JP2020106755A - Photosensitive resin composition for light-shielding film and cured product of the same, and method for manufacturing color filter and touch panel using the cured product - Google Patents

Abstract

To provide a photosensitive resin composition for a light-shielding film, from which a coating film can be obtained that ensures sufficient development adhesiveness and has excellent adhesiveness to a glass substrate even when a thin line is formed, while maintaining high-definition and high light-shielding properties, and that can have high resistance characteristics.SOLUTION: The photosensitive resin composition for a light-shielding film comprises as essential components: (A) a polymerizable unsaturated group-containing alkali-soluble resin obtained by allowing an unsaturated group-containing monocarboxylic acid to react with an epoxy compound having at least two epoxy groups in one molecule and further allowing a polyvalent carboxylic acid or an acid anhydride thereof to react; (B) a photopolymerizable monomer having at least one ethylenic unsaturated bond; (C) a photopolymerization initiator comprising a fluorene compound having a polymerizable group at a 9-th position of a fluorene ring; and (D) at least one light-shielding component selected from the group consisting of a black organic pigment, a mixed color organic pigment and an inorganic pigment. In the composition, a weight ratio (A)/(B) of the (A) component to the (B) component is 50/50 to 90/10; and the composition contains the (C) component by 2 to 30 pts.mass with respect to 100 pts.mass in total of the (A) component and the (B) component and contains the (D) component by 20 to 80 mass% with respect to the whole solid content of the composition.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a photosensitive resin composition for a light-shielding film and a cured product thereof, and more specifically, an alkaline aqueous solution-developing photosensitive resin composition for a light-shielding film suitable for forming a fine light-shielding film on a transparent substrate. And a cured product thereof, and the light-shielding film obtained by curing is suitably used when forming a color filter (CF) or a touch panel.

A color liquid crystal display device has a liquid crystal part for controlling the amount of transmitted or reflected light and a color filter as constituent elements, and the method for manufacturing the color filter is usually a glass, a surface of a transparent substrate such as a plastic sheet. A method is used in which a black matrix is formed, and subsequently, different hues of red, green, and blue are sequentially formed in a stripe-shaped or mosaic-shaped color pattern.

In recent years, color liquid crystal display devices have been used in various fields such as liquid crystal televisions, liquid crystal monitors, and color liquid crystal mobile phones. The color filter is one of the important members that affect the visibility of the color liquid crystal display device. In order to improve the visibility, that is, to obtain a clear image, the red (R), green ( G), blue (B), and other pixels need to have higher color purity than ever, and a black matrix needs to achieve high light shielding. For that purpose, a colorant is added to the photosensitive resin composition more than ever before. Must also be added in large amounts.

In recent years, ultra-high definition (400 Pixel Per Inch or higher) technology to obtain Full High Definition resolution has been required for small and medium-sized panels such as smartphones, and high definition has become an essential technology trend. .. In order to achieve high definition, it is necessary to make each pixel size of red, green, and blue small, but the aperture ratio of the color filter (area ratio of RGB pixels through which the backlight light passes) cannot be reduced. It is necessary for high brightness, and thinning of the black matrix is also required. That is, the line width of the black matrix has conventionally been 6 to 8 μm, but recently, the line width has been required to be 4 to 5 μm.

Further, the backlight intensity tends to be increased for higher brightness, and accordingly, in order to prevent light leakage from the black matrix, it is necessary to make the black matrix around RGB highly light-shielded. The thickness of the black matrix may be increased in order to secure high light shielding. However, if the thickness of the black matrix is increased, it is easily affected by the development process, and the variation of the line width of the black matrix in the mother glass surface becomes large. .. In particular, in the case of a thin line of 4 to 5 μm, variations in line width have a great influence on display performance such as occurrence of display unevenness. Therefore, it is necessary to improve the light blocking property per unit film thickness in order to secure the target light blocking degree with the thinnest possible film thickness. However, in general, since the content of the black pigment in the resin composition is increased, as a result, the blending ratio of the binder resin and the acrylate component that contribute to the curability becomes relatively small, and the coating film is sufficiently cured. It becomes difficult, and the adhesion between the coating film and the glass substrate is lowered, so that peeling or the like is likely to occur.

By the way, a PCT (Pressure Cooker Test) is generally performed as a durability test (reliability test) in a liquid crystal panel, and this test method is performed under severe conditions such as a temperature of 121° C., a humidity of 100%, and an atmospheric pressure of 2 atm. The liquid crystal panel is allowed to stand for a period of time, and the presence or absence of leakage of liquid crystal enclosed between the color filter substrate and the TFT substrate of the liquid crystal panel is confirmed. The black matrix exists between each color of red, green, and blue, and in addition to the role of improving contrast, it also functions as the outer frame light-shielding film of the color filter. A part of the outer frame light-shielding film is connected to the counter substrate through the sealing material. Pasted together. Therefore, the black matrix is also required to have high adhesion strength so that the black matrix does not peel off from the glass substrate even under severe conditions such as PCT. In particular, in recent years, there is a strong need for high light shielding even for the outer frame light shielding film in order to improve the visibility of the liquid crystal panel.

Further, in CF for IPS (FFS) mode panels used for small and medium-sized panels such as smartphones and mobiles, it is preferable that the black matrix has high resistance. Since increasing the light-shielding component to increase the light-shielding property lowers the resistance value, it is a very high technical hurdle to secure thin lines, high light-shielding, high adhesion (high reliability) and high resistance.
By the way, although carbon black is generally known as a light-shielding material (black color material) for a resin black matrix, since carbon black has a relatively low electric resistance, it may cause a malfunction of the display device. .. Particularly, in an in-plane switching (IPS) type liquid crystal display device that can obtain a wide viewing angle, an electric field is applied in the in-plane direction of the liquid crystal layer, so if the resistance value of the black matrix is low, the electric field is not normally applied, and the liquid crystal orientation is Disturbance occurs and causes display unevenness.

Therefore, as a method of increasing the electrical resistance of the black matrix using carbon black, a technique of coating the surface of carbon black with a resin has been applied (see Patent Document 1). However, if the value is increased, there is a limit to the degree of light shielding that can be realized while sufficiently maintaining the optical patterning property, and it has become difficult to achieve the required high light shielding and high resistance. Therefore, although a technique (see Patent Document 2) using specific titanium nitride particles capable of realizing relatively high resistance and high light shielding as a light shielding material has been developed, there is concern that the photopatterning property and storage stability may be insufficient. To be done.

As described above, as the need for a black matrix satisfying various required characteristics increases, specifically, in a photosensitive resin composition containing a large amount of a light-shielding material and difficult to be photocured, the pattern size is reduced at a low exposure amount. A glass substrate capable of obtaining a fine line pattern having excellent stability, pattern adhesion, and sharpness of the edge shape of the pattern with a wide development margin, and also having high light shielding, preferably high resistance, even in a durability test such as PCT. It is required to form a black matrix and an outer frame light-shielding film having high adhesion (high reliability) with good quality. There is an increasing demand for forming a light-shielding film on the outer frame or the like of the touch panel for the same purpose as that of the outer frame light-shielding film for the color filter.

Therefore, for example, Patent Documents 3 to 4 propose a photosensitive resin composition for a black matrix containing an oxime ester fluorene compound as a high-sensitivity photopolymerization initiator. However, it is difficult to show sufficient performance in obtaining a fine line pattern with a wide development margin, which has excellent pattern dimensional stability at a low exposure amount, pattern adhesion, and sharpness of the edge shape of the pattern. There is no description about a composition that satisfies the requirements of high light-shielding and high resistance, or a specific description about a composition that exhibits adhesion in a durability test such as PCT.

JP, 2001-207079, A JP 2008-260927 A Japanese Patent No. 5682094 Japanese Patent Publication No. 2015-523318

The present invention has been made in view of the above problems, and an object thereof is also to form a thin line of, for example, 5 μm in a photosensitive resin composition while maintaining high definition and high light shielding. Provided is a photosensitive resin composition for a light-shielding film, which is capable of forming a black matrix capable of ensuring sufficient development adhesion, excellent adhesion to a glass substrate, and having high resistance characteristics. To do. The present invention also provides a cured product such as a light-shielding film pattern formed by a photolithography method using the photosensitive resin composition, and further provides a color filter or a touch panel including the cured product.

As a result of studies conducted by the present inventors to solve the above problems, a polymerizable unsaturated group-containing alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a photosensitive resin composition containing a light-shielding component , Especially as a photopolymerization initiator, by blending an oxime ester fluorene-based photopolymerization initiator having a polymerizable group, high definition, high light shielding, while maintaining high adhesion with a glass substrate, even in the formation of fine lines A specific insulating light-shielding component capable of ensuring sufficient development adhesion and further increasing the surface resistivity when formed into a film with an optical density of 4/μm is added as a light-shielding component. As a result, they have found that it is possible to form a high-resistance light-shielding film, and have completed the present invention.
That is, the gist of the present invention is as follows.

但し、一般式（I）において、Ｒ₁及びＲ₂はそれぞれ独立に、炭素数１〜１０の直鎖状若しくは分岐状のアルキル基であるか、炭素数４〜１０のシクロアルキル基、シクロアルキルアルキル基若しくはアルキルシクロアルキル基であるか、又は炭素数１〜６のアルキル基で置換されていてもよい炭素数６〜１２のアリール基を表す。Ｒ_３はそれぞれ独立に炭素数２〜１０のアルケニル基であるか、又はエポキシ基を有する炭素数２〜１０の置換基を表し、当該アルケニル基中の−ＣＨ_２−基の一部が−Ｏ−基で置換されていてもよい。さらに、これらＲ_１〜Ｒ_３の基中の水素原子の一部がハロゲン原子で置換されていてもよい。
〔３〕前記〔１〕又は〔２〕に記載の遮光膜用感光性樹脂組成物において、(D)成分が、光学濃度が４／μｍとなるように製膜した膜の表面抵抗率を１×１０^８Ω／□以上とする絶縁性遮光成分であることを特徴とする遮光膜用感光性樹脂組成物。
〔４〕（A）成分が下記一般式（II）で表される化合物と（メタ）アクリル酸との反応物に、更に多価カルボン酸又はその無水物と反応させて得られる重合性不飽和基含有アルカリ可溶性樹脂であることを特徴とする〔１〕〜〔３〕のいずれかに記載の遮光膜用感光性樹脂組成物。

但し、一般式（II）において、Ｒ_６及びＲ_７は、独立に水素原子、炭素数１〜５のアルキル基、又はハロゲン原子を示し、Ｘ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、ｌは０〜１０の数である。
〔５〕（C）成分が、下記式(III）で表される化合物を含有する光重合開始剤であることを特徴とする〔１〕〜〔４〕のいずれかに記載の遮光膜用感光性樹脂組成物。

〔６〕（D）成分が、表面処理されたカーボンブラックを含有することを特徴とする〔１〕〜〔５〕のいずれかに記載の遮光膜用感光性樹脂組成物。
〔７〕前記〔１〕〜〔６〕のいずれかに記載の遮光膜用感光性樹脂組成物を硬化させて形成したことを特徴とする塗膜。
〔８〕前記〔１〕〜〔６〕のいずれかに記載の遮光膜用感光性樹脂組成物により作製された遮光膜を透明基板上に備えてなるカラーフィルターの製造方法であって、当該遮光膜用感光性樹脂組成物を透明基板上に塗布、プリベークした後、紫外線露光装置による露光、アルカリ水溶液による現像、及びポストベークして遮光膜を作製することを特徴とするカラーフィルターの製造方法。
〔９〕前記〔１〕〜〔６〕のいずれかに記載の遮光膜用感光性樹脂組成物により作製された遮光膜を透明基板上に備えてなるタッチパネルの製造方法であって、当該遮光膜用感光性樹脂組成物を透明基板上に塗布、プリベークした後、紫外線露光装置による露光、アルカリ水溶液による現像、及びポストベークして遮光膜を作製することを特徴とするタッチパネルの製造方法。 [1] The following components (A) to (D),
(A) a polymerizable unsaturated group obtained by reacting an unsaturated group-containing monocarboxylic acid with an epoxy compound having two or more epoxy groups in one molecule, and further reacting a polyvalent carboxylic acid or an acid anhydride thereof Containing alkali-soluble resin,
(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond,
(C) a photopolymerization initiator containing a fluorene compound having a polymerizable group at the 9-position of the fluorene ring, and
(D) A photosensitive resin composition for a light-shielding film containing as an essential component one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments and inorganic pigments,
The weight ratio (A)/(B) of the component (A) and the component (B) is 50/50 to 90/10, and (100) parts by weight of the total of the component (A) and the component (B) ( A photosensitive resin composition for a light-shielding film, which contains 2 to 30 parts by mass of the component C) and 20 to 80% by mass of the component (D) with respect to the total solid content of the composition.
[2] The photosensitive resin composition for a light shielding film as described in [1] above, wherein the component (C) is a photopolymerization initiator containing a compound represented by the following general formula (I): A photosensitive resin composition for a light shielding film.

However, in the general formula (I), R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or a cycloalkyl group. It represents an alkyl group or an alkylcycloalkyl group, or an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group having 1 to 6 carbon atoms. R ₃ is independently an alkenyl group having 2 to 10 carbon atoms or a substituent having 2 to 10 carbon atoms and having an epoxy group, and a part of —CH ₂ — group in the alkenyl group is —O. It may be substituted with a group. Furthermore, a part of hydrogen atoms in these R _{1 to} R ₃ groups may be substituted with a halogen atom.
[3] In the photosensitive resin composition for a light-shielding film according to the above [1] or [2], the component (D) has a surface resistivity of 1 when formed into a film having an optical density of 4/μm. A photosensitive resin composition for a light-shielding film, which is an insulating light-shielding component having a density of ×10 ⁸ Ω/□ or more.
[4] Polymerizable unsaturation obtained by reacting the reaction product of the compound (A) represented by the following general formula (II) with (meth)acrylic acid with a polycarboxylic acid or an anhydride thereof. The photosensitive resin composition for a light-shielding film according to any one of [1] to [3], which is a group-containing alkali-soluble resin.

However, in the general formula (II), R ₆ and R ₇ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X represents —CO—, —SO ₂ —, or —C. _{(CF 3) 2 -, -} Si (CH 3) 2 -, - CH 2 -, - C (CH 3) 2 -, - O-, shows a fluorene-9,9-diyl group or a single bond, l is It is a number from 0 to 10.
[5] The photosensitive material for a light-shielding film according to any one of [1] to [4], wherein the component (C) is a photopolymerization initiator containing a compound represented by the following formula (III). Resin composition.

[6] The photosensitive resin composition for a light-shielding film according to any one of [1] to [5], wherein the component (D) contains surface-treated carbon black.
[7] A coating film formed by curing the photosensitive resin composition for a light-shielding film according to any one of [1] to [6] above.
[8] A method for producing a color filter, comprising a light-shielding film made of the photosensitive resin composition for light-shielding film according to any one of [1] to [6] above, which is provided on a transparent substrate. A method for producing a color filter, which comprises producing a light-shielding film by applying a photosensitive resin composition for a film on a transparent substrate, pre-baking, exposing with an ultraviolet exposure device, developing with an alkaline aqueous solution, and post-baking.
[9] A method for manufacturing a touch panel, comprising a light-shielding film made of the photosensitive resin composition for light-shielding film according to any one of [1] to [6] above, on a transparent substrate, the light-shielding film A method for manufacturing a touch panel, comprising: applying a photosensitive resin composition for use on a transparent substrate, pre-baking, exposing with an ultraviolet exposure device, developing with an alkaline aqueous solution, and post-baking to form a light-shielding film.

The photosensitive resin composition for a light-shielding film of the present invention can sufficiently secure development adhesion even when a fine line having a line width of about 5 μm is formed while maintaining high definition and high light-shielding. Also, it is possible to form a high-resistance light-shielding film that has excellent adhesion to a glass substrate.

Hereinafter, the present invention will be described in detail.
As the polymerizable unsaturated group-containing alkali-soluble resin as the component (A), an unsaturated group-containing monocarboxylic acid is reacted with an epoxy compound having two or more epoxy groups in one molecule, and a polyvalent carboxylic acid or Any polymerizable unsaturated group-containing alkali-soluble resin obtained by reacting an acid anhydride can be used without particular limitation, and preferably has the following general formula having two glycidyl ether groups derived from bisphenols. The epoxy compound of (II) is reacted with (meth)acrylic acid (which means “acrylic acid and/or methacrylic acid”), and the obtained compound having a hydroxy group is added with a polyvalent carboxylic acid or an anhydride thereof. It may be an epoxy (meth)acrylate acid addition product obtained by reacting a product. The epoxy compound derived from bisphenols means an epoxy compound obtained by reacting bisphenols with epihalohydrin or an equivalent thereof. Since the component (A) has both a polymerizable unsaturated double bond and a carboxyl group, it imparts excellent photocurability, good developability and patterning characteristics to the photosensitive resin composition, and improves the physical properties of the light-shielding film.

但し、一般式（II）において、Ｒ_６及びＲ_７は、独立に水素原子、炭素数１〜５のアルキル基、又はハロゲン原子を示し、Ｘ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、ｌは０〜１０の数である。

However, in the general formula (II), R ₆ and R ₇ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X represents —CO—, —SO ₂ —, or —C. _{(CF 3) 2 -, -} Si (CH 3) 2 -, - CH 2 -, - C (CH 3) 2 -, - O-, shows a fluorene-9,9-diyl group or a single bond, l is It is a number from 0 to 10.

The epoxy compound represented by the general formula (II) is derived from bisphenols and firstly reacted with an unsaturated group-containing monocarboxylic acid. For the reaction product of this epoxy compound and an unsaturated group-containing monocarboxylic acid, as a polyvalent carboxylic acid or its anhydride, (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride, and (b) tetracarboxylic acid Alternatively, the acid dianhydride is reacted to obtain a polymerizable unsaturated group-containing alkali-soluble resin. Hereinafter, the case of obtaining the component (A) using the compound of the general formula (II) will be described.

Examples of the bisphenols giving the epoxy compound of the general formula (II) include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxy-3,5-dichlorophenyl). ) Ketone, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxy-3,5-dimethylphenyl) sulfone, bis(4-hydroxy-3,5-dichlorophenyl) sulfone, bis(4-hydroxyphenyl)hexafluoro Propane, 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-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene , 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 4,4'-biphenol, 3,3'- Biphenol etc. are mentioned. Among these, bisphenols in which X in the general formula (II) is a fluorene-9,9-diyl group can be particularly preferably used.

In obtaining the alkali-soluble resin (A), it is preferable to react the bisphenols with epichlorohydrin to obtain an epoxy compound having two glycidyl ether groups. In this reaction, since the diglycidyl ether compound is generally oligomerized, the epoxy compound of the general formula (II) is obtained. Since a plurality of values of l are usually mixed, the average value is 0 to 10 (not necessarily an integer), but the preferable average value of l is 0 to 3. When the value of l exceeds the upper limit, the viscosity of the composition becomes too large when the photosensitive resin composition is prepared by using the alkali-soluble resin synthesized by using the epoxy compound, and the coating may not be successful. Alkali solubility cannot be sufficiently imparted, and the alkali developability may be extremely deteriorated.

The polymerizable unsaturated group-containing alkali-soluble resin of the present invention can be obtained from an epoxy compound derived from the above bisphenols, but other than such an epoxy compound, for example, a phenol novolac type epoxy compound, Those obtained from epoxy compounds having two or more glycidyl ether groups such as cresol novolac type epoxy compounds can also be used.

Next, the compound of the general formula (II) is reacted with, for example, acrylic acid or methacrylic acid as an unsaturated group-containing monocarboxylic acid or both of them, and a reaction product having a hydroxy group obtained thereby is reacted. As the polyvalent carboxylic acid or its anhydride, (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride, and (b) tetracarboxylic acid or its dianhydride are reacted. At that time, it is preferable to carry out the reaction in the range of (a)/(b) molar ratio of 0.01 to 10. By this reaction, a polymerizable unsaturated group-containing alkali-soluble resin having a structure of an epoxy (meth)acrylate acid adduct is obtained.

The (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride used in the epoxy (meth)acrylate acid adduct is a chain hydrocarbon dicarboxylic acid or tricarboxylic acid or its acid anhydride or alicyclic dicarboxylic acid or tricarboxylic acid. Acids or acid anhydrides thereof, aromatic dicarboxylic acids or tricarboxylic acids or acid anhydrides thereof are used. Here, as the chain hydrocarbon dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof, for example, succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, There are compounds such as citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid, and further, a dicarboxylic acid or tricarboxylic acid having an arbitrary substituent introduced therein or an acid anhydride thereof may be used. Further, examples of the alicyclic dicarboxylic acid or tricarboxylic acid or acid anhydride thereof include compounds such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, and further optional It may be a dicarboxylic acid or tricarboxylic acid in which the substituent is introduced or an acid anhydride thereof. Furthermore, examples of the aromatic dicarboxylic acid or tricarboxylic acid or acid anhydride thereof include compounds such as phthalic acid, isophthalic acid and trimellitic acid, and further, a dicarboxylic acid or tricarboxylic acid having any substituent introduced therein or its It may be an acid anhydride.

Further, as the (b) tetracarboxylic acid or its dianhydride used in the epoxy (meth) acrylate acid addition product, a chain hydrocarbon tetracarboxylic acid or its dianhydride or alicyclic tetracarboxylic acid or The acid dianhydride, the aromatic polycarboxylic acid or the acid dianhydride is used. Here, as the chain hydrocarbon tetracarboxylic acid or an acid dianhydride thereof, there are, for example, butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, etc., and tetra substituted with any substituent. It may be a carboxylic acid or its dianhydride. The alicyclic tetracarboxylic acid or its dianhydride, for example, cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, and the like, Further, it may be a tetracarboxylic acid having an arbitrary substituent introduced or its dianhydride. Further, examples of the aromatic tetracarboxylic acid and its acid dianhydride include, for example, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid or its acid dianhydride, and further any It may be a tetracarboxylic acid having a substituent introduced therein or its dianhydride.

The molar ratio (a)/(b) of (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride and (b) tetracarboxylic acid or its dianhydride used for the epoxy (meth)acrylate acid adduct is It is preferably 0.01 to 10 as described above. When the molar ratio (a)/(b) deviates from the above range, the optimum molecular weight cannot be obtained, and in the photosensitive resin composition using (A), alkali developability, heat resistance, solvent resistance, pattern shape, etc. It is not preferable because it deteriorates. The smaller the molar ratio (a)/(b), the higher the alkali solubility and the higher the molecular weight.

The epoxy (meth)acrylate acid adduct can be produced by the above-mentioned steps by a known method, for example, the method described in JP-A-8-278629 or JP-A-2008-9401. First, as a method of reacting an unsaturated group-containing monocarboxylic acid with an epoxy compound of the general formula (I), for example, an epoxy group of the epoxy compound and an equimolar unsaturated group-containing monocarboxylic acid are added to a solvent, In the presence of a catalyst (triethylbenzylammonium chloride, 2,6-diisobutylphenol, etc.), there is a method of reacting by heating and stirring at 90 to 120° C. while blowing air. Next, as a method of reacting an acid anhydride with a hydroxyl group of an epoxy acrylate compound which is a reaction product, a predetermined amount of an epoxy acrylate compound, an acid dianhydride and an acid monoanhydride is added to a solvent, and a catalyst (odor In the presence of tetraethylammonium chloride, triphenylphosphine, etc.), the reaction is performed by heating and stirring at 90 to 130° C.

The weight average molecular weight (Mw) of the polymerizable unsaturated group-containing alkali-soluble resin (A) is preferably in the range of 2,000 to 50,000, more preferably in the range of 2,000 to 7,000. If the weight average molecular weight (Mw) is less than 2000, the pattern adhesion during development of the photosensitive resin composition using the component (A) cannot be maintained, pattern peeling occurs, and the weight average molecular weight (Mw) ) Is more than 50,000, development residues and residual films in unexposed areas tend to remain. Further, the component (A) preferably has an acid value in the range of 30 to 200 mgKOH/g. If this value is less than 30 mgKOH/g, the alkali development of the photosensitive resin composition using this component (A) may not be successful, or special developing conditions such as strong alkali are required, and if it exceeds 200 mgKOH/g, The alkali developer penetrates into the photosensitive resin composition containing the component A) too quickly and peeling development occurs, which is not preferable. As for the polymerizable unsaturated group-containing alkali-soluble resin as the component (A), only one kind thereof may be used or a mixture of two or more kinds may be used.

Next, (B) as the photopolymerizable monomer having at least one ethylenically unsaturated bond, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-ethylhexyl (meth) (Meth)acrylic acid esters having a hydroxyl group such as 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, di Pentaerythritol 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 Examples thereof include (meth)acrylic acid esters such as oxide-modified hexa(meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate, and one or more of these can be used. The photopolymerizable monomer (B) having at least one ethylenically unsaturated bond does not have a free carboxy group.

The mixing ratio of these components (A) and (B) is 50/50 to 90/10, preferably 60/40 to 80/20 in terms of weight ratio (A)/(B). When the blending ratio of the component (A) is less than 50/50, the cured product after photocuring becomes brittle, and the acid value of the coating film in the unexposed area is low, resulting in a decrease in solubility in an alkali developing solution. There is a problem that the pattern edge is not sharp and sharp, and when it is more than 90/10, the proportion of the photoreactive functional group in the resin is small and the formation of the crosslinked structure is not sufficient. Since the valency is too high and the solubility in the exposed portion in the alkali developing solution becomes high, there arises a problem that the formed pattern becomes thinner than the target line width, or the pattern is apt to be missing. There is a fear.

Further, as the photopolymerization initiator of the component (C), a photopolymerization initiator containing a fluorene compound having a polymerizable group at the 9-position of the fluorene ring is used. By thus having a polymerizable group at the 9-position of the fluorene ring, it is expected that the amount of the photopolymerization initiator volatilized during heat curing can be suppressed especially when the amount of the photopolymerization initiator added is large. Therefore, it is preferable. Preferably, it contains a compound represented by the following general formula (I), generates a radical species by irradiation with ultraviolet light or the like, initiates radical polymerization by adding to a photopolymerizable compound, and cures the composition. Let Among them, more preferably, 1-[9,9-di(2-propenyl)-7-nitrofluoren-2-yl]-(2-methylphenyl)-methanone oxime-O- represented by the general formula (III). Acetate is particularly preferable in that high sensitivity can be achieved. Regarding the production of the general formula (I), for example, the production method is described in Japanese Patent Publication No. 2015-523318.

但し、一般式（I）において、Ｒ_１及びＲ_２はそれぞれ独立に、炭素数１〜１０の直鎖状若しくは分岐状のアルキル基であるか、炭素数４〜１０のシクロアルキル基、シクロアルキルアルキル基若しくはアルキルシクロアルキル基であるか、又は炭素数１〜６のアルキル基で置換されていてもよい炭素数６〜１２のアリール基を表す。Ｒ_３はそれぞれ独立に炭素数２〜１０のアルケニル基であるか、又はエポキシ基を有する炭素数２〜１０の置換基を表し、当該アルケニル基中の−ＣＨ_２−基の一部が−Ｏ−基で置換されていてもよい。さらに、これらＲ_１〜Ｒ_３の基中の水素原子の一部がハロゲン原子で置換されていてもよい。

However, in the general formula (I), R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or a cycloalkyl group. It represents an alkyl group or an alkylcycloalkyl group, or an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group having 1 to 6 carbon atoms. R ₃ is independently an alkenyl group having 2 to 10 carbon atoms or a substituent having 2 to 10 carbon atoms and having an epoxy group, and a part of —CH ₂ — group in the alkenyl group is —O. It may be substituted with a group. Furthermore, a part of hydrogen atoms in these R _{1 to} R ₃ groups may be substituted with a halogen atom.

Further, in the present invention, one or more kinds of other photopolymerization initiators or sensitizers can be used together with the photopolymerization initiator containing the compound represented by the general formula (I). Here, as other photopolymerization initiators or sensitizers, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert. -Acetophenones such as butylacetophenone, benzophenone, 2-chlorobenzophenone, benzophenones such as p,p'-bisdimethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers, 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5 -Diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole and other biimidazole compounds, 2-trichloromethyl-5-styryl-1 ,3,4-Oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3 ,4-Oxadiazole and other halomethyldiazole compounds, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1 ,3,5-Triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3 ,5-Triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl) -1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)- Halomethyl-S- such as 4,6-bis(trichloromethyl)-1,3,5-triazine and 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine 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-acetate, 1-( 4-methylsulfanylphenyl)butan-1-one oxime-O-acetate and other O-acyl oxime compounds, benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthio Xanthones, sulfur compounds such as 2-isopropylthioxanthone, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, anthraquinones such as 2,3-diphenylanthraquinone, azobisisobutylnitrile, benzoyl peroxide, Examples thereof include organic peroxides such as cumene peroxide, thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole.

These photopolymerization initiators and sensitizers including the photopolymerization initiator containing the compound represented by the general formula (I) can be used alone or in combination of two or more. It can also be used. Examples of preferable combinations when used in combination include a combination of a photopolymerization initiator containing a compound of the general formula (I) and a thiol compound. Examples of such thiol compounds are 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis. (3-mercaptobutyrate) and the like can be exemplified, and it is preferable to use a polyfunctional thiol compound. The amount of the thiol compound added when the photopolymerization initiator and the thiol compound are combined is 1 to 10 parts by mass based on 100 parts by mass of the total of the components (A) and (B). preferable.
Further, a compound which does not act as a photopolymerization initiator or a sensitizer by itself but which can increase the ability of the photopolymerization initiator or the sensitizer when used in combination can be added. Examples of compounds used in such a combination include tertiary amines such as triethanolamine and triethylamine, which are effective when used in combination with benzophenone.

The amount of the photopolymerization initiator used as the component (C) is 2 to 30 parts by mass, preferably 5 to 25 parts by mass, more preferably 100 parts by mass of the component (A) and the component (B). 5 to 20 parts by mass. When the compounding ratio of the component (C) is less than 2 parts by mass, the photopolymerization rate becomes slow and the sensitivity decreases, while when it exceeds 30 parts by mass, the sensitivity is too strong and the pattern line There is a possibility that the width becomes thicker than the pattern mask, a line width faithful to the mask cannot be reproduced, or the pattern edge is not sharp and sharp. The photopolymerization initiator of the component (C) contains a photopolymerization initiator represented by the general formula (I) as an essential component, but the amount thereof is independent even if the other component (C) is not added. The amount of the photopolymerization initiator represented by the general formula (I) is preferably 70 to 100% by mass based on the total amount of the component (C). It is preferable to have.

The component (D) is a light-shielding component selected from black organic pigments, mixed color organic pigments or inorganic pigments, and preferably has excellent heat resistance, light resistance and solvent resistance. Here, examples of black organic pigments include perylene black, cyanine black, aniline black, and lactam black. Examples of the mixed color organic pigment include those obtained by mixing two or more kinds of pigments selected from red, blue, green, violet, yellow, cyanine, magenta and the like to be pseudo-blackened. Examples of the inorganic pigment include carbon black, chromium oxide, iron oxide, titanium black, and the like, and two or more kinds may be appropriately selected and used.
Of these, in order to provide the light-shielding film with high resistance characteristics, it is preferable that the surface resistivity (for example, the surface resistivity at an applied voltage of 10 V) of the film formed to have an optical density of 4/μm. It is preferable to use a light-shielding component having a high insulating property such that the density is ×10 ⁸ Ω/□ or more, and a typical example thereof is carbon black subjected to an insulating surface treatment. As an example of the surface-treated carbon black, carbon black in which a substituted aryl group or the like is bonded to the surface by reacting with a diazonium salt shown in Japanese Patent Publication No. H10-510861, is disclosed in JP 2001-207079 A. The carbon black whose surface is coated with a resin, and the carbon black whose surface is coated with a dye as shown in the republished WO 2013/129554 can be exemplified, but carbon black subjected to high resistance treatment has an optical density of 4/ Any film can be used without particular limitation as long as the film has a surface resistivity of 1×10 ⁸ Ω/□ or more. The surface resistivity of the film was formed so that the optical concentration of 4 / [mu] m is more preferably 1 × ¹⁰ 10 Ω / □ or more, and particularly not more 1 × 10 ¹² Ω / □ or more preferable.

Then, these light-shielding components are preferably dispersed in a dispersion medium in advance to prepare a light-shielding dispersion liquid, and then blended as a light-shielding film photosensitive resin composition. Here, examples of the dispersion medium include propylene glycol monomethyl ether acetate and 3 methoxybutyl acetate. The blending ratio of the light-shielding component (D) in the light-shielding dispersion liquid is 20 to 80% by mass, preferably 40 to 70% by mass, based on the total solid content of the composition of the present invention. .. At that time, when using an organic pigment such as aniline black, cyanine black, or lactam black, or a carbon-based light-shielding component such as carbon black, the range of 40 to 60 mass% is particularly preferable. When it is less than 20% by mass, the light-shielding property becomes insufficient. When it exceeds 80% by mass, the content of the photosensitive resin that serves as the original binder decreases, so that the development characteristics are impaired and the film forming ability is impaired, which is an undesirable problem.

In the photosensitive resin composition for a light-shielding film of the present invention, it is preferable to use a solvent in addition to the above (A) to (D) to adjust the viscosity. Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone and N-methyl-2-. Ketones such as pyrrolidone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, cellosolve, methylcellosolve, ethylcellosolve, carbitol, methylcarbitol, ethylcarbitol, butylcarbitol, 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, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve Acetates such as acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. can be mentioned. It can be a solution-like composition.

Further, the light-shielding film photosensitive resin composition of the present invention, if necessary, a curing accelerator, a thermal polymerization inhibitor and an antioxidant, a plasticizer, a filler, a leveling agent and a defoaming agent, a coupling agent, Additives such as surfactants can be added. Examples of the thermal polymerization inhibitor and antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and the like, and examples of the plasticizer include dibutylphthalate, dioctylphthalate, tricresyl phosphate, and the like. Examples of the filler include glass fiber, silica, mica, alumina, and the like, and examples of the leveling agent and the defoaming agent include silicone-based, fluorine-based, and acrylic-based compounds. Further, examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant, and examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, A silane coupling agent such as 3-ureidopropyltriethoxysilane can be mentioned.

The photosensitive resin composition for a light shielding film of the present invention contains the above-mentioned components (A) to (D) or these and a solvent as main components. It is desirable that the solid content excluding the solvent (the solid content includes a monomer that becomes a solid content after curing) contains the components (A) to (D) in a total amount of 80% by mass, preferably 90% by mass or more. The amount of the solvent varies depending on the target viscosity, but it is preferable that the amount of the solvent be contained in the photosensitive resin composition in the range of 70 to 90% by mass.

The photosensitive resin composition for a light-shielding film in the present invention is excellent as a resin composition for forming a color filter light-shielding film, for example, and the following photolithography method can be used to form the light-shielding film. First, the photosensitive resin composition is applied on a transparent substrate, then the solvent is dried (prebaking), a photomask is applied to the coating film thus obtained, and ultraviolet rays are applied to expose the exposed portion. Examples include a method of curing, followed by development using an aqueous alkaline solution to elute unexposed areas to form a pattern, and post-baking (thermal baking) as post-curing.

As the transparent substrate to which the photosensitive resin composition is applied, in addition to a glass substrate, a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone) on which transparent electrodes such as ITO and gold are vapor-deposited or patterned, etc. Can be illustrated. As a method for applying the solution of the photosensitive resin composition on the transparent substrate, any of known solution dipping method, spray method, roller coater machine, land coater machine, slit coater machine, spinner machine and the like can be used. The method can also 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 prebaking 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 pre-baking is performed by an ultraviolet exposure device, and only the resist corresponding to the pattern is exposed by exposing through the photomask. The exposure apparatus and its exposure irradiation conditions are appropriately selected, and light exposure is performed using a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and 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 resist in the unexposed portion, and a desired pattern is formed by this development. Examples of the developer suitable for this alkali development include an aqueous solution of an alkali metal carbonate or an alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like, and particularly sodium carbonate, potassium carbonate, lithium carbonate. It is preferable to develop at a temperature of 23 to 28° C. using a weak alkaline aqueous solution containing 0.05 to 3 mass% of a carbonate such as, and a fine image can be obtained by using a commercially available developing machine or an ultrasonic cleaner. It can be precisely formed.

After the development, heat treatment (post-baking) is preferably performed at a temperature of 180 to 250° C. for 20 to 60 minutes. This post-baking is performed for the purpose of increasing the adhesion between the patterned light-shielding 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 light-shielding film of the present invention is formed through the above steps of the photolithography method.

The photosensitive resin composition for a light-shielding film of the present invention is suitable for forming a fine pattern by operations such as exposure and alkali development, as described above. The photosensitive resin composition for a light-shielding film of the present invention can be preferably used as a coating material, and is particularly suitable as an ink for a color filter used in a liquid crystal display device or a photographing element, and formed by this. The light-shielding film is useful as a color filter, a black matrix for liquid crystal projection, a light-shielding film, a light-shielding film for a touch panel, etc.

Hereinafter, embodiments of the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited thereto.

First, Synthesis Example 1 of the (A) polymerizable unsaturated group-containing alkali-soluble resin of the present invention will be shown. Evaluation of the resin in the synthesis example was performed as follows.

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

[Acid value]
The resin solution was dissolved in dioxane and titrated with a 1/10 N-KOH aqueous solution using a potentiometric titrator [trade name COM-1600 manufactured by Hiranuma Seisakusho Co., Ltd.].

[Molecular weight]
Gel permeation chromatography (GPC) [trade name: HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuper- H5000 (one) [manufactured by Tosoh Corp.], temperature: 40° C., speed: 0.6 ml/min], and measured as standard polystyrene [PS-Oligomer Kit manufactured by Tosoh Corp.] weight average molecular weight ( Mw).

The abbreviations used in the synthesis examples are as follows.
BPFE: A reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane. The compound of the general formula (II), wherein X is a fluorene-9,9-diyl group, and R ₆ and R ₇ are hydrogen.
BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride
THPA: 1,2,3,6-tetrahydrophthalic anhydride
TPP: Triphenylphosphine
PGMEA: Propylene glycol monomethyl ether acetate

[Synthesis example 1]
Into a 500 ml four-necked flask equipped with a reflux condenser, BPFE 78.63g (0.17mol), acrylic acid 24.50g (0.34mol), TPP 0.45g, and PGMEA 114g were charged and stirred under heating at 100 to 105°C for 12 hours. And a reaction product was obtained.
Next, 25.01 g (0.085 mol) of BPDA and 12.93 g (0.085 mol) of THPA were added to the obtained reaction product, and the mixture was stirred for 6 hours under heating at 120 to 125° C. to give a polymerizable unsaturated group-containing alkali-soluble resin solution ( A)-1 was obtained. The solid content concentration of the obtained resin solution was 55.8 wt%, the acid value (solid content conversion) was 103 mgKOH/g, and the Mw by GPC analysis was 2,600.

[Comparative Synthesis Example 1]
Methacrylic acid 51.65 g (0.60 mol), methyl methacrylate 38.44 g (0.38 mol), cyclohexyl methacrylate 36.33 g (0.22 mol), AIBN 5.91 g, and DMDG 368 g in a 1000 ml four-necked flask equipped with a nitrogen introduction tube and a reflux tube. After charging, the mixture was polymerized by stirring at 80 to 85°C under a nitrogen stream for 8 hours. Furthermore, 39.23 g (0.28 mol) of glycidyl methacrylate, 1.44 g of TPP, and 0.055 g of 2,6-di-tert-butyl-p-cresol were charged into the flask, and the mixture was stirred at 80 to 85° C. for 16 hours to be polymerizable unsaturated. A group-containing alkali-soluble resin solution (A)-2 was obtained. The polymerizable unsaturated group-containing alkali-soluble resin thus obtained had a solid content concentration of 32% by mass, an acid value (in terms of solid content) of 110 mgKOH/g, and an Mw by GPC analysis of 18080.

[Synthesis example 2]
As the component (C), a synthesis example of the compound represented by the formula (III) is shown.

<STEP1>
250 parts by mass of tetrahydrofuran (THF) and 42.2 parts by mass of potassium tert-butoxide (KTB) were charged into a reaction vessel, and 25.0 parts by mass of fluorene was added. Next, 40.0 parts by mass of 3-bromo-1-propene was added dropwise to the reaction vessel. This solution was heated to 40° C. and stirred for 3 hours. Next, this liquid was cooled to room temperature, ethyl acetate and water were injected, the oil layer was separated, and washing with water was repeated twice. Then, the oil layer was dried over anhydrous magnesium sulfate, the anhydrous magnesium sulfate was filtered off, and the filtrate was concentrated to obtain 37.0 parts by mass of 9,9-di(2-propenyl)-fluorene.

<STEP2>
The obtained 9,9-di(2-propenyl)-fluorene (36.3 parts by mass), methylene chloride (370 parts by mass) and aluminum chloride (29.5 parts by mass) were charged into a reaction vessel and stirred. This liquid was cooled to 10° C., 22.8 parts by mass of o-toluoyl chloride was added dropwise, and the mixture was further stirred for 4 hours. The reaction solution was poured into 370 parts by mass of water cooled to 10° C. or lower, the oil layer was separated, and washed with an aqueous potassium carbonate solution. Then, the oil layer was dried over anhydrous magnesium sulfate, the anhydrous magnesium sulfate was filtered off, and the filtrate was concentrated to form an o-trioil group at the 2-position of 9,9-di(2-propenyl)-fluorene. 50.6 parts by mass of 1-[9,9-di(2-propenyl)-fluoren-2-yl]-(2-methylphenyl)-methanone (Compound 1-A) introduced were obtained.

<STEP3>
50.0 parts by mass of the obtained compound 1-A and 500 parts by mass of acetic acid were charged into a reaction vessel, 11.3 parts by mass of fuming nitric acid was added dropwise, and this liquid was heated to 80°C. 13.7 parts by mass of concentrated sulfuric acid was added dropwise to this reaction solution, and the mixture was stirred at 80° C. for 3 hours. After stirring, the mixture was cooled to room temperature, water and ethyl acetate were injected, the oil layer was separated, and washing with water and an aqueous potassium carbonate solution was repeated. Then, the oil layer was dried over anhydrous magnesium sulfate, the anhydrous magnesium sulfate was filtered off, and the filtrate was concentrated. The obtained oily substance was isolated and purified by silica gel column chromatography, and 1-[9,9-di(2-propenyl)-7-nitrofluorene in which a nitro group was introduced at the 7-position of the fluorene skeleton of compound 1-A. -2-yl]-(2-methylphenyl)-methanone (Compound 1-B) was obtained in an amount of 33.4 parts by mass.

<STEP4>
30.0 parts by mass of the obtained compound 1-B, 90 parts by mass of propylene glycol monomethyl ether (PGME), and 35 parts by mass of pyridine were charged into a reaction vessel and stirred. Then, 30.5 parts by mass of hydroxylamine hydrochloride was added, and the mixture was heated to 140° C. and stirred for 4 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were injected, the oil layer was separated, and washed again with water, dilute hydrochloric acid and an aqueous sodium chloride solution. Then, the oil layer was dried over anhydrous magnesium sulfate, anhydrous magnesium sulfate was filtered off, and the filtrate was concentrated to oxime compound 1-B 1-[9,9-di(2-propenyl)- 77.7 parts by mass of 7-nitrofluoren-2-yl]-(2-methylphenyl)-methanone oxime (Compound 1-C) was obtained.

<STEP5>
25.0 parts by mass of the obtained compound 1-C and 125 parts by mass of ethyl acetate were charged into a reaction vessel, 13.8 parts by mass of acetic anhydride were added dropwise, and the mixture was stirred at room temperature for 5 hours. Water and ethyl acetate were poured into this reaction solution, the oil layer was separated, and washed with an aqueous potassium carbonate solution and an aqueous sodium chloride solution. Next, the oil layer was dried over anhydrous magnesium sulfate, the anhydrous magnesium sulfate was filtered off, and the filtrate was concentrated. The resulting product was recrystallized from ethyl acetate/hexane to give the compound of formula (III), 1-[9,9-di(2-propenyl)-7-nitrofluoren-2-yl]-. 17.2 parts by mass of (2-methylphenyl)-methanone oxime-O-acetate (Compound 1) was obtained.

[Comparative Synthesis Example 2]
1-[9,9-di(Synthesis Example 2) is the same as Synthesis Example 2 except that n-butyl bromide is used in place of 3-bromo-1-propene in STEP 1. n-Butyl)-7-nitrofluoren-2-yl]-(2-methylphenyl)-methanone oxime-O-acetate (Compound 2) was obtained.

[Comparative Synthesis Example 3]
Similar to Synthesis Example 2 except that in Synthesis Example 2, n-propyl bromide was used in place of 3-bromo-1-propene in STEP 1, and acetyl chloride was used in place of o-toluoyl chloride in STEP 2. By going through each reaction step, ethanone, 1-[9,9-di-n-propyl-7-nitrofluoren-2-yl]-O-acetyloxime (Compound 3) was obtained.

(Examples 1 to 4, Comparative Examples 1 to 4)
Next, the present invention will be specifically described based on Examples and Comparative Examples relating to the production of a photosensitive resin composition and a cured product thereof, but the present invention is not limited thereto. Here, the raw materials and abbreviations used in the production of the photosensitive resin compositions of the following Examples and Comparative Examples and cured products thereof are as follows.

(Polymerizable unsaturated group-containing alkali-soluble resin)
(A)-1 component: A polymerizable unsaturated group-containing alkali-soluble resin solution obtained in Synthesis Example 1 above.
(A)-2 component: Polymerizable unsaturated group-containing alkali-soluble resin solution obtained in Comparative Synthesis Example 1 above

(Photopolymerizable monomer)
(B)-1: Mixture of dipentaerythritol pentaacrylate and hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.)
(B)-2: Mixture of pentaerythritol triacrylate and tetraacrylate (manufactured by Toagosei Co., Ltd., trade name M-450)

(Photopolymerization initiator)
(C)-1: Compound 1 obtained in Synthesis Example 2 above (compound represented by formula (III))
(C)-2: Compound 2 obtained in Comparative Synthesis Example 2 above
(C)-3: Compound 3 obtained in Comparative Synthesis Example 3 above
(C)-4: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(0-acetyloxime) (manufactured by BASF Japan Ltd., product name Irgacure OXE02)

(Shading component dispersion)
(D)-1: Propylene glycol monomethyl ether acetate dispersion having a surface-treated carbon black A concentration of 25.0% by mass and a polymer dispersant concentration of 4.0% by mass (solid content 29.0%).
(D)-2: Propylene glycol monomethyl ether acetate dispersion having a surface-treated carbon black B concentration of 25.0% by mass and a polymer dispersant concentration of 3.8% by mass (solid content 28.8%).
(D)-3: Propylene glycol monomethyl ether acetate dispersion liquid having a surface-treated carbon black C concentration of 25.0% by mass and a polymer dispersant concentration of 5.0% by mass (solid content: 30.0%)

(Silane coupling agent)
(E): 3-mercaptopropyltrimethoxysilane [trade name: KBM-803: manufactured by Shin-Etsu Chemical Co., Ltd.]

(Thiol compound)
(F): Pentaerythritol tetrakis (3-mercaptobutyrate) [Product name: Karenz MT PE1: Showa Denko KK]

(solvent)
(G)-1: Propylene glycol monomethyl ether acetate (PGMEA)
(G)-2: Cyclohexanone (ANON)

(Surfactant)
(H): BYK-330 (manufactured by Big Chemie)

[Evaluation of light-shielding components]
<Preparation of composition for evaluating characteristics of light-shielding component>
Resin solution [(A)-1 component], light-shielding component dispersion [(D)-1 component to (D)-3 component] and solvent [(G)-1 component] so that the solid content concentration is 20%. A composition for measuring surface resistivity was prepared by mixing. At this time, a composition capable of forming a cured film with OD=4/μm was prepared by changing the ratio of the resin and the light-shielding component while measuring the optical density (OD).

<Optical density>
The composition for measuring surface resistivity obtained above was applied onto a glass substrate having a thickness of 1.2 mm by a spin coater so that the film thickness after heat curing treatment would be 1.1 μm, and at 90° C. Prebaked for 1 minute. After that, heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer to obtain a cured film of the composition. Next, the optical density of the obtained cured film was measured using a Macbeth transmission densitometer and evaluated by the optical density per unit film thickness.

<Surface resistivity measurement>
The surface resistivity of the cured film whose optical density was measured was measured at a voltage of 10 V using a surface resistivity meter (HIRESTA UP manufactured by Mitsubishi Chemical Analytech Co., Ltd.).
Table 1 shows the composition ratios of the compositions and the measurement results for the compositions capable of forming a cured film with OD=4/μm.

The above-mentioned components were mixed in the proportions shown in Table 2 to prepare the photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 4.

[Evaluation]
Using the photosensitive resin compositions for light-shielding films of Examples 1 to 4 and Comparative Examples 1 to 4, the following evaluations were performed. The results of these evaluations are shown in Table 3.

<Evaluation of development characteristics (pattern line width/pattern linearity)>
Each of the light-shielding film photosensitive resin compositions obtained above was applied onto a 125 mm×125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking would be 1.1 μm, Prebaked at 90° C. for 1 minute. After that, the exposure gap was adjusted to 100 μm, a 5 μm negative photomask was covered on the dry coating film, and a short-wavelength cut filter [Model LU0350, manufactured by Asahi Spectroscopy Co., Ltd. (340 nm or less The wavelength of the mercury lamp was cut)), and an ultraviolet ray of 80 mJ/cm ² was irradiated with an ultrahigh pressure mercury lamp having an i-line illuminance of 30 mW/cm ² to carry out a photocuring reaction on the photosensitive portion.

Next, the exposed coated plate was subjected to a shower development pressure of 1 kgf/cm ^{2 in} a 0.08% potassium hydroxide aqueous solution at 25° C., from the development time (break time=BT) at which a pattern began to appear, +10 seconds, +15. After development for 2 seconds, spray washing with 5 kgf/cm ² pressure is performed to remove the unexposed portion of the coating film to form a pixel pattern on the glass substrate, and then heat at 230° C. for 30 minutes using a hot air dryer. After the post-baking, the line width with respect to the mask width of the 5 μm line and the pattern linearity were evaluated. When the pattern image did not appear even after the development time of 80 seconds, it was determined that development was impossible. The evaluation methods are as follows.

Pattern line width: A pattern line width with a mask width of 5 μm was measured using a length measuring microscope (“XD-20” manufactured by Nikon Corporation).
Pattern linearity: A 5 μm mask pattern after post-baking is observed under a microscope, and no peeling from the substrate or jagged edges of the pattern edge is observed, ◯, some are observed, and all are observed. It was evaluated as x.

<Evaluation of residual film sensitivity>
Each of the light-shielding film photosensitive resin compositions obtained above was applied onto a 125 mm×125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking would be 1.1 μm, The film thickness of the dried coating film after prebaking at 90° C. for 1 minute was measured. After that, a short-wavelength cut filter [Model No. LU0350, manufactured by Asahi Bunko Co., Ltd. (cuts the wavelength of the mercury lamp of 340 nm or less)] is placed on the dried coating film, and an ultrahigh-pressure mercury lamp with an i-line illuminance of 30 mW/cm ² is placed. At 10 mJ/cm ² to irradiate it with light, and the photocuring reaction of the photosensitive portion was carried out. By making coated plates having different exposure doses by the same method, exposed coated plates were exposed at 10 to 100 mJ/cm ² every 5 mJ/cm ² .
Next, the exposed coated plate was developed in a 0.08% potassium hydroxide aqueous solution at 25° C. under a shower developing pressure of 1 kgf/cm ^{2 and} a developing time (break time=BT)+15 seconds after development was started. Spray washing with a pressure of 5 kgf/cm ² is performed, and the film thickness of the coating film formed at each exposure amount is measured. The residual film sensitivity was defined as the exposure amount at which the film thickness was 95% or more compared to the film thickness before development.

<Evaluation of OD/μm>
The photosensitive resin composition for each light-shielding film obtained above was applied on a 125 mm×125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking would be 1.1 μm, Prebaked at 90° C. for 1 minute. After that, a short wavelength cut filter [model number LU0350, manufactured by Asahi Bunko Co., Ltd. (cuts mercury lamp wavelength of 340 nm or less)] is placed on the dried coating film without covering with a negative photomask, and i-line illuminance Ultraviolet light of 80 mJ/cm ² was irradiated with an ultra-high pressure mercury lamp of 30 mW/cm 2 to carry out a photocuring reaction on the photosensitive portion.

Next, the exposed coated plate was developed in a 0.08% aqueous potassium hydroxide solution at 25° C. at a shower development pressure of 1 kgf/cm ² for 60 seconds, and then spray washed with 5 kgf/cm ² pressure. After hot post-baking at 230° C. for 30 minutes using a hot air dryer, the OD of the light irradiation part was evaluated using a Macbeth transmission densitometer. Further, the film thickness of the light irradiation portion was measured, and the value obtained by dividing the OD value by the film thickness was defined as OD/μm.

<Adhesion evaluation>
Each of the light-shielding film photosensitive resin compositions obtained above was applied onto a 125 mm×125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking would be 1.1 μm, Prebaked at 90° C. for 1 minute. After that, a short-wavelength cut filter [model number LU0350 manufactured by Asahi Bunko Co., Ltd. (cuts a mercury lamp wavelength of 340 nm or less)] was placed on the coating film without using a negative photomask, and the i-line illuminance was 30 mW/cm. and solid exposed by ² extra-high pressure mercury lamp at 80 mJ / cm ^2, 230 ° C. using a hot air dryer to heat post-baked for 30 minutes. Then, the post-baked substrate obtained above was evaluated for adhesion strength with the seal glass substrate by the evaluation method according to the three-point bending adhesion test method of JIS K6856-1994 as follows.

Each of the above post-baked substrate and the glass substrate (Corning 1737) not coated with the resin composition was cut into a strip of 20 mm×63 mm to prepare a test piece. A post-baked coating plate and a glass substrate not coated with the photosensitive resin composition are overlapped with a certain amount of a sealant epoxy adhesive (Structbond XN-21s (manufactured by Mitsui Chemicals)) Both substrates (test pieces) were bonded together so that the thickness was 8 mm. The shape of the sealant epoxy adhesive when superposed is circular and the diameter is about 5 mm. After that, the laminated test pieces were prebaked at 90° C. for 20 minutes, and then post-baked at 150° C. for 2 hours to form three-point bent test pieces. Further, 20 mm×63 mm uncoated glass pieces were also laminated in the same manner as above to prepare a sample for a comparative test.

In the test piece obtained above, the coated plate and the counter substrate (non-coated substrate) or the uncoated glass substrate for the comparative test are supported by two supports so that the overlapping portion is centered (2 The length of the support at the point is 3 cm), and the weight is applied at a speed of 1 mm/minute from just above the overlay to just below it using "UCT-100" manufactured by Orientec Co., and the peeled surface is observed. Then, the weight at that time was read, divided by the application area of the sealant epoxy adhesive, and the weight per unit area was taken as the adhesion strength. Further, after performing PCT (pressure cooker test) under the conditions of 121° C., 100% RH, 2 atm, and 5 hours, the same adhesion strength test was performed to evaluate the adhesion strength before and after PCT. The adhesion strength of each composition is shown as a relative value, where the adhesion strength between the glasses not coated with the resist before and after PCT is 100. Before and after PCT, 60 or more was evaluated as ◯, and less than 60 was evaluated as x.

<Volume resistivity>
Each of the light-shielding film photosensitive resin compositions obtained above had a thickness of 3 after heat curing using a spin coater on a portion of the 1.2-mm thick Cr-deposited glass substrate excluding the electrodes. It was applied so as to have a thickness of 0.5 μm, and prebaked at 90° C. for 1 minute. After that, heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition. Then, an aluminum electrode was formed on the cured film to prepare a substrate for measuring volume resistivity. Next, the volume resistivity at an applied voltage of 1V to 10V was measured using an electrometer (“6517A type” manufactured by Keithley). The volume resistivity was measured under the condition that the voltage was held for 60 seconds at each applied voltage in 1 V steps, and the volume resistivity when 1 V, 5 V and 10 V was applied are shown in Table 3.

Claims (9)

The following (A) ~ (D) components,
(A) a polymerizable unsaturated group obtained by reacting an unsaturated group-containing monocarboxylic acid with an epoxy compound having two or more epoxy groups in one molecule, and further reacting a polyvalent carboxylic acid or an acid anhydride thereof Containing alkali-soluble resin,
(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond,
(C) a photopolymerization initiator containing a fluorene compound having a polymerizable group at the 9-position of the fluorene ring, and
(D) A photosensitive resin composition for a light-shielding film, which contains as an essential component one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments and inorganic pigments,
The weight ratio (A)/(B) of the component (A) and the component (B) is 50/50 to 90/10, and (100) parts by weight of the total of the component (A) and the component (B) ( A photosensitive resin composition for a light-shielding film, which contains 2 to 30 parts by mass of the component C) and 20 to 80% by mass of the component (D) with respect to the total solid content of the composition. The photosensitive resin composition for a light-shielding film according to claim 1, wherein the component (C) is a photopolymerization initiator containing a compound represented by the following general formula (I). Resin composition.

However, in the general formula (I), R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or a cycloalkyl group. It represents an alkyl group or an alkylcycloalkyl group, or an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group having 1 to 6 carbon atoms. R ₃ is independently an alkenyl group having 2 to 10 carbon atoms or a substituent having 2 to 10 carbon atoms and having an epoxy group, and a part of —CH ₂ — group in the alkenyl group is —O. It may be substituted with a group. Furthermore, a part of hydrogen atoms in these R _{1 to} R ₃ groups may be substituted with a halogen atom. The photosensitive resin composition for a light-shielding film according to claim 1 or 2, wherein the component (D) has a surface resistivity of 1×10 ⁸ Ω/□ formed so as to have an optical density of 4/μm. A photosensitive resin composition for a light-shielding film, which is an insulating light-shielding component as described above. (A) a polymerizable unsaturated group-containing alkali obtained by further reacting a reaction product of a compound represented by the following general formula (II) and (meth)acrylic acid with a polycarboxylic acid or an anhydride thereof. It is a soluble resin, The photosensitive resin composition for light-shielding films in any one of Claims 1-3 characterized by the above-mentioned.

However, in the general formula (II), R ₆ and R ₇ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X represents —CO—, —SO ₂ —, or —C. _{(CF 3) 2 -, -} Si (CH 3) 2 -, - CH 2 -, - C (CH 3) 2 -, - O-, shows a fluorene-9,9-diyl group or a single bond, l is It is a number from 0 to 10. The photosensitive resin composition for a light-shielding film according to claim 1, wherein the component (C) is a photopolymerization initiator containing a compound represented by the following formula (III).

The photosensitive resin composition for a light shielding film according to any one of claims 1 to 5, wherein the component (D) contains surface-treated carbon black. A coating film formed by curing the photosensitive resin composition for a light-shielding film according to claim 1. A method for producing a color filter comprising a transparent substrate and a light-shielding film produced from the photosensitive resin composition for a light-shielding film according to any one of claims 1 to 6, wherein the photosensitive resin composition for a light-shielding film is provided. A method for producing a color filter, comprising: applying a product on a transparent substrate, pre-baking, exposing with an ultraviolet exposure device, developing with an alkaline aqueous solution, and post-baking to produce a light-shielding film. A method for producing a touch panel, comprising a light-shielding film prepared from the light-shielding film photosensitive resin composition according to any one of claims 1 to 6 on a transparent substrate, wherein the light-shielding film photosensitive resin composition is provided. Is applied on a transparent substrate, pre-baked, exposed with an ultraviolet exposure device, developed with an alkaline aqueous solution, and post-baked to produce a light-shielding film.