JP7345252B2 - Photosensitive resin composition for light-shielding film, cured product thereof, and method for producing color filters and touch panels using the cured product - Google Patents

Description

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 developable photosensitive resin composition for a light-shielding film suitable for forming a fine light-shielding film on a transparent substrate. , and its cured product, and the light-shielding film obtained by curing is suitably used when forming color filters (CF) and touch panels.

A color liquid crystal display device consists of a liquid crystal part that controls the amount of light transmitted or reflected, and a color filter.The manufacturing method for the color filter is usually to attach the liquid crystal to the surface of a transparent substrate such as glass or plastic sheet. A method is used in which a black matrix is formed, and then different hues of red, green, and blue are sequentially formed in a striped or mosaic 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. Color filters are one of the important components that affect the visibility of color liquid crystal display devices.In order to improve visibility, that is, to obtain clear images, red (R) and green ( It is necessary to achieve higher color purity for pixels such as G) and blue (B) than ever before, as well as to achieve high light shielding in the black matrix. must also be added in large quantities.

In addition, in recent years, ultra-high definition (400 Pixel Per Inch or higher) technology is required to obtain Full High Definition resolution 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 reduce the size of each red, green, and blue pixel, but it is important not to reduce the aperture ratio of the color filter (the area ratio of RGB pixels through which backlight light passes). This is necessary for increasing brightness, and thinning of the black matrix is also required. That is, while the line width of the black matrix has traditionally been 6 to 8 μm, recently a line width of 4 to 5 μm has been required.

Furthermore, there is a tendency to increase the intensity of the backlight in order to increase the 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-shielding. In order to ensure high light shielding, the thickness of the black matrix can be increased, but as the thickness increases, it becomes more susceptible to the effects of the development process, and the variation in the line width of the black matrix within the mother glass surface increases. . Particularly in the case of thin lines of 4 to 5 μm, variations in line width have a large effect on display performance, such as the occurrence of display unevenness. Therefore, in order to ensure the target light-shielding degree with the thinnest film thickness possible, it is necessary to increase the light-shielding property per unit film thickness. However, since the content of black pigment in the resin composition is usually increased, the blending ratio of binder resin and acrylate components that contribute to curability becomes relatively small, and the coating film is not sufficiently cured. This causes a problem in that the adhesion between the coating film and the glass substrate decreases, making peeling more likely.

By the way, PCT (Pressure Cooker Test) is generally performed as a durability test (reliability test) for LCD panels, but this test method requires several tests under the harsh conditions of temperature 121°C, humidity 100%, and atmospheric pressure 2 atm. The liquid crystal panel is left alone for a period of time, and the presence or absence of leakage of liquid crystal sealed between the color filter substrate and TFT substrate of the liquid crystal panel is checked. The black matrix exists between each color of red, green, and blue, and in addition to improving contrast, it also functions as an outer frame light-shielding film of the color filter, and a part of the outer frame light-shielding film is connected to the opposite substrate through a sealing material. It's pasted together. Therefore, the black matrix is also required to have high adhesion strength so that it will not peel off from the glass substrate even under severe conditions such as PCT. In particular, in recent years, there has been a strong need for high light shielding even in the outer frame light shielding film in order to improve the visibility of liquid crystal panels.

Furthermore, in CF for IPS (FFS) mode panels used in small and medium-sized panels such as smartphones and mobile devices, the black matrix is preferably required to have high resistance. Increasing the light-shielding component to improve light-shielding properties lowers the resistance value, so ensuring thin lines, high light-shielding, high adhesion (high reliability), and high resistance is an extremely high technical hurdle.
By the way, carbon black is generally known as a light-shielding material (black coloring material) for a resin black matrix, but since carbon black has a relatively low electrical resistance, it may cause malfunctions of display devices. . In an in-plane switching (IPS) type liquid crystal display device that provides a particularly 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 will not be applied properly and the liquid crystal alignment will be affected. Disturbance occurs and causes display unevenness.

Therefore, as a method of increasing the electrical resistance of a black matrix using carbon black, a technique of coating the surface of carbon black with a resin (see Patent Document 1) has been applied, but in order to increase the resistance, the amount of resin coating has been applied. When increasing the amount of light, there is a limit to the degree of light shielding that can be achieved while maintaining sufficient optical patterning properties, and it has become difficult to achieve the required levels of high light shielding and high resistance. Therefore, a technology has been developed that uses specific titanium nitride particles as a light shielding material (see Patent Document 2), which can achieve high light shielding with relatively high resistance, but there are concerns that optical patterning properties and storage stability may be insufficient. be done.

As the need for a black matrix that satisfies various required characteristics increases, specifically, in photosensitive resin compositions that contain a large proportion of light-shielding materials and are difficult to photocure, pattern dimensions can be improved at low exposure doses. To obtain a fine line pattern with good stability, pattern adhesion, and sharpness of pattern edge shape with a wide development margin, and also to have high light shielding, preferably high resistance, and to be suitable for glass substrates even in durability tests such as PCT. There is a need to form a black matrix and an outer frame light-shielding film of good quality with high adhesion (high reliability). Note that there is also an increasing demand for forming a light shielding film on the outer frame of a touch panel for the same purpose as the color filter outer frame light shielding film.

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

Japanese Patent Application Publication No. 2001-207079 Japanese Patent Application Publication No. 2008-260927 Patent No. 5682094 Special table 2015-523318 publication

The present invention has been made in view of the above problems, and its purpose is to maintain high definition and high light shielding in a photosensitive resin composition even when a thin line of, for example, 5 μm is formed. Provided is a photosensitive resin composition for a light-shielding film that can form a black matrix that has sufficient development adhesion, excellent adhesion to a glass substrate, and also has high resistance characteristics. It's about doing. Another object of the present invention is to provide a cured product such as a light-shielding film pattern formed by photolithography using the photosensitive resin composition, and furthermore, to provide a color filter or touch panel containing the cured product.

The present inventors conducted studies to solve the above problems, and found that a photosensitive resin composition containing an alkali-soluble resin containing a polymerizable unsaturated group, a photopolymerizable monomer, a photopolymerization initiator, and a light-shielding component. In particular, by blending an oxime ester fluorene-based photopolymerization initiator with a polymerizable group as a photopolymerization initiator, it is possible to maintain high definition, high light shielding, and high adhesion to glass substrates, while also forming fine lines. A specific insulating light-shielding component that can ensure sufficient development adhesion and can increase the surface resistivity when a film is formed with an optical density of 4/μm is added as a light-shielding component. The inventors have discovered that it is possible to form a high-resistance light-shielding film by this method, 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] Ingredients (A) to (D) below,
(A) Polymerizable unsaturated group obtained by reacting an epoxy compound having two or more epoxy groups in one molecule with an unsaturated group-containing monocarboxylic acid, and further reacting with a polyhydric carboxylic acid or its acid anhydride. Contains 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 a black organic pigment, a color-mixing organic pigment, and an inorganic pigment,
The weight ratio (A)/(B) of component (A) and component (B) is 50/50 to 90/10, and ( A photosensitive resin composition for a light-shielding film, characterized in that it contains 2 to 30 parts by mass of component C) and 20 to 80 mass % of component (D) based on the total solid content of the composition.
[2] In the photosensitive resin composition for a light-shielding film as described in [1] above, the component (C) is a photopolymerization initiator containing a compound represented by the following general formula (I). Photosensitive resin composition for light-shielding films.

However, in 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 having 4 to 10 carbon atoms. It represents an alkyl group, 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 each independently represents an alkenyl group having 2 to 10 carbon atoms or a substituent having 2 to 10 carbon atoms having an epoxy group, and some of the -CH ₂ - groups in the alkenyl group are -O - may be substituted with a group. Furthermore, some of the hydrogen atoms in these groups R ₁ to R ₃ may be substituted with halogen atoms.
[3] In the photosensitive resin composition for a light-shielding film according to [1] or [2] above, the component (D) increases the surface resistivity of the film formed so that the optical density is 4/μm. A photosensitive resin composition for a light-shielding film, characterized in that it is an insulating light-shielding component having a resistance of 10 ⁸ Ω/□ or more.
[4] Component (A) is a polymerizable unsaturated product obtained by reacting a reaction product of a compound represented by the following general formula (II) and (meth)acrylic acid with a polyhydric carboxylic acid or its anhydride. 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 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 -, -C (CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, fluorene-9,9-diyl group or single bond, l is It is a number from 0 to 10.
[5] The photosensitive material for light-shielding films 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, on a transparent substrate, a light-shielding film prepared from the photosensitive resin composition for a light-shielding film according to any one of [1] to [6] above, the method comprising: A method for producing a color filter, which comprises applying a photosensitive resin composition for film onto a transparent substrate, pre-baking it, exposing it to light using an ultraviolet exposure device, developing it with an alkaline aqueous solution, and post-baking to prepare a light-shielding film.
[9] A method for producing a touch panel comprising a light-shielding film prepared from the photosensitive resin composition for a light-shielding film according to any one of [1] to [6] above on a transparent substrate, the method comprising: A method for manufacturing a touch panel, comprising applying a photosensitive resin composition on a transparent substrate, pre-baking, exposing the composition to an ultraviolet exposure device, developing with an alkaline aqueous solution, and post-baking to prepare a light-shielding film.

The photosensitive resin composition for a light-shielding film of the present invention can maintain high definition and high light-shielding while ensuring sufficient development adhesion even when a thin line with a line width of about 5 μm is formed, for example. It also has excellent adhesion to glass substrates and can be used as a high-resistance light-shielding film.

The present invention will be explained in detail below.
The polymerizable unsaturated group-containing alkali-soluble resin of component (A) is prepared by reacting an epoxy compound having two or more epoxy groups in one molecule with an unsaturated group-containing monocarboxylic acid, and then reacting a polycarboxylic acid or its Any alkali-soluble resin containing a polymerizable unsaturated group obtained by reacting an acid anhydride can be used without any particular restriction, and preferably the following general formula having two glycidyl ether groups derived from bisphenols is used. The epoxy compound of (II) is reacted with (meth)acrylic acid (this means "acrylic acid and/or methacrylic acid"), and the resulting hydroxy group-containing compound is reacted with a polyhydric carboxylic acid or its anhydride. It is preferable to use an epoxy (meth)acrylate acid adduct obtained by reacting epoxy (meth)acrylate acids. The epoxy compound derived from bisphenols means an epoxy compound obtained by reacting bisphenols with epihalohydrin, or an equivalent thereof. Since component (A) has both a polymerizable unsaturated double bond and a carboxyl group, it provides the photosensitive resin composition with excellent photocurability, good developability, and patterning properties, 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 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 -, -C (CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, fluorene-9,9-diyl group or single bond, l is It is a number from 0 to 10.

This epoxy compound of general formula (II) is derived from bisphenols, and is first 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 polyhydric carboxylic acid or its anhydride, (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride, and (b) tetracarboxylic acid Alternatively, an alkali-soluble resin containing a polymerizable unsaturated group is obtained by reacting the acid dianhydride. Hereinafter, the case where component (A) is obtained using the compound of general formula (II) will be explained.

Examples of bisphenols that give the epoxy compound of general formula (II) 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)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-hydroxy-3-chlorophenyl)propane -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'- Examples include biphenol. Among these, bisphenols in which X in general formula (II) is a fluorene-9,9-diyl group can be particularly preferably used.

In obtaining the alkali-soluble resin (A), preferably, the above bisphenols and epichlorohydrin are reacted to obtain an epoxy compound having two glycidyl ether groups. Since this reaction generally involves oligomerization of the diglycidyl ether compound, an epoxy compound of general formula (II) is obtained. Normally, since a plurality of values are mixed, l has an average value of 0 to 10 (not necessarily an integer), but a preferable average value of l is 0 to 3. If the value of l exceeds the upper limit, when a photosensitive resin composition is made using an alkali-soluble resin synthesized using the epoxy compound, the viscosity of the composition becomes too large and coating may not be successful. The alkali solubility may not be sufficiently imparted and the alkali developability may become very poor.

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

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

(a) Dicarboxylic acid or tricarboxylic acid or its acid anhydride used in the epoxy (meth)acrylate acid adduct includes chain hydrocarbon dicarboxylic acid or tricarboxylic acid or its acid anhydride, alicyclic dicarboxylic acid or tricarboxylic acid, or alicyclic dicarboxylic acid or tricarboxylic acid. Acids or their acid anhydrides, aromatic dicarboxylic acids or tricarboxylic acids or their acid anhydrides are used. Here, examples of the chain hydrocarbon dicarboxylic acid or tricarboxylic acid or its acid anhydride include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citralic acid, malonic acid, glutaric acid, Examples include compounds such as citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid, and furthermore, dicarboxylic acids or tricarboxylic acids into which arbitrary substituents have been introduced, or acid anhydrides thereof may be used. Examples of alicyclic dicarboxylic acids or tricarboxylic acids or their acid anhydrides include compounds such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and norbornanedicarboxylic acid. It may also be a dicarboxylic acid or tricarboxylic acid into which a substituent has been introduced, or an acid anhydride thereof. Furthermore, examples of aromatic dicarboxylic acids or tricarboxylic acids or their acid anhydrides include compounds such as phthalic acid, isophthalic acid, and trimellitic acid; An acid anhydride may also be used.

In addition, as (b) tetracarboxylic acid or its acid dianhydride used in the epoxy (meth)acrylate acid adduct, chain hydrocarbon tetracarboxylic acid or its acid dianhydride, alicyclic tetracarboxylic acid or The acid dianhydride or the aromatic polyhydric carboxylic acid or the acid dianhydride is used. Here, examples of the chain hydrocarbon tetracarboxylic acid or its acid dianhydride include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and tetracarboxylic acid into which any substituent has been introduced. It may also be a carboxylic acid or its acid dianhydride. Further, examples of alicyclic tetracarboxylic acids or acid dianhydrides include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, and the like. Furthermore, it may be a tetracarboxylic acid or its acid dianhydride into which any substituent has been introduced. Furthermore, examples of aromatic tetracarboxylic acids and their acid dianhydrides include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenyl ethertetracarboxylic acid, and their acid dianhydrides; A tetracarboxylic acid having a substituent introduced therein or an acid dianhydride thereof may also be used.

The molar ratio (a)/(b) of (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride and (b) tetracarboxylic acid or its acid dianhydride used in the epoxy (meth)acrylate acid adduct is , as mentioned above, is preferably from 0.01 to 10. If the molar ratio (a)/(b) deviates from the above range, the optimum molecular weight will not be obtained, and the photosensitive resin composition using (A) will have poor alkali developability, heat resistance, solvent resistance, pattern shape, etc. This is not desirable because it deteriorates. Note that 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 a known method, for example, the method described in JP-A-8-278629, JP-A-2008-9401, etc., using the above-mentioned steps. First, as a method for reacting an unsaturated group-containing monocarboxylic acid with the epoxy compound of general formula (I), for example, an unsaturated group-containing monocarboxylic acid in an equimolar amount to the epoxy group of the epoxy compound is added to a solvent, There is a method in which the reaction is carried out by heating and stirring at 90 to 120°C while blowing air in the presence of a catalyst (triethylbenzylammonium chloride, 2,6-diisobutylphenol, etc.). Next, as a method for reacting an acid anhydride with the hydroxyl group of the epoxy acrylate compound, which is a reaction product, a predetermined amount of the epoxy acrylate compound, an acid dianhydride, and an acid monoanhydride are added to a solvent, and a catalyst (odor) is added to the solvent. There is a method in which the reaction is carried out by heating and stirring at 90 to 130°C in the presence of tetraethylammonium chloride, triphenylphosphine, etc.).

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 adhesion of the pattern during development of the photosensitive resin composition using this component (A) cannot be maintained, pattern peeling occurs, and the weight average molecular weight (Mw ) exceeds 50,000, development residues and residual films in unexposed areas tend to remain. Furthermore, the acid value of component (A) is preferably in the range of 30 to 200 mgKOH/g. If this value is less than 30 mgKOH/g, the photosensitive resin composition using this component (A) may not be well developed with alkali, or special developing conditions such as strong alkali will be required; if it exceeds 200 mgKOH/g, this ( Neither of these is preferred because the alkaline developer penetrates into the photosensitive resin composition using component A too quickly, causing peeling development. Regarding the polymerizable unsaturated group-containing alkali-soluble resin of component (A), only one type thereof or a mixture of two or more types thereof may be used.

Next, (B) photopolymerizable monomers having at least one ethylenically unsaturated bond include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. (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, alkylene of phosphazene Examples include (meth)acrylic esters such as oxide-modified hexa(meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate, and one or more of these may be used. Note that (B) the photopolymerizable monomer having at least one ethylenically unsaturated bond does not have a free carboxyl group.

The weight ratio (A)/(B) of these components (A) and (B) is 50/50 to 90/10, preferably 60/40 to 80/20. If the blending ratio of component (A) is less than 50/50, the cured product after photocuring will become brittle, and the acid value of the coating film will be low in the unexposed areas, resulting in a decrease in solubility in alkaline developers. Problems arise in that the pattern edges are jagged and not sharp, and if the ratio is more than 90/10, the proportion of photoreactive functional groups in the resin is small and the formation of a crosslinked structure is insufficient, and furthermore, the acid in the resin component If the concentration is too high, the solubility in the alkaline developer in the exposed area increases, resulting in problems such as the formed pattern being narrower than the target line width and the pattern becoming more likely to be missing. There is a fear.

Furthermore, as the photopolymerization initiator for component (C), a photopolymerization initiator containing a fluorene compound having a polymerizable group at the 9-position of the fluorene ring is used. By having a polymerizable group at the 9-position of the fluorene ring, effects such as suppressing the amount of photopolymerization initiator volatilized during heat curing are expected, especially when the amount of photopolymerization initiator added is large. It is preferable because Preferably, the composition contains a compound represented by the following general formula (I), generates radical species by irradiation with ultraviolet light, etc., and adds the radical species to a photopolymerizable compound to initiate radical polymerization, thereby curing the composition. let Among them, 1-[9,9-di(2-propenyl)-7-nitrofluoren-2-yl]-(2-methylphenyl)-methanone oxime-O- represented by general formula (III) is more preferable. Acetate is particularly preferred since it can achieve high sensitivity. Regarding the production of 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 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 having 4 to 10 carbon atoms. It represents an alkyl group, 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 each independently represents an alkenyl group having 2 to 10 carbon atoms or a substituent having 2 to 10 carbon atoms having an epoxy group, and some of the -CH ₂ - groups in the alkenyl group are -O - may be substituted with a group. Furthermore, some of the hydrogen atoms in these groups R ₁ to R ₃ may be substituted with halogen atoms.

Furthermore, in the present invention, one or more other photopolymerization initiators or sensitizers can be used together with the photopolymerization initiator containing the compound represented by general formula (I). Here, other photoinitiators or sensitizers include, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert - Acetophenones such as butylacetophenone, benzophenones such as benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5 -Biimidazole compounds such as diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole, 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, 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-oneoxime-O - O-acyloxime compounds such as acetate, sulfur compounds such as benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone , anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, cumene peroxide, 2-mercapto Examples include thiol compounds such as benzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole.

These photopolymerization initiators and sensitizers, including photopolymerization initiators containing the compound represented by general formula (I), can be used alone or in combination of two or more. You can also use An example of a preferable combination when used in combination is a combination of a photopolymerization initiator containing the compound of general formula (I) and a thiol compound. Such thiol compounds include 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), and pentaerythritol tetrakis. (3-mercaptobutyrate), etc., and it is preferable to use a polyfunctional thiol compound. In addition, when a photopolymerization initiator and a thiol compound are combined in this way, the amount of the thiol compound added is 1 to 10 parts by mass based on the total of 100 parts by mass of components (A) and (B). preferable.
Further, it is also possible to add a compound that does not act as a photopolymerization initiator or sensitizer by itself, but can increase the ability of the photopolymerization initiator or sensitizer when used in combination. 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 photopolymerization initiator used as component (C) is 2 to 30 parts by mass, preferably 5 to 25 parts by mass, more preferably 5 to 25 parts by mass, based on the total of 100 parts by mass of components (A) and (B). The amount is 5 to 20 parts by mass. If the blending ratio of component (C) is less than 2 parts by mass, the speed of photopolymerization becomes slow and the sensitivity decreases, while if it exceeds 30 parts by mass, the sensitivity is too strong and the pattern line The width becomes thicker than the pattern mask, and there is a risk that a line width that is faithful to the mask cannot be reproduced, or that pattern edges are jagged and not sharp. The photopolymerization initiator of component (C) contains the photopolymerization initiator represented by the general formula (I) as an essential component, but the amount is The amount of the photopolymerization initiator represented by general formula (I) is often 70 to 100% by mass of the total amount of component (C). It is preferable that there be.

Component (D) is a light-shielding component selected from black organic pigments, color-mixing organic pigments, and inorganic pigments, and preferably has excellent heat resistance, light resistance, and solvent resistance. Here, examples of the black organic pigment include perylene black, cyanine black, aniline black, and lactam black. Examples of mixed-color organic pigments include those obtained by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta, etc. to create a pseudo-black color. Examples of inorganic pigments include carbon black, chromium oxide, iron oxide, titanium black, and the like, and two or more types can be appropriately selected and used.
Among these, in order to provide the light-shielding film with high resistance characteristics, preferably the surface resistivity of the film formed so that the optical density is 4/μm (for example, the surface resistivity at an applied voltage of 10 V) is 1 It is preferable to use a light-shielding component with high insulating properties such as ×10 ⁸ Ω/□ or more, and a typical example thereof is carbon black that has been subjected to an insulating surface treatment. Examples of surface-treated carbon black include the carbon black shown in Japanese Patent Publication No. H10-510861, which is reacted with a diazonium salt to bond a substituted aryl group, etc. to the surface, and the carbon black shown in Japanese Patent Application Publication No. 2001-207079. Examples include carbon black whose surface is coated with a resin, and carbon black whose surface is coated with a dye as shown in republished WO 2013/129554. Any film can be used without any particular limitation as long as it has a surface resistivity of 1×10 ⁸ Ω/□ or more. The surface resistivity of the film formed to have an optical density of 4/μm is more preferably 1× ¹⁰ Ω/□ or more, and particularly preferably 1×10 ¹² Ω/□ or more. preferable.

These light-shielding components are preferably dispersed in a dispersion medium in advance to form a light-shielding dispersion liquid, and then blended into the photosensitive resin composition for a light-shielding film. Here, examples of the dispersion medium include propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and the like. The blending ratio of the light-shielding component (D) in the light-shielding dispersion is preferably 20 to 80% by mass, preferably 40 to 70% by mass based on the total solid content of the composition of the present invention. . 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 amount is particularly preferably in the range of 40 to 60% by mass. If it is less than 20% by mass, the light shielding properties will not be sufficient. If it exceeds 80% by mass, the content of the photosensitive resin that is the original binder decreases, resulting in undesirable problems such as impairing development characteristics and film-forming ability.

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, N-methyl-2- Ketones such as pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene Glycol ethers such as glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve Examples include acetate esters such as acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. It can be made into a solution-like composition.

In addition, the photosensitive resin composition for a light-shielding film of the present invention may optionally contain a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a coupling agent, Additives such as surfactants can be blended. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and phenothiazine; examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of the filler include glass fiber, silica, mica, alumina, etc., and examples of the leveling agent and antifoaming agent include silicone-based, fluorine-based, and acrylic-based compounds. In addition, examples of the surfactant include fluorine-based surfactants and silicone-based surfactants, and examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, Examples include silane coupling agents such as 3-ureidopropyltriethoxysilane.

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 monomers that become solid content after curing) contains components (A) to (D) in a total of 80% by mass, preferably 90% by mass or more. The amount of the solvent varies depending on the target viscosity, but it is preferably 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 as a method for forming the light-shielding film. First, a photosensitive resin composition is applied onto a transparent substrate, and then the solvent is dried (prebaking). A photomask is placed on the film thus obtained, and the exposed area is exposed to ultraviolet rays. Examples include a method in which a pattern is formed by curing and further developing to elute unexposed areas using an alkaline aqueous solution, and then post-baking (thermal baking) is performed as post-curing.

Transparent substrates to which the photosensitive resin composition is applied include glass substrates, as well as transparent films (e.g., polycarbonate, polyethylene terephthalate, polyethersulfone, etc.) on which transparent electrodes such as ITO or gold are deposited or patterned. can be exemplified. As a method for applying the solution of the photosensitive resin composition onto the transparent substrate, in addition to the well-known solution immersion method and spray method, any method using a roller coater machine, land coater machine, slit coater machine, or spinner machine can be used. method can also be adopted. By these methods, a film is formed by applying the film to a desired thickness and then removing the solvent (prebaking). Prebaking is performed by heating with an oven, hot plate, or the like. The heating temperature and heating time in prebaking are appropriately selected depending on the solvent used, and is carried out, for example, at a temperature of 60 to 110° C. for 1 to 3 minutes.

Exposure performed after prebaking is performed using an ultraviolet exposure device, and by exposing through a photomask, only the portions of the resist corresponding to the pattern are exposed. The exposure device and its exposure irradiation conditions are appropriately selected, and exposure is performed using a light source such as an ultra-high-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a far-ultraviolet lamp, etc., and the photosensitive resin composition in the coating film is photocured.

Alkaline development after exposure is performed for the purpose of removing the resist in unexposed areas, and a desired pattern is formed by this development. Examples of developing solutions suitable for this alkaline development include aqueous solutions of carbonates of alkali metals and alkaline earth metals, aqueous solutions of alkali metal hydroxides, and particularly sodium carbonate, potassium carbonate, lithium carbonate, etc. It is best to develop at a temperature of 23 to 28°C using a weakly alkaline aqueous solution containing 0.05 to 3% by mass of carbonates such as carbonates. Can be formed precisely.

After development, heat treatment (post-bake) 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. Similar to pre-baking, this is done by heating with an oven, hot plate, etc. The patterned light-shielding film of the present invention is formed through the steps of the photolithography method described above.

As described above, 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. Further, the photosensitive resin composition for light-shielding films of the present invention can be suitably used as a coating material, and is particularly suitable as an ink for color filters used in liquid crystal display devices or photographic elements. 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 touch panels, and the like.

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

[Acid value]
It was determined by dissolving the resin solution in dioxane and titrating it with a 1/10N-KOH aqueous solution using a potentiometric titration device (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 columns) + TSKgelSuperH-3000 (1 column) + TSKgelSuperH-4000 (1 column) + TSKgelSuper- The weight average molecular weight ( Mw) was calculated.

Further, the abbreviations used in the synthesis examples are as follows.
BPFE: A reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane. A compound of general formula (II) in which 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]
BPFE 78.63g (0.17mol), acrylic acid 24.50g (0.34mol), TPP 0.45g, and PGMEA 114g were placed in a 500ml four-necked flask equipped with a reflux condenser, and stirred for 12 hours under heating at 100 to 105°C. 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 form 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 equivalent) was 103 mgKOH/g, and the Mw by GPC analysis was 2600.

[Comparative synthesis example 1]
In a 1000 ml four-necked flask equipped with a nitrogen inlet tube and a reflux tube, 51.65 g (0.60 mol) of methacrylic acid, 38.44 g (0.38 mol) of methyl methacrylate, 36.33 g (0.22 mol) of cyclohexyl methacrylate, 5.91 g of AIBN, and 368 g of DMDG were added. The mixture was charged and polymerized by stirring for 8 hours at 80 to 85°C under a nitrogen stream. 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 remove polymerizable unsaturation. A group-containing alkali-soluble resin solution (A)-2 was obtained. The obtained polymerizable unsaturated group-containing alkali-soluble resin had a solid content concentration of 32% by mass, an acid value (in terms of solid content) of 110 mgKOH/g, and an Mw of 18,080 by GPC analysis.

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

<STEP1>
A reaction vessel was charged with 250 parts by mass of tetrahydrofuran (THF) and 42.2 parts by mass of potassium tert-butoxide (KTB), and 25.0 parts by mass of fluorene was added thereto. Then, 40.0 parts by mass of 3-bromo-1-propene was added dropwise to the reaction vessel. This liquid was heated to 40°C and stirred for 3 hours. Next, this liquid was cooled to room temperature, ethyl acetate and water were poured into it, the oil layer was separated, and water washing was repeated twice. Next, 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>
36.3 parts by mass of the obtained 9,9-di(2-propenyl)-fluorene, 370 parts by mass of methylene chloride, and 29.5 parts by mass of aluminum chloride 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. This reaction solution was poured into 370 parts by mass of water cooled to 10° C. or lower, and the oil layer was separated and washed with an aqueous potassium carbonate solution. Next, 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-trioyl group at the 2-position of 9,9-di(2-propenyl)-fluorene. 50.6 parts by mass of the introduced 1-[9,9-di(2-propenyl)-fluoren-2-yl]-(2-methylphenyl)-methanone (compound 1-A) was 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 added to separate the oil layer, and the mixture was washed repeatedly with water and an aqueous potassium carbonate solution. Next, the oil layer was dried over anhydrous magnesium sulfate, then the anhydrous magnesium sulfate was filtered off, and the filtrate was concentrated. The obtained oil was isolated and purified by silica gel column chromatography to obtain 1-[9,9-di(2-propenyl)-7-nitrofluorene with a nitro group introduced at the 7-position of the fluorene skeleton of compound 1-A. 33.4 parts by mass of -2-yl]-(2-methylphenyl)-methanone (compound 1-B) was obtained.

<STEP 4>
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. Next, 30.5 parts by mass of hydroxylamine hydrochloride was added, heated to 140°C, and stirred for 4 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were poured into it, and the oil layer was separated, and washed again with water, dilute hydrochloric acid, 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 to obtain oxime-formed compound 1-B, 1-[9,9-di(2-propenyl)- 27.7 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 placed in a reaction vessel, 13.8 parts by mass of acetic anhydride was added dropwise, and the mixture was stirred at room temperature for 5 hours. Water and ethyl acetate were poured into this reaction solution, and 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 obtained product was recrystallized from ethyl acetate/hexane to obtain 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]
In Synthesis Example 2, 1-[9,9-di( n-Butyl)-7-nitrofluoren-2-yl]-(2-methylphenyl)-methanone oxime-O-acetate (Compound 2) was obtained.

[Comparative synthesis example 3]
Synthesis Example 2 was the same as Synthesis Example 2 except that n-propyl bromide was used instead of 3-bromo-1-propene in STEP 1, and acetyl chloride was used instead 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 explained based on Examples and Comparative Examples related to the production of photosensitive resin compositions and cured products thereof, but the present invention is not limited thereto. Here, the raw materials and abbreviations used in the production of photosensitive resin compositions and cured products thereof in Examples and Comparative Examples below are as follows.

(Polymerizable unsaturated group-containing alkali-soluble resin)
(A)-1 component: 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 (manufactured by Nippon Kayaku Co., Ltd., trade name DPHA)
(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, product name Irgacure OXE02)

(Light blocking component dispersion)
(D)-1: Propylene glycol monomethyl ether acetate dispersion with 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 with 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 with 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 [Product name: KBM-803: Manufactured by Shin-Etsu Chemical Co., Ltd.]

(thiol compound)
(F): Pentaerythritol tetrakis(3-mercaptobutyrate) [Product name: Karenz MT PE1: Manufactured by Showa Denko K.K.]

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

(surfactant)
(H): BYK-330 (manufactured by BYK Chemie)

[Evaluation regarding 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] to a solid content concentration of 20%. A composition for surface resistivity measurement was prepared by mixing. At this time, a composition capable of forming a cured film with an OD of 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 coated on a 1.2 mm thick glass substrate using a spin coater so that the film thickness after heat curing was 1.1 μm, and heated at 90°C. Prebaked for 1 minute. Thereafter, 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 in terms of 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).
Table 1 shows the composition ratio and measurement results for a composition capable of forming a cured film with an OD of 4/μm.

The above ingredients were blended in the proportions shown in Table 2 to prepare photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 4.

[evaluation]
The following evaluations were conducted using the photosensitive resin compositions for light-shielding films of Examples 1 to 4 and Comparative Examples 1 to 4. Table 3 shows these evaluation results.

<Evaluation of development characteristics (pattern line width/pattern linearity)>
Each of the photosensitive resin compositions for light-shielding films obtained above was applied onto a 125 mm x 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.1 μm, Prebaked at 90°C for 1 minute. After that, the exposure gap was adjusted to 100 μm, and a 5 μm negative photomask was placed on top of the dry coating film. mercury lamp wavelength cut)] and irradiated with 80 mJ/cm ² of ultraviolet rays using an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW/cm ² to perform a photocuring reaction on the photosensitive area.

Next, this exposed coated plate was heated at 25°C in a 0.08% potassium hydroxide aqueous solution at a shower development pressure of 1 kgf/cm ² to +10 seconds and +15 seconds from the development time (break time = BT) at which the pattern began to appear. After development for 2 seconds, spray washing with water at 5 kgf/cm ² pressure was performed to remove the unexposed areas of the coating film to form a pixel pattern on the glass substrate. After post-baking, the line width with respect to the mask width of the 5 μm line, the pattern linearity, and the pattern linearity were evaluated. If the pattern image did not appear even after the development time of 80 seconds, it was determined that development was not possible. The evaluation methods are as follows.

Pattern line width: The 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: Observe the 5 μm mask pattern after post-baking with a microscope. ○ indicates that no peeling from the substrate or jagged edges of the pattern is observed, △ indicates that it is observed in some areas, and △ indicates that it is observed throughout the entire area. Rated as ×.

<Evaluation of residual film sensitivity>
Each of the photosensitive resin compositions for light-shielding films obtained above was applied onto a 125 mm x 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.1 μm, After prebaking at 90° C. for 1 minute, the thickness of the dried coating film was measured. After that, a short-wavelength cut filter [model number LU0350, manufactured by Asahi Bunko Co., Ltd. (cuts mercury lamp wavelengths of 340 nm or less)] is placed on top of the dried paint film, and an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW/cm ² is used. 10 mJ/cm ² of ultraviolet rays were irradiated to perform a photocuring reaction on the photosensitive area. By preparing coated plates with different exposure amounts using the same method, exposed coated plates exposed to 10 to 100 mJ/cm ² at every 5 mJ/cm ² were obtained.
Next, this exposed coated plate was developed at 25°C in a 0.08% potassium hydroxide aqueous solution at a shower development pressure of 1 kgf/cm ² for a development time (break time = BT) + 15 seconds at which a pattern begins to appear. , 5 kgf/cm ² pressure of spray water washing is performed, and the film thickness of the coating film created at each exposure amount is measured. The exposure amount at which the film thickness was 95% or more compared to the film thickness before development was defined as the residual film sensitivity.

<Evaluation of OD/μm>
Each of the photosensitive resin compositions for light-shielding films obtained above was applied onto a 125 mm x 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.1 μm, Prebaked at 90°C for 1 minute. After that, a short wavelength cut filter [model number LU0350, manufactured by Asahi Spectroscopy Co., Ltd. (cuts mercury lamp wavelengths of 340 nm or less)] is placed on the dried paint film without covering it with a negative photomask, and the i-line illuminance is UV rays of 80 mJ/cm 2 were irradiated with a 30 mW/cm ² ultra-high pressure mercury lamp to perform a photocuring reaction on the photosensitive areas.

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

<Evaluation of adhesion>
Each of the photosensitive resin compositions for light-shielding films obtained above was applied onto a 125 mm x 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.1 μm, Prebaked at 90°C for 1 minute. Then, without using a negative photomask, a short wavelength cut filter [model number LU0350 manufactured by Asahi Bunko Co., Ltd. (cuts mercury lamp wavelengths of 340 nm or less)] was placed on top of the coating film, and the i-line illuminance was adjusted to 30 mW/cm. The film was exposed to light at 80 mJ/cm ² using an ultra-high pressure mercury lamp ( ^{No. 2} ), and post-baked at 230° C. for 30 minutes using a hot air dryer. Then, the adhesion strength of the post-baked substrate obtained above to the seal glass substrate was evaluated as follows by an evaluation method based on the three-point bending adhesion test method of JIS K6856-1994.

The above-mentioned post-baked substrate and a glass substrate (Corning 1737) not coated with the resin composition were each cut into strips of 20 mm x 63 mm to prepare test pieces. The post-baked coated plate and the glass substrate to which the photosensitive resin composition has not been applied are bonded together using a certain amount of sealant epoxy adhesive (Structbond XN-21s (manufactured by Mitsui Chemicals)). Both substrates (test pieces) were bonded together so that the distance was 8 mm. When stacked, the sealant epoxy adhesive has a circular shape and a diameter of about 5 mm. Thereafter, the stacked test pieces were pre-baked at 90°C for 20 minutes, and then post-baked at 150°C for 2 hours to create a three-point bending test piece. Furthermore, a sample for a comparative test was prepared by laminating uncoated glass pieces of 20 mm x 63 mm together in the same manner as described above.

In the test piece obtained above, the coated plate and the counter substrate (non-coated substrate), or the uncoated glass substrate for comparative testing, are supported by two supports (2 The length of the point support is 3 cm), and the peeled surface is observed by applying a load at a speed of 1 mm/min using Orientech's "UCT-100" from just above to below the overlapping part. The load at that time was read and divided by the applied area of the sealing agent epoxy adhesive, and the load per unit area was taken as the adhesion strength. In addition, after performing PCT (pressure cooker test) under the conditions of 121° C., 100% RH, 2 atm, and 5 hours, a similar 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, with the adhesion strength between glasses not coated with resist before and after PCT being 100. Before and after PCT, scores of 60 or more were marked as ○, and scores of less than 60 were marked as ×.

<Volume resistivity>
Each of the photosensitive resin compositions for a light-shielding film obtained above was applied onto a 1.2 mm thick Cr-deposited glass substrate, excluding the electrodes, using a spin coater so that the film thickness after heat curing was 3 mm. It was coated to a thickness of .5 μm and prebaked at 90° C. for 1 minute. Thereafter, 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. Thereafter, an aluminum electrode was formed on the cured film to create a substrate for measuring volume resistivity. Next, the volume resistivity was measured at an applied voltage of 1 V to 10 V using an electrometer (manufactured by Keithley, Model 6517A). Measurement was performed under the condition that each applied voltage was held for 60 seconds in 1 V steps, and the volume resistivity when 1 V, 5 V, and 10 V was applied is shown in Table 3.

Claims (7)

Ingredients (A) to (D) below,
(A) Polymerizable unsaturated group obtained by reacting an epoxy compound having two or more epoxy groups in one molecule with an unsaturated group-containing monocarboxylic acid, and further reacting with a polyhydric carboxylic acid or its acid anhydride. Contains 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 a black organic pigment, a color-mixing organic pigment, and an inorganic pigment,
Component (C) is a photopolymerization initiator containing a compound represented by the following general formula (I),
Component (D) is an insulating light-shielding component that makes the surface resistivity of the film formed so as to have an optical density of 4/μm to be 1× ¹⁰ Ω/□ or more,
The weight ratio (A)/(B) of component (A) and component (B) is 50/50 to 90/10, and ( A photosensitive resin composition for a light-shielding film, characterized in that it contains 2 to 30 parts by mass of component C) and 20 to 80 mass % of component (D) based on the total solid content of the composition.

However, in 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 having 4 to 10 carbon atoms. It represents an alkyl group, 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 each independently represents an alkenyl group having 2 to 10 carbon atoms or a substituent having 2 to 10 carbon atoms having an epoxy group, and some of the -CH 2 - groups in the alkenyl group are _-O - may be substituted with a group. Furthermore, some of the hydrogen atoms in these groups R ₁ to R ₃ may be substituted with halogen atoms. (A) A polymerizable unsaturated group-containing alkali obtained by reacting a reaction product of a compound represented by the following general formula (II) and (meth)acrylic acid with a polyhydric carboxylic acid or its anhydride. The photosensitive resin composition for a light-shielding film according to claim 1 , which is a soluble resin.

However, in 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 -, -C (CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, fluorene-9,9-diyl group or 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 or 2, wherein the component (C) is a photopolymerization initiator containing a compound represented by the following formula (III).

4. The photosensitive resin composition for a light-shielding film according to claim 1 , wherein component (D) contains surface-treated carbon black. A coating film formed by curing the photosensitive resin composition for a light-shielding film according to any one of claims 1 to 4 . 5. A method for producing a color filter comprising, on a transparent substrate, a light-shielding film prepared using the photosensitive resin composition for light-shielding film according to any one of claims 1 to 4 , the method comprising: 1. A method for producing a color filter, which comprises coating a material on a transparent substrate, pre-baking it, exposing it to light using an ultraviolet exposure device, developing it with an alkaline aqueous solution, and post-baking it to produce a light-shielding film. 5. A method for producing a touch panel comprising, on a transparent substrate, a light-shielding film prepared using the photosensitive resin composition for light-shielding film according to any one of claims 1 to 4 , comprising: the photosensitive resin composition for light-shielding film. 1. A method for manufacturing a touch panel, which comprises coating a transparent substrate on a transparent substrate, pre-baking it, exposing it to light using an ultraviolet exposure device, developing it with an alkaline aqueous solution, and post-baking it to produce a light-shielding film.