JP6749437B2 - Method for producing alkali-soluble resin, alkali-soluble resin, photosensitive resin composition containing alkali-soluble resin, and cured product using photosensitive resin composition - Google Patents

Description

The present invention provides an alkali-soluble resin suitable for a photosensitive resin composition capable of forming a desired pattern and having excellent light discoloration resistance, a method for producing the same, and a photosensitive resin composition using the alkali-soluble resin. And a cured product thereof, and further to a touch panel and a color filter containing the cured product as a constituent component. In particular, since the photosensitive resin composition according to the present invention can be used as a white photosensitive resin composition for forming a white cured product that is greatly affected by light discoloration resistance, for example, white for decorating a touch panel. It is suitable as a material. Other than that, as a color filter, a component of a display device such as a touch panel, etc., it can be applied to a transparent cured film, a light-shielding film or the like that requires light resistance. Therefore, the photosensitive resin composition of the present invention has a transparent photosensitive property. It is also useful as a resin composition, a black photosensitive resin composition, and the like.

Due to the diversification of information devices and the trend toward smaller and lighter mobile terminals in recent years, input displays have been constructed with a touch panel integrated with a flat display such as a liquid crystal display panel, including mobile phones, mobile information terminals, and car navigation systems. 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 the detection method. Among them, the capacitive touch panel has a transparent conductive film (transparent electrode) on one substrate, and has a capacitance formed by touching with a finger or a pen. The contacted position is specified by detecting a change in the amount of weak current flowing therethrough, and receives the instructed content as an input signal to drive the liquid crystal display device or the like. The capacitance type touch panel has an advantage that a higher transmittance can be obtained as compared with the resistive film type touch panel.

In any of the touch panel types, a transparent protective plate such as a cover glass is usually used on the upper surface of the touch panel to detect an input signal or to protect 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 are provided with a functional film such as a low reflection film, an anti-glare film, a hard coat film, and an electromagnetic shield film.

In addition, with the recent trend of fashion of electronic devices, it is common that decoration such as shielding of LCD (liquid crystal display) wiring is applied by various printing methods on transparent protective plates of mobile terminal devices such as mobile phones. Is. For example, in Patent Document 1 and Patent Document 2, there is provided a protective panel in which a window-forming layer having a transparent window portion is preliminarily formed on the back surface of a hard coat film on a transparent protective plate surface, and a decorative film is attached in a laminated state. An electronic device comprising: the transparent protective plate, the movable electrode film laminated with a decorative film, and the movable electrode film bonded to the movable electrode film at a peripheral edge portion so as to form an air layer between the movable electrode film and the movable electrode film. An electronic device including a touch panel including the fixed electrode plate is disclosed. Conventionally, as described above, it is general that the decorated transparent protective plate and the touch panel are separately formed and combined in a later step. However, there is a strong need for thinner mobile phones in recent years, and reduction of the number of processes by directly forming a touch panel on the decorative transparent protective plate has been considered, and thin patterning is possible as a decoration method. A method using various photosensitive resins has been attracting attention. A method for manufacturing a touch panel 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 a touch panel, but white decoration is required as the electronic devices become fashionable.

However, particularly in the case of a white photosensitive resin, discoloration may occur due to the 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. Further, if the light resistance is insufficient, the touch panel may be colored or the light reflectance may be reduced while the touch panel is being used. In the case of a white photosensitive resin for a touch panel, discoloration and a decrease in reflectance are particularly noticeable, which may cause a decrease in commercial value, and a solution is required.

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

Therefore, an object of the present invention is to solve the above-mentioned problems in the prior art, and to have a sufficient light discoloration resistance, an alkali-soluble resin capable of obtaining a white photosensitive resin composition having excellent developing characteristics, and It is intended to provide a method for producing the same, a photosensitive resin composition using the alkali-soluble resin, a cured product using the same, and a touch panel including the cured product as a constituent component. Further, in a photosensitive resin composition containing no colorant or a photosensitive resin composition containing a colorant other than white, by using a polymerizable unsaturated group-containing alkali-soluble resin having a specific structure, light resistance is required. In that case, it is an effective technique, and a cured product to which this technique is applied can be applied to an overcoat having good light resistance, an insulating film, and a colored pixel. That is, the present invention can be applied to other than the white photosensitive resin composition, and can be used as a component of a touch panel or a color filter having good light resistance, for example.

As a result of intensive studies to solve the above problems, the present inventors have found that by using an alkali-soluble resin (A) having a carboxyl group and a polymerizable unsaturated group in one molecule having a specific structure, It was found that it is possible to obtain a photosensitive resin composition that satisfies the requirements for light resistance. That is, it is a photosensitive resin composition containing a photopolymerization initiator (B) as an essential component in addition to the component (A), and also a photopolymerizable monomer (C) and/or an epoxy compound or an epoxy resin (D). ) Is further added, and the dispersoid (E) is further added to the photosensitive resin composition. Among these, it is suitable as a white photosensitive resin composition containing a white light shielding material as the dispersoid (E), capable of forming a pattern by light, and obtaining a cured product having excellent light discoloration resistance, For example, they have found that they are useful as decorations for 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、ｎは１〜２０の平均値を示し、Ｚ’は水素原子又は一般式（６）で示される置換基を示して、Ｚ’の少なくとも１つは一般式（６）で示される置換基である。）

（但し、Ｌは２又は３価のカルボン酸残基を示し、ｒは１又は２である。） The gist of the present invention is as follows.
(1) The present invention provides a reaction product of an epoxy compound (a-1) represented by the following general formula (4) and having two epoxycycloalkyl groups in one molecule, and an unsaturated group-containing monocarboxylic acid. In contrast, by reacting a dicarboxylic acid or a tricarboxylic acid or an acid monoanhydride thereof (b) with a tetracarboxylic acid or an acid dianhydride thereof (c), an intramolecular compound represented by the following general formula (5) is obtained. A method for producing an alkali-soluble resin, characterized in that an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group is obtained.

(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, n represents an average value of 1 to 20, Z′ represents a hydrogen atom or a substituent represented by the general formula (6), and at least one Z′ is represented by the general formula (6). It is a substituted group.)

(However, L represents a divalent or trivalent carboxylic acid residue, and r is 1 or 2.)

〔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（６）で示される置換基を示して、Ｚ’の少なくとも１つは一般式（６）で示される置換基であり、ｆは１〜２０の平均値を表す。ここで、一般式（２４）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であり、Ｗ'＝Ｑである場合はｆ_P≠０である。

（但し、Ｒ₁は水素原子またはメチル基を示し、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｍ、ｅは一般式（８）に示したものと同義である。）

（但し、Ｌは２又は３価のカルボン酸残基を示し、ｒは１又は２である。）〕 (2) 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 with respect to a dicarboxylic acid or tricarboxylic acid or its acid monoanhydride. In the alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule obtained by reacting the compound (b) with tetracarboxylic acid or its acid dianhydride (c), 1 as the epoxy compound (a) An epoxy compound having two epoxy groups in one molecule, which is 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 A method for producing an alkali-soluble resin characterized by having a carboxyl group and a polymerizable unsaturated group in one molecule, which is represented by the following general formula (24) by using (a-2) together.

_{[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. Further, M _{-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, and e represents an average value of 0 to 10 (excluding 0). ]

[However, W 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) Represents a valent organic group, Y represents a tetravalent carboxylic acid residue, Z′ represents a hydrogen atom or a substituent represented by the following general formula (6), and at least one of Z′ represents a general formula ( 6) is a substituent represented by 6), and 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 the organic groups P and Q in the molecule is f _P and f, respectively. _{When Q} is set, f=f _P +f _Q. In addition, W 'If you are a = P is the f _Q ≠ 0, W' If you are a = Q is f _P ≠ 0.

(However, R ₁ represents a hydrogen atom or a methyl group, and R ₃ , R ₄ , R ₅ , R ₆ , M, and e have the same meanings as shown in formula (8).)

(However, L represents a divalent or trivalent carboxylic acid residue, and r is 1 or 2.)

(3) The present invention also provides (A) an alkali-soluble resin of the general formula (5) obtained by the method described in (1) above, or a general formula obtained by the method described in (2) above. Either or both of the alkali-soluble resin of (24),
(B) a photopolymerization initiator,
It is a photosensitive resin composition characterized by containing.

(4) The present invention also comprises, in addition to the component (A) and the component (B), two (C) a photopolymerizable monomer having at least one polymerizable unsaturated group and/or (D) an epoxy group. The photosensitive resin composition as described in (3) above, which contains the epoxy compound or the epoxy resin containing the above.

(5) The present invention is also the photosensitive resin composition as described in (3) or (4) above, which further contains (E) a dispersoid.
(6) The present invention is also the white photosensitive resin composition as described in (5) above, wherein the (E) dispersoid is (E-1) a white pigment.
(7) The present invention also provides the white photosensitive resin composition according to (6), wherein the component (A) is 1 to 55 mass% and the component (C) is 100 parts by mass in the solid content. To 100 parts by mass, the component (B) is 0.1 to 40 parts by mass, and the component (E) is 1 to 95 parts by mass based on 100 parts by mass of the total of the components (A) and (C). It is a white photosensitive resin composition characterized by being contained by mass %.
(8) The present invention is also a cured product obtained by patterning the photosensitive resin composition according to any one of the above (3) to (7) by a photolithography method and subsequently thermally curing it.
(9) The present invention is also a touch panel having the cured product according to (8).
(10) The present invention also provides a color filter having the cured product according to (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て、少なくとも１つは下記一般式（２）で示される置換基であり、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 will be described in detail below.
In the present invention, the alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule is a reaction between an epoxy compound (a) having two epoxy groups in one molecule and an unsaturated group-containing monocarboxylic acid. Obtained by reacting a dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (b) with a tetracarboxylic acid or its acid dianhydride (c). An alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule represented by the following general formula (1), which is characterized by using an epoxy compound (a-1) having an epoxycycloalkyl 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 general formula (2), at least one is a substituent represented by the following general formula (2), and G represents a hydrogen atom or a general formula ( 3) represents a substituent, and n represents an average value of 1 to 20.)

(However, 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 is 0 or 1. p and q are 0 or 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 general formula (1)”) will be described in detail. explain.
First, an epoxy compound (a-1) represented by the general formula (4) and having two epoxycycloalkyl groups in one molecule is reacted with an unsaturated group-containing monocarboxylic acid, preferably (meth)acryl. An epoxy (meth)acrylate compound is obtained by reacting an acid. Examples of unsaturated group-containing monocarboxylic acid compounds include, in addition to acrylic acid and methacrylic acid, compounds obtained by reacting acrylic acid and methacrylic acid with acid dianhydrides such as succinic anhydride, maleic anhydride, and phthalic anhydride. To be

(However, X has the same meaning as 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 between such an epoxy compound and (meth)acrylic acid, a known method can be used. For example, about 2 mol of (meth)acrylic acid is added to 1 mol of the epoxy compound having two epoxy groups. Do using. The reaction product obtained by this reaction is described in, for example, JP-A-4-355450. The reaction product obtained by this reaction is a diol compound having a polymerizable unsaturated group, and is an epoxy (meth)acrylate compound (d) represented by the following general formula (12).

(However, R ₁ and X have the same meanings as 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 therein. Is a divalent organic group. The divalent organic group having 1 to 20 carbon atoms which may contain a hetero element inside is a divalent hydrocarbon group or a divalent hydrocarbon group having a carboxyl group at one or two ends of the hydrocarbon group. And the like, and the hydrocarbon group may have an ether bond-forming oxygen atom or an ester bond inside. Examples of such a divalent hydrocarbon group include straight-chain hydrocarbon groups such as methylene group, ethylene group, propylene group, isopropylidene group, sec-butylene group, methylisobutylene group, hexylene group, decylene group and dodecylene group. 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 the general formula (13), g is 1, in the general formula (14), h is 5 and i is 1, j in the general formula (15) is 2, and k is in the general formula (16). Is preferably 4 and 1 is 1.

(However, g represents an integer of 1 to 20, h represents an integer of 2 to 20, i represents an integer of 0 to 10, j represents an integer of 1 to 20, and k represents an integer of 0 to 18. Represents, and 1 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 the 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 the 4-position and the 5-position may be bonded at random.

（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). And two or more kinds may be used in combination at the same time. From the viewpoint of easy availability and physical properties of the cured product, the epoxy compound represented by the general formula (20) or (21) is preferable, and it is preferable that g is 1, h is 5 and i is 1.

(However, g to l have the same meanings as shown in the general formulas (13) to (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 its anhydride, and further polymerization having reactivity with carboxyl group When a monofunctional epoxy compound having an unsaturated group is reacted to produce an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in the molecule represented by the general formula (1), it is usually necessary in a solvent. The reaction is carried out using a catalyst according to the above. Here, the solvent to be used, the reaction conditions such as a catalyst is not particularly limited, for example, it is preferable to use a solvent having no hydroxyl group and a boiling point higher than the reaction temperature as a reaction solvent, and such a solvent is For example, a cellosolve-based solvent such as ethyl cellosolve acetate, butyl cellosolve acetate or the like, a high-boiling point ether- or ester-based solvent such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, cyclohexanone, diisobutyl ketone. It is preferable that the solvent is a ketone solvent or the like. Further, it is preferable to use a catalyst in the reaction between the carboxyl group and the epoxy group, and examples of the catalyst to be used include tetraethylammonium bromide, ammonium salts such as triethylbenzylammonium chloride, triphenylphosphine, tris(2,6- Known compounds such as 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して、Ｚ’の少なくとも１つは一般式（６）で示される置換基である。）

（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 between the epoxy compound and (meth)acrylic acid is reacted with the acid components (b) and (c) to give the compound represented by the general formula (5). It is possible to obtain an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in the molecule represented by (hereinafter, referred to as “alkali-soluble resin of general formula (5)”).

(However, R ₁ , X, Y, and n have the same meanings as shown in formula (1), Z′ represents a hydrogen atom or a substituent represented by formula (6), and at least Z′ is represented by One is a substituent represented by the general formula (6).)

(However, L has the same meaning as in 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 the hydroxyl group in the molecule of the epoxy (meth)acrylate compound, such as 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 have a bond containing a hetero element such as -O-, -S-, or a carbonyl group. May be included. Among them, the dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (b) is, for example, a chain hydrocarbon dicarboxylic acid or tricarboxylic acid, an alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, an aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid. , Or their acid monoanhydrides can be used. The tetracarboxylic acid or its acid dianhydride (c) may be a chain hydrocarbon tetracarboxylic acid, an alicyclic hydrocarbon tetracarboxylic acid, an aromatic hydrocarbon tetracarboxylic acid, or an acid dianhydride thereof. Can be used. In addition, it is advantageous to use acid monoanhydride for (b) and acid dianhydride for (c) from the viewpoint of reactivity and reaction control.

Specific examples of the acid component used are shown below.
First, the dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (b) is shown. Examples of dicarboxylic acid or tricarboxylic acid are shown below, but it is preferable to use the acid monoanhydride, and two or more kinds can be used in combination.
Examples of the saturated chain hydrocarbon dicarboxylic acid and/or tricarboxylic acid include succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacine. Acid, suberic acid, diglycolic acid, etc. can be mentioned. Further, a saturated chain hydrocarbon dicarboxylic acid or tricarboxylic acid having a substituent such as an alicyclic hydrocarbon group or an unsaturated hydrocarbon group may be used. Next, examples of the alicyclic hydrocarbon dicarboxylic acid and tricarboxylic acid include hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornanedicarboxylic acid, and hexahydrotrimellitic acid. Further, an alicyclic dicarboxylic acid or tricarboxylic acid having a substituent such as a chain hydrocarbon or an unsaturated hydrocarbon group may be used. Examples of unsaturated dicarboxylic acids and tricarboxylic acids include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid and trimellitic acid. Further, unsaturated dicarboxylic acids and tricarboxylic acids having a substituent such as a saturated chain hydrocarbon group, an alicyclic hydrocarbon group and an unsaturated hydrocarbon group may be used. Of these, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid and trimellitic acid are preferable, and succinic acid, itaconic acid and tetrahydrophthalic acid are more preferable.

Next, tetracarboxylic acid or its acid dianhydride (c) is shown. An example of a tetracarboxylic acid is shown below, but it is preferable to use the acid dianhydride, and it is also possible to use two or more kinds in combination.
As the chain hydrocarbon tetracarboxylic acid, for example, butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid and the like can be mentioned, and further substitution of alicyclic hydrocarbon group, unsaturated hydrocarbon group and the like. It may be a chain hydrocarbon tetracarboxylic acid having a group.

Examples of the alicyclic tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, and the like. It may be an alicyclic tetracarboxylic acid having 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, diphenyl sulfone tetracarboxylic acid and the like. Among 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 of reacting the above-mentioned epoxy (meth)acrylate compound (d) with the acid components (b) and (c) is not particularly limited and is described in, for example, JP-A-9-325494. As described above, a known method of reacting an epoxy (meth)acrylate compound with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140° C. can be adopted. Preferably, an epoxy (meth)acrylate compound (d), a dicarboxylic acid or a tricarboxylic acid or an acid monoanhydride thereof (b), a tetracarboxylic acid dianhydride (c) is used so that the terminal of the compound becomes a carboxyl group. It is desirable to carry out the reaction so that the molar ratio is (d):(b):(c)=1:0.01-1.0:0.2-1.0. Here, a quantitative explanation will be given taking the case of using (b) acid monoanhydride and (c) acid dianhydride as an example. A diol compound (epoxy (meth)acrylate compound) containing a polymerizable unsaturated group. Reaction so that the molar ratio [(d)/[(b)/2+(c)]] of the amount of acid component [(b)/2+(c)] to (d) is 0.5 to 1.0. It is desirable to let When the molar ratio exceeds 1.0, the content of the unreacted polymerizable unsaturated group-containing diol compound increases, and there is a concern that the stability of the alkali-soluble resin composition with time may deteriorate. 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 the unreacted acid dianhydride increases to increase the alkali-solubility. There is concern that the stability of the resin composition over time may be reduced. The molar ratio of each of the components (d), (b) and (c) can be arbitrarily changed within the above range for the purpose of adjusting the acid value and the molecular weight of the alkali-soluble resin represented by the general formula (1). ..

（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。） The alkali-soluble resin obtained by the reaction of the above-mentioned polymerizable unsaturated group-containing diol compound (d) with the acid components (b) and (c) is such that all G in the general formula (1) are hydrogen atoms. And has the structure of the above general formula (5). In the present invention, the unsaturated group-containing epoxy compound represented by the following general formula (7) is reacted with the carboxyl group of the above general formula (5). The reaction between the general formula (5) and the unsaturated group-containing epoxy compound represented by the general formula (7) can be carried out by a known method, for example, as represented by the general formula (12). A method for producing an epoxy (meth)acrylate compound can be used.

(However, R ₁ , R ₂ and m have the same meanings as those shown in the general formulas (1), (2) and (3).)

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 determined by the photoreaction of the alkali-soluble resin represented by the general formula (1). It can be arbitrarily changed for the purpose of adjusting the sensitivity (depending on the amount of the polymerizable double bond) and the 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 the number of moles of the component (c) being 90% or less, alkali developability can be imparted. Therefore, it can be used for a photosensitive resin composition having photopatternability. Further, when it is desired to provide the effect of improving the sensitivity of photoreaction, it is necessary to set the content to 10% or more, and therefore it is preferably 10 to 90%. Furthermore, it is more preferably 30 to 70%. The acid value of the alkali-soluble resin of the general formula (1) used is preferably 20 to 180, more preferably 30 to 120.

Further, the weight average molecular weight (Mw) in terms of polystyrene of the alkali-soluble resin of the general formula (1) of the present invention measured by gel permeation chromatography (GPC) is usually 1000 to 100000, 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 make the solution viscosity of the photosensitive resin composition suitable for coating, and it takes too much time for alkali development, which is not preferable.

〔但し、Ｗ及びＷ'は、一般式（１０）で表される２価の有機基Ｐ、及び／又は一般式（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て、少なくとも１つは一般式（２）で示される置換基であり、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。〕 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 an alkali-soluble resin represented by the following general formula (9) can be carried out by the method for producing an alkali-soluble resin represented by the general formula (1), but it has two epoxy groups in one molecule in the first step. When the epoxy compound (a) is reacted with the unsaturated group-containing monocarboxylic acid, it is derived from the epoxy compound (a-1) having two epoxy cycloalkyl groups in one molecule and the bisphenol as the component (a). It is characterized in that the epoxy resin (a-2) is used together.

[Wherein W and W′ are each a divalent organic group P represented by the general formula (10) and/or a divalent organic group Q represented by the divalent organic group Q represented by the general formula (11). Represents an organic group, Y represents a tetravalent carboxylic acid residue, Z represents a hydrogen atom or a substituent represented by the following general formula (2), and at least one of them represents a substituent represented by the general formula (2). G is a hydrogen atom or a substituent represented by the following general formula (3). ]

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 general formula (8).

Here, R ₃ , R ₄ , R ₅ , and R ₆ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group. Further, M _{-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, 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 obtained by reacting bisphenols with epichlorohydrin. During this reaction, since the diglycidyl ether compound is generally oligomerized, an oligomer as shown in the general formula (8) is obtained, but each molecule has a different value of e, and the average value of e is as described above. Is 0 or more and 10 or less, and 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)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane , Bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2, 2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis (4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxy-3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-) Examples thereof include dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 4,4′-biphenol, 3,3′-biphenol and derivatives thereof. Of these, 2,2-bis(4-hydroxyphenyl)propane is preferably used. Two or more kinds of bisphenols can be used as the raw material of the component (a-2).

The first step in the production of the compound of the general formula (9) is such that the component (a-1) and the component (a-2) are added in an amount of 10 to 10 parts (a-2) per 100 parts by mass of the component (a-1). 100 parts by mass, preferably, added in an amount of 30 to 60 parts by mass, and is 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 mentioned above, this reaction is preferably carried out using a catalyst in a solvent. It should be noted that an epoxy acrylate obtained by reacting 2 moles of (meth)acrylic acid with respect to 1 mole of (a-1) and 2 moles of (meth)acryl separately with respect to 1 mole of (a-2). The epoxy (meth)acrylate compound (d′) may be obtained by mixing with an acid-reacted epoxy acrylate.

The second step is to add the dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (b) and tetracarboxylic acid or its acid dianhydride (c) to the epoxy (meth)acrylate compound (d') obtained in the first step. To give 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 each 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). Represents a valent organic group, and Y and Z′ have the same meanings as those in the general formula (5). f represents the average value of 1-20. 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 f _P and f _Q , respectively. In that case, f=f _P +f _Q. In addition, W 'If you are a = P is the f _Q ≠ 0, W' = case is Q is a f _P ≠ 0, W 'comprises a W is always Q when P, W' is Q When, W always contains P.

(However, R ₁ has the same meaning as shown in formula (1), and R ₃ , R ₄ , R ₅ , R ₆ , M, and e have the same meaning as shown 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. are the same as those of the general formula (5). This is similar to 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 represented by the general formula (24). Also in this reaction, 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), the alkali-soluble resin of the general formula (24) is converted into the alkali-soluble resin of the general formula (9). 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 the number of moles of the component (c) being 90% or less, alkali developability can be imparted. Therefore, it can be used for a photosensitive resin composition having photopatternability. Further, when it is desired to provide the effect of improving the sensitivity of photoreaction, it is necessary to set the content to 10% or more, and therefore it is preferably 10 to 90%. Furthermore, it is more preferably 30 to 70%.

The weight average molecular weight of the alkali-soluble resin represented by the general formula (9) is preferably 1,000 to 100,000, and more preferably 2,000 to 30,000. The acid value of the alkali-soluble resin represented by the general formula (9) is preferably 20 to 180, and more 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.
The preferable component ratio of the photosensitive resin composition is different between the case where (E) the dispersoid is contained and the case where the dispersoid is not contained. First, the case where (E) the dispersoid is not contained will be described.
(A) A photopolymerization initiator (B) is added to the alkali-soluble resin represented by the general formula (1) and/or the general formula (9), and a solvent has a solution viscosity suitable for forming a coating film. 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 contained in an amount of 50 to 95% by mass in the solid content including a component which becomes solid after photocuring, and the component (B) is 100 mass of the component (A). When there is a component that solidifies by the photocuring reaction in addition to parts ((A) component, 0.1 to 40 parts by mass of the component amount (mass part) is added).

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, and benzoin isobutyl ether. Ethers, 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)- Biimidazole compounds such as 4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole, 2-trichloromethyl-5- Styryl-1,3,4-oxadiazol, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyryl)- Halomethyldiazole compounds such as 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-trimethoxy Halomethyl such as styryl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine -S-triazine compounds, 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, benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethyl Sulfur compounds such as thioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone and 2,3-diphenylanthraquinone, azobis Organic peroxides such as isobutyl nitrile, benzoyl peroxide, cumene peroxide, thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine And so on. Among these, it is preferable to use O-acyl oxime compounds from the viewpoint of easily obtaining a highly sensitive photosensitive resin composition. Further, two or more kinds of these photopolymerization initiators can be used. The photopolymerization initiator as used in the present invention is meant to include 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, and the like. Methyl ethyl ketone, cyclohexanone, ketones such as N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene and 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 monomethyl ether, glycol ethers such as triethylene glycol monoethyl ether, ethyl acetate, acetic acid Butyl, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxy-3-methylbutyl acetate, etc. Examples thereof include acetic acid esters and the like, and by dissolving and mixing them, a composition in a uniform solution form can be obtained. Although the amount of the solvent varies depending on the target viscosity, it is preferably in the range of 60 to 90 mass% in the photosensitive resin composition solution.

The photosensitive resin composition of the present invention contains (C) at least one ethylenic resin in addition to the above-mentioned (A) alkali-soluble resin having a specific structure and (B) a photopolymerization initiator. A photopolymerizable monomer having an unsaturated bond, an epoxy compound or an epoxy resin containing two or more (D) epoxy groups can be added, and these (C) component and (D) component should be used in combination. You can

Examples of the (C) photopolymerizable monomer include (meth)acrylic acid esters having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. , Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth) Acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol(meth)acrylate, Sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene alkylene oxide modified hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa Examples thereof include (meth)acrylic acid esters such as (meth)acrylate, and dendrimer-type polyfunctional acrylate, and one or more of these can be used. Further, as the photopolymerizable monomer having at least one ethylenically unsaturated bond, one having two or more photopolymerizable groups and capable of crosslinking the molecules of the unsaturated group-containing alkali-soluble resin is used. It is preferable. The (C) 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 fluorene type epoxy resin and other bisphenol type epoxy resins, phenol novolac type epoxy resin Resin, novolak type epoxy resins such as cresol novolac type epoxy resin, glycidyl ether of polyhydric alcohol, glycidyl ester of polycarboxylic acid, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate, Aliphatic epoxy compounds such as 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, epoxy resins having a silicone skeleton such as epoxy silicone resin Etc. Preferred are epoxy compounds or epoxy resins having two or more epoxy groups.

In the photosensitive resin composition which does not contain the component (E) of the present invention, the preferable blending ratio when the component (C) and/or the component (D) is used is that the component (C) is 100 parts by mass of the component (A). To 0 to 100 parts by mass, and when the component (D) is used, the amount is preferably 5 to 30 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (C). 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 addition amount increases. However, if it is added in a larger amount than the component (A), the alkali solubility of the photosensitive resin composition will be insufficient and the developability will decrease. On the other hand, the purpose of adding the component (D) is to improve the physical properties of the photo-patterned film by photo-curing reaction, followed by alkali development, followed by thermal curing, and in particular, a commercially available epoxy compound having two or more epoxy groups is used. When used, the surface hardness can be improved by crosslinking the resin component. However, if the amount is too large with respect to the photocurable component, the photopatternability will be adversely affected.

The above-mentioned photosensitive resin composition can also be used as a photosensitive resin composition to which (E) a dispersoid is further added. When used as a photosensitive resin composition containing a dispersoid, the preferable blending ratio 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 the component (D) is used, it is preferably 5 to 30 parts by mass based on 100 parts by mass of the total amount of the components (A) and (C). ..

The (E) dispersoid that can be used in the present invention is dispersed with an average particle size of 1 to 1000 nm (average particle size measured by laser diffraction/scattering particle size distribution meter or dynamic light scattering particle size distribution meter). Any known dispersoid conventionally used in photosensitive resin compositions can be used without particular limitation. For example, azo pigment, condensed azo pigment, azomethine pigment, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, isoindoline pigment, dioxazine pigment, slene pigment, perylene pigment, perinone pigment, quinophthalone pigment, diketopyrrolopyrrole pigment, thioindigo pigment, etc. The organic pigments described above, inorganic pigments such as titanium oxide pigments and complex oxide pigments, and pigments such as carbon black pigments (colorants that are substantially insoluble in the medium) can be preferably used. Further, 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. Further, nanoparticles of metal or metal oxide can be exemplified.

These (E) dispersoids may be used alone or in combination according to the intended function of the photosensitive resin composition. For example, as a light-shielding resist used for producing a black matrix of a color filter, carbon black, titanium may be used. Black, black organic pigments or the like can be used, and red, orange, yellow, green, blue, or purple organic pigments or the like can be used as the colored resist used for manufacturing the pixel of the color filter. As the solder resist used in the production of the insulating film, organic pigments, inorganic pigments, inorganic fillers and the like can be used, and as the decorative resist used for the design of the front glass of the touch panel, carbon black, titanium black, black As a transparent resist having high hardness and high durability, a transparent filler such as silica can be used, and an organic pigment, a white pigment or the like can be appropriately selected and used.

The organic pigments that can be used as the component (E) include Pigment Red 2, 3, 4, 5, 5, 9, 12, 12, 14, 22, 23, and 31 by the color index name. 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, same 187, same 188, same 202, same 207, same 208, same 209, same 210, same 213, same 214, same 220, same 221, same 242, same 247, same 253, same 254, same 255, 256, 257, 262, 264, 266, 272, 279, Pigment Orange 5, 13, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, Pigment Yellow 1, 3, 3, 12, 13, 14, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130. , Same 136, Same 138, Same 139, Same 150, Same 151, Same 153, Same 154, Same 155, Same 173, Same 174, Same 175, Same 176, Same 180, Same 181, Same 183, Same 185, Same 185 191, 194, 199, 213, 213, 214, Pigment Green 7, 36, 58, Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 16, 60, 80, Pigment Violet 19, 23, 37, and the like, but not limited thereto.

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, in applications requiring light resistance. As another embodiment, there is a white photosensitive resin composition which is a white cured product obtained by photo-patterning and which is intended for applications requiring light resistance.

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 (9), (B) a photopolymerization initiator, and (E) a dispersoid ( E-1) A white pigment is contained as an essential component, and (C) a photopolymerizable monomer and/or (D) an epoxy compound or an epoxy resin, depending on the properties required for the process such as photopatterning and the physical properties of the cured product. Can be added. The details of the components (A) to (D) are as described above.

Examples of the (E-1) white pigment in the white photosensitive resin composition of the present invention include white organic pigments and white inorganic pigments. As the white organic pigment, an organic compound salt of the general formula An-n[B] shown in JP-A No. 11-129613 (A is a substituted stilbene-based fluorescent whitening agent having an anionic group and a sulfonic acid group, a substituted coumarin) Fluorescent whitening agent, fluorescent whitening agent component such as substituted thiophene fluorescent whitening agent, 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) or , White organic pigments such as ethylene bismelamine and alkylene bismelamine derivatives such as ethylene bismelamine and N,N'-dicyclohexylethylene bismelamine disclosed in JP-A-6-122674 (commercially available products are Shigenox OWP, Shigenox OWPL (manufactured by Hakkol Chemical Co.). )), hollow particles using the thermoplastic resin described in JP 2008-1072 A, for example, hollow particles made of styrene-acrylic copolymer, hollow particles made of cross-linked styrene-acrylic copolymer (commercially available products are: SX866, SX8782 (manufactured by JSR Corporation) and the like.

Examples of white inorganic pigments include chromium oxide, iron oxide, titanium oxide, titanium white, titanium oxynitride, and titanium nitride. These light-shielding materials can be used alone or in appropriate combination of two or more including white organic pigments and white inorganic pigments, and titanium white is particularly suitable for light-shielding property, surface smoothness, It is preferable in that the dispersion stability and the affinity with the resin are good. The average particle size (volume average particle size measured by a laser diffraction/scattering particle size measuring device) of the white organic white pigment or organic/inorganic pigment used is preferably 20 to 1000 nm, and 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 or the like depending on the application or to adjust the light-shielding property. You can Examples of the colored inorganic pigment used in combination include carbon black, chromium oxide, iron oxide, titanium oxide, titanium black, titanium oxynitride, titanium nitride and the like. When the wiring layer is formed for the purpose of concealing the wiring layer, such as a decorative layer of a touch panel, a black light shielding layer and a two-layer structure may be used for the purpose of adjusting the light shielding property. In the case of a two-layer structure, for example, a white cured film layer may be formed on a glass plate for surface protection, and a light-shielding layer may be formed thereon by using a black photosensitive resin composition.

Colored inks (black, cyan, magenta, and yellow inks) to be used in combination are not particularly limited, and known water-soluble dyes and oil-soluble dyes can be used as long as they can achieve a hue and color density suitable for the purpose of use of the ink. And pigments can be appropriately selected and used. Above all, it is preferable to use an oil-soluble dye or pigment that is easily dispersed and dissolved uniformly in a water-insoluble liquid. When the oil-soluble dye is used, 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 is added within a range not exceeding the content of the component (E).

Regarding the composition ratio of each of the components (A) to (C) and the component (E-1) in the white photosensitive resin composition, the content of the component (A) in the solid content of the white photosensitive resin is 1 to It is preferably 55% by mass, and preferably 3 to 50% by mass. If the content of the component (A) in the solid content is low, the strength of the cured product will decrease. On the other hand, if the amount is too large, the ratio of the white light shielding material as the component (E) in the photosensitive resin composition of the present invention decreases, and the light shielding property deteriorates. (C) is 0 to 100 parts by mass with respect 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 to 95% by mass in the solid content (including the monomer component that becomes the solid content by the photocuring reaction). Preferably, (C) is 30 to 50 parts by mass with respect to 100 parts by mass of (A), and (B) is 3 to 30 parts by mass with respect to 100 parts by mass of the total amount of (A) and (C). And (E-1) is 40 to 90 mass% in the solid content. Further, when the component (D) is used, it is preferably 5 to 30 parts by mass based on 100 parts by mass of the total amount of the components (A) and (C). The solid content as used herein includes a component that becomes solid by photocuring, in other words, a component other than the solvent contained in the white photosensitive resin composition.

If (C) is more than 100 parts by mass with respect to 100 parts by mass of (A), the solubility of the coating film in the developing solution becomes too low, resulting in poor photolithography performance.

When (B) is less than 0.1 parts by mass based on 100 parts by mass of the total amount of (A) and (C), the coating film does not cure, and when it exceeds 40 parts by mass, an area larger than the mask opening area is obtained. Since it cures, the photolithography performance deteriorates.

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

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

In the white photosensitive resin composition of the present invention, it is preferable to adjust the viscosity by using a solvent in addition to the above (A) to (D) and (E-1). The solvent used is as exemplified above.

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

Further, the white photosensitive resin composition of the present invention, if necessary, a curing accelerator, an antioxidant, a thermal polymerization inhibitor, a plasticizer, a leveling agent, a defoaming agent, a coupling agent, a surfactant, etc. Additives can be added. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and phenothiazine. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate, and examples of the defoaming agent and leveling agent include silicone-based, fluorine-based, and acryl-based compounds. Further, examples of the surfactant include fluorine-based surfactants and silicone-based surfactants, and 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 containing 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 the photolithography method using the photosensitive resin composition of the present invention. As the manufacturing process, first, the photosensitive resin composition solution is applied to the surface of the substrate, and then the solvent is dried (prebaking), and then a photomask is applied onto the coating film thus obtained, and ultraviolet rays are applied. Examples include a method of irradiating to cure the exposed portion, further developing using an alkaline aqueous solution to elute the unexposed portion to form a pattern, and post-baking as post-curing. Here, as the substrate to which the photosensitive resin composition solution is applied, glass, a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.) or the like is used.

As a method of applying the photosensitive resin composition solution to the substrate, any method such as a known solution dipping method, a spray method, a roller coater machine, a land coater machine, a slit coater machine or a spinner machine may be used. Can be adopted. By these methods, after coating to a desired thickness, the solvent is removed (prebaking) to form a film. Prebaking 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 used, and for example, the heating is performed at a temperature of 60 to 110° C. for 1 to 3 minutes.

The exposure performed after the prebaking is performed by an exposure device, and by exposing through a photomask, only the portion of the photosensitive resin composition corresponding to the pattern is exposed. The exposure machine and its exposure irradiation conditions are appropriately selected, and light exposure is carried out using a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a far ultraviolet ray 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 portion, and a desired pattern is formed by this development. Examples of the developer suitable for the alkali development include an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal, an aqueous solution of an alkali metal hydroxide, and the like. In particular, sodium carbonate, potassium carbonate, etc. It is preferable to develop at a temperature of 23 to 27° C. using a weak alkaline aqueous solution containing 0.03 to 1% by weight of carbonate, and a fine image can be precisely formed using a commercially available developing machine or an ultrasonic cleaner. Can be formed.

After the development in this way, a heat curing treatment (post-baking) is performed at a temperature of 200 to 240° C. for 20 to 60 minutes. This post-baking is performed for the purpose of increasing 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 a light-resistant photosensitive resin composition, and the photosensitive resin composition can form a pattern by photolithography. Therefore, it is possible to obtain a cured product which is particularly excellent in development characteristics and light resistance. For example, it can be suitably used for obtaining a white cured film having excellent light discoloration resistance.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Hereinafter, the present invention will be described in more detail based on examples of synthesizing the alkali-soluble resin represented by 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. Further, evaluation of resins in the following synthetic examples was performed as follows unless otherwise specified.

[Solid content concentration]
A glass filter [weight: w ₀ (g)] was impregnated with 1 g of the resin solution obtained in the Synthesis Example, weighed [w ₁ (g)], and the weight [w ₂ ( g)] from the following formula.
Solid content concentration (% by weight)=100×(w ₂ −w ₀ )/(w ₁ −w ₀ ).

[Acid value]
The resin solution was dissolved in dioxane and titrated with a 1/10N-KOH aqueous solution using a potentiometric titrator (trade name: COM-1600 manufactured by Hiranuma Sangyo Co., Ltd.), and the amount of KOH required per 1 g of solid content. Was defined as 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 ( One) (manufactured by Tosoh Corporation), temperature: 40° C., speed: 0.6 ml/min), and weight average molecular weight (Mw) as standard polystyrene (PS-Oligomer Kit manufactured by Tosoh Corporation) 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
An epoxy compound in which g is 1 in the 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)
An epoxy compound in which R ₃ , R ₄ , R ₅ , and R ₆ are hydrogen, M is -C(CH ₃ ) ₂ -, and e (average value)=2.3 in the general formula (8)

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]
Charge EP(a-1-1) 0.34mol, AA 0.68mol, PGMEA 139.0g and TEAB 2.15g into a 500ml four-necked flask equipped with a carbonization condenser, and stir for 20 hours while heating at 100 to 105°C to react. Let Next, 0.12 mol of BPDA and 0.27 mol of THPA were charged in the flask, and the mixture was stirred at 120 to 125° C. for 8 hours under heating to react. Further, 0.28 mol of GMA was charged and the mixture was stirred at 100 to 105° C. for 8 hours under heating to obtain an alkali-soluble resin (A)-1. The solid content concentration of the obtained resin solution was 66.7 wt%, the acid value (solid content conversion) was 55 mgKOH/g, and the Mw by GPC analysis was 4,200. The average value of n in the general formula (1) calculated from Mw by GPC analysis was 3.9.

[Example 2]
Charge EP(a-1-1) 0.34mol, AA 0.68mol, PGMEA 139.0g and TEAB 2.14g into a 500ml four-necked flask equipped with a reflux condenser and stir for 20 hours under heating at 100 to 105°C to react. Let Next, 0.12 mol of BuTDA and 0.27 mol of THPA were charged into the flask, and the mixture was stirred at 120 to 125° C. for 8 hours under heating to react. Further, 0.28 mol of GMA was charged and the mixture was stirred at 100 to 105° C. for 8 hours under heating to obtain an alkali-soluble resin (A)-2. The solid content concentration of the obtained resin solution was 65.6 wt%, the acid value (solid content conversion) was 58 mgKOH/g, and the Mw by GPC analysis was 4,500. The average value of n in the general formula (1) calculated from Mw by GPC analysis was 4.9.

[Example 3]
Charge EP(a-1-2) 0.28mol, AA 0.56mol, PGMEA 147.0g and TEAB 1.77g into a 500ml four-necked flask equipped with a reflux condenser, and stir for 20 hours under heating at 100-105°C to react. Let Next, 0.10 mol of BPDA and 0.22 mol of THPA were charged into the flask, and the mixture was stirred at 120 to 125° C. for 6 hours under heating to react. Further, 0.23 mol of GMA was charged, and the mixture was stirred at 100 to 105° C. for 8 hours under 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 (solid content conversion) of 48 mgKOH/g, and an Mw by GPC analysis of 6,600. The average value of n in the general formula (1) calculated from Mw by GPC analysis was 5.9.

[Example 4]
Charge EP(a-1-2) 0.28mol, AA 0.56mol, PGMEA 147.0g and TEAB 1.77g into a 500ml four-necked flask equipped with a carbonization condenser, and stir for 20 hours under heating at 100-105°C to react. Let Next, 0.10 mol of BuTDA and 0.22 mol of THPA were charged into the flask, and the mixture was stirred at 12 to 125°C for 8 hours with heating to react. Furthermore, 0.23 mol of GMA was charged, and the mixture was stirred at 100 to 105° C. for 8 hours under heating to obtain an alkali-soluble resin (A)-4. The solid content concentration of the obtained resin solution was 63.5 wt%, the acid value (solid content conversion) was 50 mgKOH/g, and the Mw by GPC analysis was 6900. The average value of n in the general formula (1) calculated from Mw by GPC analysis was 6.9.

[Example 5]
Charge 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 in a 500 ml four-necked flask with a reflux condenser, 100- The reaction was carried out by stirring at 105°C for 20 hours while heating. Then, BPDA (0.09 mol) and THPA (0.20 mol) were charged in the flask, and the mixture was stirred at 120 to 125° C. for 8 hours with heating to react. Further, 0.20 mol of GMA was charged, and the mixture was stirred at 100 to 105° C. for 8 hours under heating to obtain an alkali-soluble resin (A)-5. The solid content concentration of the obtained resin solution was 62.9 wt%, the acid value (solid content conversion) was 44 mgKOH/g, and the Mw by GPC analysis was 7,200. 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 return distillation condenser, and the mixture was reacted by stirring at 100 to 105°C for 20 hours. Next, 0.12 mol of BPDA and 0.12 mol of THPA were charged in the flask, and the mixture was stirred at 120 to 125° C. for 6 hours under heating to obtain an alkali-soluble resin (A)-6. The solid content concentration of the obtained resin solution was 55.6 wt%, the acid value (solid content conversion) was 103 mgKOH/g, and the Mw by GPC analysis was 3,600.

[Synthesis example 2]
MAA 51.65g (0.60mol), MMA 38.44g (0.38mol), CHMA 36.33g (0.22mol), AIBN5.91g, and DMDG368g were charged into a 1000ml four-necked flask equipped with a nitrogen introduction tube and a reflux tube, and 80 to 85 were charged. Polymerization was carried out by stirring at 8°C under a nitrogen stream for 8 hours. Furthermore, 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 solid content concentration of the obtained resin solution was 32% by mass, the acid value (solid content conversion) was 110 mgKOH/g, and the Mw by GPC analysis was 18080.

(Preparation of white photosensitive resin composition solution)
Blending was performed according to the composition shown in Table 1 to prepare white photosensitive resin composition solutions of Examples 6 to 13 and Comparative Example 1. The components used in the formulation are 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 of Example 1 (A)-2 Resin solution of Example 2 (A)-3 Resin solution of Example 3 (A)-4 Resin solution of Example 4 (A)-5 Implementation Resin solution of Example 5 (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-benzoyl oxime)] (BASF trade name Irgacure OXE01)
(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-methylbutylacetate (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 glass plate having a thickness of 1.2 mm under a condition of a dry film thickness of 10 μm using a spin coater. After that, a photomask was brought into close contact with the substrate, and a 500 W high-pressure mercury lamp was used to irradiate ultraviolet rays having an illuminance of 10 mW/cm ² with a wavelength of 365 nm for 10 seconds. After the exposure, it is developed with a 0.4% sodium carbonate aqueous solution at 23° C. for 60 seconds under 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. Heat curing treatment was performed to obtain a white film pattern (cured product). Then, the white film pattern formed on the glass plate was confirmed with a microscope, and the pattern formation was evaluated as follows. The results are shown in Table 2.
・Pattern formation ○: Pattern formation is possible (line and space pattern of 5 μm to 30 μm remains)
×: Not dissolved in developer or pattern peeled

(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 applied onto a degreased and washed glass plate having a thickness of 1.2 mm under a condition of a dry film thickness of 10 μm by using a spin coater. After drying, without using a photomask, the entire surface of the white film-formed glass plate similar to that described above was irradiated with ultraviolet rays having an illuminance of 10 mW/cm ^{2 at} a wavelength of 365 nm for 10 seconds using a 500 W high-pressure mercury lamp. After the exposure, the developing solution was treated with a 0.4% sodium carbonate aqueous solution at 23° C. for 60 seconds under a pressure of 0.1 MPa. After that, heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer. In order to confirm the resistance to light discoloration, ultraviolet rays having an illuminance of 130 W/cm ² having a wavelength of 254 nm were further irradiated for 2 hours using a low-pressure mercury lamp, and the b ^* value was measured by a spectrophotometer. The results are shown in Table 2.

As is clear from the results of Examples 6 to 13 and Comparative Example 1 described above, the alkali-soluble resins (A)-1 to (A)-5 of the general formula (1) or the general formula (9) of the present invention. Or 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. It was found that a white cured product which can form a pattern and has a good b ^* value can be obtained. In addition, when the b ^* value exceeds 1.5, yellowing becomes noticeable, which is unsuitable as a white eye, and the light discoloration resistance is insufficient.

Next, examples of transparent photosensitive resin compositions using the polymerizable unsaturated group-containing alkali-soluble resin of the present invention will be shown.

(Preparation of transparent photosensitive resin composition solution)
The compositions shown in Table 3 were added to prepare transparent photosensitive resin composition solutions of Examples 14 to 22 and Comparative Example 2. The components used in the formulation are as follows. In addition, the numerical value in 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)] (BASF trade name Irgacure OXE01)
(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 with titanium oxide concentration of 19.6 mass% and dispersant of 9.3 mass% (dynamic viscoelasticity measurement (Otsuka Electronics particle size analyzer FPAR -1000), the average particle size of titanium oxide by the cumulant method is 62 nm)
(E)-3 (for adjusting shrinkage): PGMEA solvent silica dispersion having a silica sol concentration of 20% by mass (YA010C manufactured by Admatechs Co., Ltd.) (cumulant by dynamic viscoelasticity measurement (Otsuka Electronics particle size analyzer FPAR-1000)) Method silica average particle size 65nm)
(E)-4 (for coloring): PGMEA solvent carbon black concentration 25% by mass, polymer dispersant 7.5% by mass (F) Solvent:
(F)-1: PGMEA
(F)-3: Diethylene glycol methyl ethyl ether (G) Surfactant: Polyether-modified polydimethylsiloxane (BYK302 manufactured by BYK Japan KK) (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 following conditions, a 500 W high-pressure mercury lamp was used without irradiation with a photomask, and ultraviolet rays with an illuminance of 10 mW/cm ^{2 at} a wavelength of 365 nm were irradiated for 10 seconds. After the exposure, the film was developed with a 0.4% sodium carbonate aqueous solution at 23° C. for 60 seconds under a pressure of 0.1 MPa, and then heat-cured at 230° C. for 30 minutes using a hot air dryer. With respect to the glass substrate on which this cured film was formed, the transparency was evaluated based on the transmittance as follows. For the transmittance, the light transmittance at 400 nm was measured using a spectrophotometer (device: Nippon Denshoku SD5000). The results are shown in Table 4.
・Transparency ○: transmittance of 85% or more ×: transmittance of 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 applied on a degreased and washed glass plate having a thickness of 1.2 mm under a condition of a dry film thickness of 1.5 μm using a spin coater. After drying, a photomask was brought into close contact, and a 500 W high-pressure mercury lamp lamp was used to irradiate ultraviolet rays having an illuminance of 10 mW/cm ² with a wavelength of 365 nm for 10 seconds. After the exposure, it is developed with a 0.4% sodium carbonate aqueous solution at 23° C. for 60 seconds under 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). Then, the transparent film pattern formed on the glass plate was confirmed with a microscope, and the pattern formation was evaluated as follows. The results are shown in Table 4.
-Developability ◯: Pattern formation possible (line and space pattern of 5 μm to 30 μm remains)
×: Not dissolved in developer or pattern peeled

(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 UV-cleaned 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 1.5 μm using a spin coater. After coating and drying under the following conditions, a 500 W high-pressure mercury lamp was used without irradiation with a photomask, and ultraviolet rays with an illuminance of 10 mW/cm ^{2 at} a wavelength of 365 nm were irradiated for 10 seconds. After the exposure, the film was developed with a 0.4% sodium carbonate aqueous solution at 23° C. for 60 seconds under a pressure of 0.1 MPa, and then heat-cured at 230° C. for 30 minutes using a hot air dryer. The light resistance of the glass substrate on which this cured film was formed was evaluated. The UV cleaning is to clean the surface of the glass substrate by irradiating with ultraviolet rays 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: 250 W/m ² ) was irradiated from the glass surface side of the glass substrate on which the cured film was formed, and the glass substrate was allowed to stand for 200 hours under the conditions of temperature 60° C. and humidity 50%. After that, using a product name "Super Cutter Guide" manufactured by Taiki Kikai Co., Ltd., a cut is made so that 100 square cells of 1 mm x 1 mm are formed on the cured film, and the squares are formed on the squares. A tape peeling test was performed in which cellophane tape (manufactured by Nichiban) was applied and then peeled off, and the following criteria were evaluated. The results are shown in Table 4.
-Light-resistant adhesion ◯: The cured product in the square is not peeled at all Δ: Less than 1/3 of the cured product in the square is peeled off x: 1/3 or more 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 under a condition of a dry film thickness of 1.5 μm using a spin coater. After coating and drying, without using a photomask, ultraviolet rays with an illuminance of 10 mW/cm ² having a wavelength of 365 nm were irradiated for 10 seconds from the transparent film formation side using a 500 W high pressure mercury lamp. After the exposure, the developing solution was treated with a 0.4% sodium carbonate aqueous solution at 23° C. for 60 seconds under a pressure of 0.1 MPa. After that, heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer. The b ^* value of this cured film was measured with a spectrophotometer (device: Nippon Denshoku SD5000). Next, in order to confirm the light discoloration resistance, a low-pressure mercury lamp was further used to irradiate ultraviolet rays having an illuminance of 130 W/cm ² with a wavelength of 254 nm for 2 hours, and b ^{* was} measured by 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 the 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 of the general formula (1) is capable of forming a pattern. It can be confirmed that, as in Comparative Example 2, no decrease in adhesion with the glass substrate after ultraviolet irradiation is observed, and the b* value does not change significantly after ultraviolet irradiation. Therefore, it was found that the present invention can provide a transparent photosensitive resin composition having excellent light resistance. In addition, the effect of improving the light resistance was obtained also in Example 17 in which the actual epoxy resin was used in combination with the constituent components of Examples 14 to 16, and the epoxy resin was used in combination for improving the surface hardness and chemical resistance. It turns out that it is possible to do. Further, even if a metal oxide such as titanium oxide or silica is added to the constituent components of Examples 14 to 16, the effect of improving the light resistance can be maintained as in Examples 18 to 20, and the adjustment of the refractive index and the It has been shown that it is also possible to control the surface hardness and curing shrinkage of the cured product. It can be seen from Example 21 that an acrylic copolymer such as (A)-7 may be used together with the alkali-soluble resin (A)-1 of the general formula (1) in the structure in 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, examples of a black photosensitive resin composition using the polymerizable unsaturated group-containing alkali-soluble resin of the present invention will be shown.

(Preparation of black photosensitive resin composition solution)
Compositions shown in Table 5 were added to prepare black photosensitive resin composition solutions of Examples 23 to 26 and Comparative Example 3. The components used in the formulation are 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-acetyl oxime (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 of PGMEA solvent having a carbon black concentration of 25 mass% and a polymeric dispersant of 7.5 mass% (E)-5 (for coloring): 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 BYK Japan KK) (1% PGMEA solution)
(H) Silane coupling agent: 3-glycidoxypropyltrimethoxysilane

(Evaluation of black photosensitive resin composition: shade ratio)
The black photosensitive resin composition solutions of Examples 23 to 26 and Comparative Example 3 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 following conditions, without using a photomask, ultraviolet rays having an illuminance of 10 mW/cm ² with a wavelength of 365 nm were irradiated from the black film side for 10 seconds using a 500 W high-pressure mercury lamp. After the exposure, the film was developed with a 0.4% sodium carbonate aqueous solution at 23° C. for 60 seconds under a pressure of 0.1 MPa, and then heat-cured at 230° C. for 30 minutes using a hot air dryer. The light-shielding rate (OD/μm) of the glass substrate on which this cured film was formed was measured. The 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 applied on a degreased and washed glass plate having a thickness of 1.2 mm under a condition of a dry film thickness of 1.1 μm using a spin coater. After drying, a photomask was brought into close contact, and a 500 W high-pressure mercury lamp lamp was used to irradiate ultraviolet rays having an illuminance of 10 mW/cm@2 with a wavelength of 365 nm for 10 seconds. After the exposure, it is developed with a 0.4% sodium carbonate aqueous solution at 23° C. for 60 seconds under 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 treatment was performed to obtain a black film pattern (cured product). Then, the black film pattern formed on the glass plate was confirmed with a microscope, and the pattern formation was evaluated as follows. The results are shown in Table 6.
-Developability ◯: Pattern formation possible (line and space pattern of 5 μm to 30 μm remains)
×: Not dissolved in developer or pattern peeled

(Evaluation of black photosensitive resin composition: light resistance)
The black photosensitive resin composition solutions of Examples 23 to 26 and Comparative Example 3 were UV-cleaned 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 1.5 μm using a spin coater. After coating and drying under the following conditions, without using a photomask, ultraviolet rays having an illuminance of 10 mW/cm ² with a wavelength of 365 nm were irradiated from the black film side for 10 seconds using a 500 W high-pressure mercury lamp. After the exposure, the film was developed with a 0.4% sodium carbonate aqueous solution at 23° C. for 60 seconds under a pressure of 0.1 MPa, and then heat-cured at 230° C. for 30 minutes using a hot air dryer. The light resistance of the glass substrate on which this cured film was formed was evaluated. The UV cleaning is to clean the surface of the glass substrate by irradiating with ultraviolet rays 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: 250 W/m ² ) was irradiated from the glass surface side of the glass substrate on which the cured film was formed, and the glass substrate was left for 200 hours under the conditions of a temperature of 60° C. and a humidity of 50%. After that, using a product name "Super Cutter Guide" manufactured by Taiki Kikai Co., Ltd., a cut is made so that 100 square cells of 1 mm x 1 mm are formed on the cured film, and the squares are formed on the squares. A tape peeling test was performed in which cellophane tape (manufactured by Nichiban) was applied and then peeled off, and evaluated according to the following criteria. The results are shown in Table 6.
-Light-resistant adhesion ◯: The cured product in the square is not peeled at all Δ: Less than 1/3 of the cured product in the square is peeled off x: 1/3 or more is peeled off

(Evaluation of black photosensitive resin composition: change in reflectance due to ultraviolet irradiation)
The black photosensitive resin composition solutions of Examples 23 to 26 and Comparative Example 3 were degreased and washed on a 1.2 mm-thick glass plate using a spin coater under the condition that a dry film thickness of 1.5 μm was obtained. After coating and drying, without using a photomask, ultraviolet rays having 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. After the exposure, the developing solution was treated with a 0.4% sodium carbonate aqueous solution at 23° C. for 60 seconds under a pressure of 0.1 MPa. After that, 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 reflectance due to UV irradiation, a low-pressure mercury lamp was used to further irradiate UV light with an illuminance of 130 W/cm ² with a wavelength of 254 nm for 2 hours, and a spectrophotometer (device: Nippon Denshoku SD5000) was used. , 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 the 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 applied on a degreased and washed glass plate having a thickness of 1.2 mm under the conditions of a dry film thickness of 3 μm using a spin coater. After drying, without using a photomask, ultraviolet rays having 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. After the exposure, the developing solution was treated with a 0.4% sodium carbonate aqueous solution at 23° C. for 60 seconds under a pressure of 0.1 MPa. After that, heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer. The maximum displacement and elastic recovery rate of this cured film were measured using a micro compression tester (trade name: HM2000, manufactured by Fisher Instruments). With a 50 μm square flat indenter, the load speed and unloading speed are both set to 5 mN/sec, a load up to 50 mN is applied, then unloading is performed, and the load-deformation curve under load and the load-deformation during unloading A curve was created. At this time, the amount of deformation under a load of 50 mN under load 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 during unloading.
Elastic recovery rate (%) = (maximum displacement-deformation amount during unloading) x 100/maximum displacement-maximum displacement ○: 0.2 micron or more x: 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, A pattern can be formed, and the adhesiveness to a glass substrate after being irradiated with ultraviolet rays is sufficient, and a pattern having good light-resistant adhesiveness as compared with Comparative Example 3 can be formed. Also, regarding the reflectance shown as the Y value, ΔY before and after irradiation with ultraviolet rays is a numerical value of less than 1, and it can be seen that the change in reflectance before and after irradiation with ultraviolet rays is smaller than that in 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 under pressure 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 a black column spacer, no remarkable difference from Comparative Example 3 is recognized, but the present invention is an effective technique if there is an application in which light resistance becomes a problem.

According to the alkali-soluble resin of the present invention, a photosensitive resin composition capable of forming a pattern and satisfying the requirement of light resistance can be obtained. Therefore, for example, it is useful for decorating a touch panel, and the white photosensitive resin composition using the alkali-soluble resin of the present invention can form a white film excellent in light discoloration resistance. That is, since the pattern can be formed by photolithography, there is an advantage that it can be formed by the existing photolithography process. Furthermore, since it can be formed by a thin film, it becomes possible to contribute to the thinning of the structure, and the white color in the touch panel manufacturing can be achieved. It is suitable for forming a film.

Claims (10)

For the reaction product of the epoxy compound (a-1) represented by the following general formula (4) and having two epoxycycloalkyl groups in one molecule and the unsaturated group-containing monocarboxylic acid, a dicarboxylic acid or tricarboxylic acid is used. By reacting an acid or its acid monoanhydride (b) with a tetracarboxylic acid or its acid dianhydride (c), a carboxyl group and a polymerizable group in one molecule represented by the following general formula (5) A method for producing an alkali-soluble resin, which comprises obtaining an alkali-soluble resin having a saturated 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, n represents an average value of 1 to 20, Z′ represents a hydrogen atom or a substituent represented by the general formula (6), and at least one Z′ is represented by the general formula (6). It is a substituted group.)

(However, L represents a divalent or trivalent carboxylic acid residue, and r is 1 or 2.) For 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 its acid monoanhydride (b), and tetracarboxylic acid In an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule obtained by reacting an acid or its acid dianhydride (c), two epoxycyclo compounds in one molecule as an epoxy compound (a) An epoxy compound (a-1) having an alkyl group and an epoxy compound (a-2) having two epoxy groups in one molecule derived from a bisphenol represented by the following general formula (8) are used in combination. Thus, the method for producing an alkali-soluble resin, which is represented by the following general formula (24) and has 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. Further, M _{-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, and e represents an average value of 0 to 10 (excluding 0). ]

[However, W 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) Represents a valent organic group, Y represents a tetravalent carboxylic acid residue, Z′ represents a hydrogen atom or a substituent represented by the following general formula (6), and at least one of Z′ represents a general formula ( 6) is a substituent represented by 6), and 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 the organic groups P and Q in the molecule is f _P and f, respectively. _{When Q} is set, f=f _P +f _Q. In addition, W 'If you are a = P is the f _Q ≠ 0, W' If you are a = Q is f _P ≠ 0.

(However, R ₁ represents a hydrogen atom or a methyl group, and R ₃ , R ₄ , R ₅ , R ₆ , M, and e have the same meanings as shown in formula (8).)

(However, L represents a divalent or trivalent carboxylic acid residue, and r is 1 or 2.) (A) either the alkali-soluble resin of the general formula (5) obtained by the method described in claim 1 or the alkali-soluble resin of the general formula (24) obtained by the method described in claim 2 One or both,
(B) a photopolymerization initiator,
A photosensitive resin composition comprising: In addition to the components (A) and (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 according to claim 3, which comprises. The photosensitive resin composition according to claim 3 or 4, further comprising (E) a dispersoid. The photosensitive composition according to claim 5, wherein the (E) dispersoid is a (E-1) white pigment. The white photosensitive resin composition according to claim 6, wherein in the solid content, the component (A) is 1 to 55% by mass, 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 contained in an amount of 0.1 to 40 parts by mass and the component (E) in an amount of 1 to 95% by mass with respect to 100 parts by mass of the total amount of the components (A) and (C). White photosensitive resin composition. A cured product obtained by patterning the photosensitive resin composition according to any one of claims 3 to 7 by a photolithography method and then thermally curing it. A touch panel comprising the cured product according to claim 8. A color filter comprising the cured product according to claim 8 .