monocarboxylic acid In an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule obtained by reacting an acid or an acid dianhydride (c), two epoxycyclohexanes in one molecule are used as the epoxy compound (a). An alkali-soluble resin represented by the following general formula (1) and having a carboxyl group and a polymerizable unsaturated group in one molecule by using an epoxy compound (a-1) having an alkyl group.

(However, R ₁ represents a hydrogen atom or a methyl group. X represents a single bond or a divalent organic group having 1 to 20 carbon atoms which may contain a hetero element therein, and Y represents a tetravalent carboxylic acid. Represents a residue, Z represents a hydrogen atom or a substituent represented by the following general formula (2), G represents a hydrogen atom or a substituent represented by the following general formula (3), n is an average of 1 to 20 Indicates the value.)

(Wherein, R ₁ is the same meaning as in general formula (1), R ₂ represents a divalent hydrocarbon group having 2 to 10 carbon atoms, L a divalent or trivalent carboxylic acid residue M is 0 or 1. p and q are 0, 1 or 2, and p + q is 1 or 2.) For a reaction product of an epoxy compound (a-1) represented by the following general formula (4) having two epoxycycloalkyl groups in one molecule and an unsaturated group-containing monocarboxylic acid, dicarboxylic acid or tricarboxylic acid In the carboxyl group of the polymerizable unsaturated group-containing alkali-soluble resin represented by the following general formula (5) obtained by reacting an acid or its acid monoanhydride (b) and a tetracarboxylic acid or its acid dianhydride (c) On the other hand, the alkali-soluble resin according to claim 1, wherein an unsaturated group-containing epoxy compound represented by the following general formula (7) is further reacted.

(However, R ₁ , X, Y, and n are as defined in formula (1), and Z ′ represents a hydrogen atom or a substituent represented by formula (6).)

(However, L is synonymous with what was shown in General formula (2), and r is 1 or 2.)

(However, R ₁ , R ₂ and m are synonymous with those shown in the general formulas (1), (2) and (3).) Dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (b), and tetracarboxylic acid as a reaction product of an epoxy compound (a) having two epoxy groups in one molecule and an unsaturated group-containing monocarboxylic acid In an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule obtained by reacting an acid or an acid dianhydride (c), two epoxycyclohexanes in one molecule are used as the epoxy compound (a). Together with the epoxy compound (a-1) having an alkyl group, the epoxy compound (a-2) having two epoxy groups in one molecule derived from bisphenols represented by the following general formula (8) Thus, an alkali-soluble resin represented by the following general formula (9), having a carboxyl group and a polymerizable unsaturated group in one molecule.

_{[However, R 3, R 4, R} 5, and R ₆ represents independently a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, a halogen atom or a phenyl group. M is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, fluorene -9,9-diyl group or a single bond, e represents an average value of 0 to 10 (however, 0 is not included). ]

[W 2 and W ′ are represented by a divalent organic group P represented by the following general formula (10) and / or a divalent organic group Q represented by the following general formula (11). Y represents a tetravalent carboxylic acid residue, Z represents a hydrogen atom or a substituent represented by the following general formula (2), and G represents a hydrogen atom or the following general formula (3). The substituents shown are shown.

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a divalent hydrocarbon group having 2 to 10 carbon atoms, L represents a divalent or trivalent carboxylic acid residue, and m represents 0 or 1. p and q are 0, 1 or 2, and p + q is 1 or 2. f represents an average value of 1-20. Here, f is an integer in each molecule of the alkali-soluble resin represented by the general formula (9), and the number of units represented by the organic groups P and Q in the molecule is represented by f _P and f, respectively. _{When Q is} assumed, f = f _P + f _Q. Note that when W ′ = P, f _Q ≠ 0, and when W ′ = Q, f _P ≠ 0.

(However, R ₁ has the same meaning as that shown in the general formula (2), and R ₃ , R ₄ , R ₅ , R ₆ , M, and e have the same meanings as those shown in the general formula (8).)] (A) either one or both of the alkali-soluble resin of the general formula (1) described in claim 1 or the alkali-soluble resin of the general formula (9) described in claim 3;
(B) a photopolymerization initiator;
A photosensitive resin composition comprising:   In addition to the component (A) and the component (B), (C) a photopolymerizable monomer having at least one polymerizable unsaturated group and / or (D) an epoxy compound or epoxy resin containing two or more epoxy groups. The photosensitive resin composition of Claim 4 containing.   The photosensitive resin composition according to claim 4 or 5, further comprising (E) a dispersoid.   The photosensitive composition of Claim 6 WHEREIN: (E) Dispersoid is (E-1) white pigment, The white photosensitive resin composition characterized by the above-mentioned.   In the white photosensitive resin composition of Claim 7, (A) component is 1-55 mass% in solid content, (C) component is 0-100 mass parts with respect to 100 mass parts of (A) component, (B) 0.1-40 mass parts of component with respect to 100 mass parts of total amounts of (A) component and (C) component, and (E) component are contained 1-95 mass%, It is characterized by the above-mentioned. White photosensitive resin composition.   Hardened | cured material obtained by patterning the photosensitive resin composition in any one of Claims 4-8 by the photolithographic method, and continuing thermosetting.   A touch panel having the cured product according to claim 9.   A color filter having the cured product according to claim 9.