JP2022158969A - Photosensitive resin composition for light-shielding film, and light-shielding film, color filter and display device using the same - Google Patents

Abstract

To provide a photosensitive resin composition for a light-shielding film from which a light-shielding film that can achieve both high light-shielding property and high resistance, and is excellent in development adhesion when a thin line is formed can be obtained.SOLUTION: A photosensitive resin composition for a light-shielding film contains (A) an epoxy compound, (B) a polymerizable unsaturated group-containing alkali-soluble resin, (C) a photopolymerizable monomer having at least one ethylenically unsaturated bond, (D) a light-shielding component containing a carbon black as a light-shielding material, (E) a polymerization initiator, and (F) a solvent, as essential components, wherein the component (A) has an aromatic ring in a main chain, the number of aromatic rings to the number of glycidyl groups occupying in the component (A) is 0.5-10, and an epoxy equivalent is 100-400 g/eq.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a photosensitive resin composition for a light-shielding film suitable for forming a black matrix having fine line patterns with high light-shielding and high resistance.

Color filters are one of the important components that affect the visibility of liquid crystal display devices. ), blue (B) pixels, etc., have higher color purity than before, and the black matrix needs to achieve high light shielding. A large amount of agent must be added.

Carbon black is generally known as a light-shielding material for a resin black matrix. Although carbon black has excellent light-shielding properties, it has low electrical resistance, and thus may cause malfunction of display devices. Therefore, as a method of increasing the electrical resistance of the black matrix using carbon black, a method of reducing the ratio of carbon black, which is conductive, or a method of applying a material in which the carbon black surface is pre-coated with a resin has been proposed. However, there is a limit to the degree of light shielding that can be achieved while maintaining sufficient patterning properties, and it has been difficult to achieve the required high light shielding property.

Further, in response to the above-described prior art, the applicant of the present application has found that even when a thin line of 10 μm or less is formed while maintaining the optical density OD and the volume resistivity, it has excellent development adhesion and adhesion to the glass substrate. As a photosensitive resin composition for a light-shielding film that can sufficiently ensure the properties, a method of blending a polymerizable unsaturated group-containing alkali-soluble resin having a specific structure and acid value has been proposed (see Patent Document 1). ). However, even with this method, there is room for further improvement in terms of achieving both high light shielding and high resistance, as the performance of display devices is becoming more sophisticated and the properties required of the black matrix are becoming higher and higher.

Japanese Patent Application Laid-Open No. 2015-200881 JP 2014-145821 A Japanese Patent Application Laid-Open No. 2019-070720

Therefore, the inventors of the present application further studied a photosensitive resin composition for a light-shielding film that can achieve both high light-shielding and high resistance in response to the above-described conventional attempts, and found the following. I got the idea.
That is, while adding a large amount of carbon black as a light shielding material so as to achieve high light shielding, it is possible to reduce the contact probability of carbon black as a means of achieving high resistance without reducing the amount. The idea that contact between carbon blacks would be avoided by suppressing thermal shrinkage during thermal curing of the film, and that normal carbon black, which has been untreated or subjected to oxidation treatment, has It is known that it has many acidic functional groups, and by blending other compounds with functional groups that can preferentially react with them during the thermosetting process of the light-shielding film, it is possible to make such groups near the surface of the carbon black. I arrived at the idea that it would be meaningful to have other resins such as those present.

Regarding such an idea, it has a high heat resistance that can suppress heat shrinkage during heat curing, and a functional group that can preferentially react with the acidic functional group of carbon black during heat curing. As a result of intensive studies on compounds having By blending a fixed amount, it is possible to achieve both high light shielding and high resistance, and to obtain a cured product (light shielding film) that has excellent development adhesion even when a fine line of, for example, 3 to 8 μm is formed. newly discovered.

The applicants of the present application have already proposed a technique for blending an epoxy compound in a photosensitive resin composition (see Patent Document 2 and Patent Document 3), but the technology described in Patent Document 2 is It relates to a black photosensitive resin composition for touch panel applications, and discloses the inclusion of a relatively large amount of an epoxy compound, particularly for the demand for high chemical resistance to chemicals used in the processing process. be. Further, in Patent Document 3, in order to form a resin film pattern on a plastic substrate or the like having a heat resistance of at most 140° C., a curing agent and/or a curing accelerator are essentially blended into the photosensitive resin composition, and It is characterized by setting the total amount of these and the epoxy compound within a specific range, and it merely discloses the essential components especially when aiming at low-temperature curing.
In other words, the compositions described in Patent Documents 2 and 3 require the above formulation, and it was difficult to satisfy all of high light shielding, high resistance, and thinning.

Therefore, the present invention was invented based on the above findings, and the object thereof is to achieve both high light shielding and high resistance, and to provide excellent development adhesion even when thin lines are formed. It is an object of the present invention to provide a photosensitive resin composition for a light-shielding film which gives a light-shielding cured product (light-shielding film).

Another object of the present invention is to provide a light-shielding film formed by curing such a photosensitive resin composition for a light-shielding film, and to provide a color filter comprising the light-shielding film and the color filter. An object of the present invention is to provide a display device with a filter.

That is, the gist of the present invention is as follows.
[1] Components (A) to (F) below,
(A) an epoxy compound,
(B) a polymerizable unsaturated group-containing alkali-soluble resin,
(C) a photopolymerizable monomer having at least one ethylenically unsaturated bond;
(D) a light-shielding component containing carbon black as a light-shielding material;
(E) a photopolymerization initiator, and (F) a photosensitive resin composition for a light-shielding film containing a solvent as essential components,
The component (A) has an aromatic ring in its main chain, the number of aromatic rings relative to the number of glycidyl groups in the component (A) is 0.5 to 10, and the epoxy equivalent is 100 to 400 g/eq. A photosensitive resin composition for a light shielding film characterized by:
[2] The mass ratio (B)/(C) between component (B) and component (C) is 50/50 to 90/10, and component (A) is 0 per 100 parts by mass of component (D). .5 to 15 parts by mass, and the component (D) is contained in the solid content of the photosensitive resin composition for a light shielding film in an amount of 40 to 70% by mass. A photosensitive resin composition.
[3] A light-shielding film formed by curing the photosensitive resin composition for a light-shielding film according to [1] or [2].
[4] A color filter comprising the light-shielding film described in [3].
[5] A display device comprising the color filter of [4].

According to the present invention, it is possible to achieve both high light shielding and high resistance, and for example, even when a fine line of 3 to 8 μm is formed, a light shielding product (light shielding film) that has excellent development adhesion can be obtained. A photosensitive resin composition for a film can be provided.

As described above, the photosensitive resin composition for a light-shielding film of the present invention comprises at least (A) an epoxy compound, (B) an alkali-soluble resin containing a polymerizable unsaturated group, and (C) at least one ethylenically unsaturated bond. (D) a light-shielding component using carbon black as a light-shielding material, (E) a photopolymerization initiator, and (F) a solvent as essential components. These components will be mainly described in detail below.

<(A) epoxy compound>
The (A) epoxy compound in the photosensitive resin composition for a light-shielding film of the present invention must have an aromatic ring in its main chain. By having an aromatic ring in the main chain, it has excellent heat resistance and mechanical properties. It is preferable in that it is possible to suppress the heat shrinkage that occurs in. Here, "having in the main chain" means having at least one aromatic ring in the structure serving as the skeleton of the molecule having the maximum number of carbon atoms, as is commonly used in the art. In addition, the aromatic ring includes a benzene ring, a naphthalene ring, a biphenyl ring, a bisphenol ring, and the like, and their structures may be unsubstituted, or each independently having one or more substituents. good. The substituent may be an alkyl group having 1 to 10 carbon atoms or an aryl group, and is not particularly limited as long as it is within the scope of the object of the present invention.

The component (A) used here has an epoxy equivalent of 100 to 400 g/eq, preferably 120 to 380 g/eq, and more preferably 150 to 360 g/eq. When the epoxy equivalent is less than 100 g/eq, the reaction with the acidic functional group responsible for developing solubility contained in the component (B) may proceed, resulting in deterioration in developability. In this case, the control of the distance between carbon blacks becomes poor, and there is a possibility that an improvement in resistance cannot be expected.

In the component (A), the number of aromatic rings per glycidyl group is 0.5 to 10, preferably 1.1 to 4, more preferably 1.1 to 4. is 1.3-4, particularly preferably 2-4. The number of aromatic rings referred to here is the number of benzene rings, for example, 2 for naphthalene rings, 2 for biphenyl, 3 for anthracene, and 4 for bisphenolfluorene rings. The aromatic ring is preferably bulky (having a large number of aromatic rings), more preferably having a condensed ring structure such as a bisphenol fluorene ring or naphthalene. When the number of aromatic rings/number of glycidyl groups is less than 0.5, the decrease in resistance due to the decrease in heat resistance due to the small number of aromatic rings, or the acidic functionalities contained in component (B) responsible for development solubility due to the large number of glycidyl groups. The reaction with the group proceeds, and the developability may deteriorate. On the contrary, when the number of aromatic rings/number of glycidyl groups exceeds 10, the control of the distance between carbon blacks becomes poor due to the small number of glycidyl groups, and there is a possibility that improvement in resistance cannot be expected.

上記式（１）の場合、芳香環数／グリシジル基数＝（４ｍ_１＋４）／２であり、例えば、ｍ_１＝１の場合は４である。この時、エポキシ当量は４３５である。同様に、ｍ_１＝２の時の芳香環数／グリシジル基数は６、エポキシ当量は６３８である。この関係から、（エポキシ当量）＝１０２×（芳香環数／グリシジル基数）＋２８となるため、エポキシ当量から芳香環数／グリシジル基数を算出することが可能である。 Here, as shown below, the number of aromatic rings/number of glycidyl groups is calculated from the epoxy equivalent based on the proportional relationship between the number of aromatic rings/number of glycidyl groups and the epoxy equivalent when considering the repeating unit of the epoxy compound. It turns out that it is possible. That is, although the number of aromatic rings and the number of glycidyl groups varies depending on the chemical structure and repeating unit of each epoxy compound, in this way, after specifically applying some of the repeating units, the relational expression with the epoxy equivalent is calculated. By grasping in advance, it becomes possible to calculate the number of aromatic rings/number of glycidyl groups according to the measured value of the epoxy equivalent. Here, as a specific example, the compounds represented by the following chemical formulas (1) to (4) are shown as examples, but epoxy compounds other than these can also be obtained in the same manner.
・Bisphenol fluorene type epoxy compound

In the case of the above formula (1), the number of aromatic rings/the number of glycidyl groups=(4m ₁ +4)/2, for example, 4 when m ₁ =1. At this time, the epoxy equivalent is 435. Similarly, when m ₁ =2, the number of aromatic rings/number of glycidyl groups is 6, and the epoxy equivalent is 638. From this relationship, (epoxy equivalent)=102×(aromatic ring number/glycidyl group number)+28, so it is possible to calculate the aromatic ring number/glycidyl group number from the epoxy equivalent.

上記式（２）の場合、芳香環数／グリシジル基数＝（３ｍ_２＋２）／（２ｍ_２＋２）であり、例えば、ｍ_２＝１の場合は１．２５である。この時、エポキシ当量は１６２である。同様に、ｍ_２＝２の時の芳香環数／グリシジル基数は１．３３、エポキシ当量は１７０である。この関係から、（エポキシ当量）＝１０２×（芳香環数／グリシジル基数）＋３４となる。 ・1,6-naphthalenediol aralkyl type epoxy compound

In the case of the above formula (2), the number of aromatic rings/the number of glycidyl groups=(3m ₂ +2)/(2m ₂ +2), for example, 1.25 when m ₂ =1. At this time, the epoxy equivalent is 162. Similarly, when m ₂ =2, the number of aromatic rings/number of glycidyl groups is 1.33 and the epoxy equivalent is 170. From this relationship, (epoxy equivalent)=102×(number of aromatic rings/number of glycidyl groups)+34.

上記式（３）の場合、芳香環数／グリシジル基数＝（３ｍ_３＋２）／（ｍ_３＋１）であり、例えば、ｍ_３＝１の場合は２．５である。この時、エポキシ当量は２５２である。同様に、ｍ_３＝２の時の芳香環数／グリシジル基数は２．６７、エポキシ当量は２６９である。この関係から、（エポキシ当量）＝１０２×（芳香環数／グリシジル基数）－３となる。 ・1-Naphthol aralkyl type epoxy compound

In the case of the above formula (3), the number of aromatic rings/the number of glycidyl groups=(3m ₃ +2)/(m ₃ +1), for example, 2.5 when m ₃ =1. At this time, the epoxy equivalent is 252. Similarly, when m ₃ =2, the number of aromatic rings/number of glycidyl groups is 2.67 and the epoxy equivalent is 269. From this relationship, (epoxy equivalent)=102×(number of aromatic rings/number of glycidyl groups)−3.

上記式（４）の場合、芳香環数／グリシジル基数＝（ｍ_４＋２）／（ｍ_４＋２）であり、エポキシ当量にかかわらず（芳香環数／グリシジル基数）＝１となる。 ・Phenol novolac type epoxy compound

In the case of the above formula (4), the number of aromatic rings/number of glycidyl groups=(m ₄ +2)/(m ₄ +2), and (number of aromatic rings/number of glycidyl groups)=1 regardless of the epoxy equivalent.

As for the component (A), those having a weight average molecular weight of 300 to 10,000 are preferably used.

Such (A) epoxy compound is not particularly limited as long as it has an aromatic ring in the main chain, but for example, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol fluorene type epoxy compound , bisnaphtholfluorene-type epoxy compounds, diphenylfluorene-type epoxy compounds, phenol novolac-type epoxy compounds, cresol novolac-type epoxy compounds, phenol aralkyl-type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (for example, NC-7000L manufactured by Nippon Kayaku Co., Ltd.). , naphthol aralkyl-type epoxy compounds, trisphenolmethane-type epoxy compounds, tetrakisphenolethane-type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polycarboxylic acids, copolymers of methacrylic acid and glycidyl methacrylate. A copolymer of a monomer having a (meth)acrylic group containing glycidyl (meth)acrylate as a unit, an epoxy compound having a silicone skeleton, and the like can be mentioned. Among these, it is preferable to use a polycyclic aromatic epoxy compound from the viewpoint of good affinity with carbon black.
In addition, the said (A) component may use only 1 type of compound, and may use it combining multiple.

The blending amount of the component (A) is preferably 1 to 25 parts by mass, more preferably 1 to 18 parts by mass with respect to a total of 100 parts by mass of the components (B) and (C) described later. parts by mass, more preferably 1.5 to 16 parts by mass. By setting the blending amount of the component (B) and the component (C) within the above ranges, it is possible to obtain good patterning properties, which is preferable.
Further, the component (A) is preferably blended in an amount of 0.5 to 15 parts by mass, more preferably 1 to 13 parts by mass, and further It is preferably 1.0 to 9.0 parts by mass. By optimizing the amount with respect to carbon black in this way, it is possible to achieve both sufficient light shielding properties and resistance while maintaining good affinity with carbon black, which is preferable.

<(B) Polymerizable Unsaturated Group-Containing Alkali-Soluble Resin>
The (B) polymerizable unsaturated group-containing alkali-soluble resin in the photosensitive resin composition for a light-shielding film of the present invention can be used without particular limitation as long as it is a resin having a polymerizable unsaturated group and an acidic group in the molecule. However, as a first example that can be preferably applied, a compound having two or more epoxy groups and (meth)acrylic acid (which means acrylic acid and / or methacrylic acid) are reacted to obtain An epoxy (meth)acrylate compound having a hydroxy group is reacted with (a) a dicarboxylic acid or tricarboxylic acid or its monoanhydride and/or (b) a tetracarboxylic acid or its dianhydride (epoxy (meth)acrylate). ) is an acrylate acid adduct. A bisphenol type epoxy compound and a novolak type epoxy compound can be exemplified as the compound having two or more epoxy groups that are induced to form an epoxy (meth)acrylate acid adduct. Specifically, bisphenol-type epoxy compounds represented by the following general formula (I) can be preferably used.

In formula (I), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and A is - CO—, —SO ₂ —, —C(CF ₃ ) ₂ —, —Si(CH ₃ ) ₂ —, —CH ₂ —, —C(CH ₃ ) ₂ —, —O—, fluorene-9,9- represents a diyl group or a direct bond. l is an integer from 0 to 10; Preferred R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms, and preferred A is fluorene-9,9-diyl group. Also, since l usually has a plurality of values, the average value of l is 0 to 10 (not necessarily an integer), but the preferred average value of l is 0 to 3.

A bisphenol-type epoxy compound is an epoxy compound having two glycidyl ether groups obtained by reacting a bisphenol with epichlorohydrin. This reaction generally involves oligomerization of a diglycidyl ether compound, so that the bisphenol skeleton contains an epoxy compound containing two or more of Bisphenols used in this reaction include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxy-3,5-dichlorophenyl)ketone, bis( 4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl)sulfone, bis(4-hydroxy-3,5-dichlorophenyl)sulfone, bis(4-hydroxyphenyl)hexafluoropropane, bis(4 -hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5- dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy- 3,5-dibromophenyl)methane, 2,2-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, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene , 4,4′-biphenol, 3,3′ - includes biphenols and the like. Among these, bisphenols having a fluorene-9,9-diyl group can be particularly preferably used.

As the (a) dicarboxylic acid or tricarboxylic acid unianhydride to be reacted with the epoxy (meth)acrylate, a chain hydrocarbon dicarboxylic acid or tricarboxylic acid unianhydride, an alicyclic dicarboxylic acid or tricarboxylic acid 1 Anhydrides, monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids are used. Examples of acid monoanhydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citralalic acid, malonic acid, glutaric acid, Acid unianhydrides such as citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid, and dicarboxylic or tricarboxylic acid unianhydrides with optional substituents introduced. good. Examples of acid unihydrides of alicyclic dicarboxylic acids or tricarboxylic acids include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, Acid unianhydrides such as chlorendic acid, hexahydrotrimellitic acid, norbornanedicarboxylic acid, and the like, and further dicarboxylic acid or tricarboxylic acid unianhydrides into which arbitrary substituents have been introduced may be used. Furthermore, the unianhydrides of aromatic dicarboxylic acids or tricarboxylic acids include unianhydrides such as phthalic acid, isophthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid, and 2,3-naphthalenedicarboxylic acid. It may also be an acid monoanhydride of dicarboxylic acid or tricarboxylic acid into which an optional substituent is introduced.

In addition, the (b) tetracarboxylic acid dianhydride to be reacted with the epoxy (meth)acrylate includes a chain hydrocarbon tetracarboxylic acid dianhydride, an alicyclic tetracarboxylic acid dianhydride, or , dianhydrides of aromatic tetracarboxylic acids are used. Here, the acid dianhydrides of chain hydrocarbon tetracarboxylic acids include, for example, acid dianhydrides such as butanetetracarboxylic acid, pentanetetracarboxylic acid, and hexanetetracarboxylic acid. The acid dianhydride of the introduced tetracarboxylic acid may also be used. Examples of alicyclic tetracarboxylic acid dianhydrides include acid dianhydrides such as cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, and norbornanetetracarboxylic acid. It may be an acid dianhydride of a tetracarboxylic acid into which any substituent has been introduced. Furthermore, the acid dianhydrides of aromatic tetracarboxylic acids include, for example, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, naphthalene-1,4,5 ,8-tetracarboxylic acid, naphthalene-2,3,6,7-tetracarboxylic acid dianhydrides such as tetracarboxylic acid dianhydrides introduced with optional substituents may also be used. .

The molar ratio (a)/(b) of (a) dicarboxylic acid or tricarboxylic acid anhydride and (b) tetracarboxylic acid dianhydride reacted with epoxy (meth)acrylate is 0.01 to 10. 0.0, more preferably 0.02 or more and less than 3.0. When the molar ratio (a)/(b) is within the above range, the optimum molecular weight for forming a photosensitive resin composition having good photopatterning properties can easily be obtained, and the alkali solubility is not impaired, which is preferable. .

〔式(II)中、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ独立して水素原子、炭素数１～５のアルキル基、ハロゲン原子又はフェニル基を表し、Ａは、－ＣＯ－、－ＳＯ_２－、－Ｃ（ＣＦ_３）_２－、－Ｓｉ（ＣＨ_３）_２－、－ＣＨ_２－、－Ｃ（ＣＨ_３）_２－、－Ｏ－、フルオレン－９,９－ジイル基又は直結合を表し、Ｘは４価のカルボン酸残基を表し、Ｙ_１及びＹ_２は、それぞれ独立して水素原子又は－ＯＣ－Ｚ－（ＣＯＯＨ）m（但し、Ｚは２価又は３価カルボン酸残基を表し、ｍは１～２の数を表す）を表し、ｎは１～２０の整数を表す。〕 Epoxy (meth)acrylate acid adducts can be produced by known methods such as those described in JP-A-8-278629 and JP-A-2008-9401. First, as a method of reacting (meth)acrylic acid with an epoxy compound, for example, (meth)acrylic acid is added to a solvent in an amount equivalent to the epoxy group of the epoxy compound, and a catalyst (triethylbenzylammonium chloride, 2,6 -Diisobutylphenol, etc.), heating to 90 to 120°C while blowing air and stirring to react. Next, as a method for reacting the acid anhydride with the hydroxyl group of the epoxy acrylate compound that is the reaction product, a predetermined amount of the epoxy acrylate compound and the acid dianhydride and the acid dianhydride are added to a solvent, and a catalyst (odor tetraethylammonium chloride, triphenylphosphine, etc.), heating and stirring at 90 to 130° C. for reaction. The epoxy acrylate acid adduct obtained by this method has the skeleton of general formula (II).

[In formula (II), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group; , -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, fluorene-9,9-diyl group or represents a direct bond, X represents a tetravalent carboxylic acid residue, Y ₁ and Y ₂ each independently represent a hydrogen atom or -OC-Z-(COOH) m (where Z is divalent or trivalent represents a carboxylic acid residue, m represents a number of 1-2), and n represents an integer of 1-20. ]

Another example of component (B) is a copolymer of (meth)acrylic acid, (meth)acrylic acid ester, and the like, which has a (meth)acrylic group and a carboxyl group. For example, in the first step, a copolymer obtained by copolymerizing (meth)acrylic acid esters containing glycidyl (meth)acrylate in a solvent is reacted with (meth)acrylic acid in the second step, and It is an alkali-soluble resin containing a polymerizable unsaturated group obtained by reacting an anhydride of dicarboxylic acid or tricarboxylic acid in a step.

Another example of component (B) is a polyol compound having an ethylenically unsaturated bond in the molecule as the first component, a diol compound having a carboxyl group in the molecule as the second component, and a diisocyanate as the third component. A urethane compound obtained by reacting a compound can be mentioned. As the resin of this type, reference can be made to those disclosed in JP-A-2017-76071.

The polymerizable unsaturated group-containing alkali-soluble resin of the component (B) is preferably incorporated in the solid content of the photosensitive resin composition for a light-shielding film of the present invention in an amount of 10 to 40% by mass, more preferably 20 to 40%. % by mass. Also, the weight average molecular weight (Mw) is generally preferably between 2,000 and 10,000, more preferably between 3,000 and 7,000. If the weight average molecular weight (Mw) is less than 2,000, the adhesion of the pattern cannot be maintained during development, causing pattern peeling. A film tends to remain. Furthermore, the component (B) preferably has an acid value in the range of 30 to 200 KOHmg/g. If this value is less than 30 mg KOH/g, alkali development may not be performed well, or special development conditions such as strong alkali may be required. This is because peeling development is likely to occur.
The polymerizable unsaturated group-containing alkali-soluble resin (A) may be used alone or as a mixture of two or more thereof.

<(C) Photopolymerizable monomer having at least one ethylenically unsaturated bond>
Examples of (C) the photopolymerizable monomer having at least one ethylenically unsaturated bond in the photosensitive resin composition for a light-shielding film of the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) acrylate, 2-hydroxyhexyl (meth) acrylate and other hydroxyl group (meth) acrylic esters, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetra Ethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate , pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol (meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta( meth)acrylates, or (meth)acrylates such as dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene alkylene oxide-modified hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc. and dendritic polymers having (meth)acryloyl groups, etc., and one or more of these can be used. As a dendritic polymer having a (meth)acryloyl group, for example, a part of the carbon-carbon double bond in the (meth)acryloyl group of a polyfunctional (meth)acrylate compound has a thiol group in the polyvalent mercapto compound. Known dendritic polymers obtained by addition can be exemplified.

The component (C) can play a role of cross-linking the molecules of the alkali-soluble resin, and in order to exhibit this function, it is preferable to use one having two or more ethylenically unsaturated bonds. Further, the acrylic equivalent obtained by dividing the molecular weight of the monomer by the number of (meth)acryloyl groups in one molecule may be 50 to 300.

Regarding the blending amount of component (C), the mass ratio (B)/(C) is 50/50 to 90/10, preferably 60/40 to 80/20, as a blending ratio with the above component (B). is. If the blending ratio of component (B) 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 reduced solubility in an alkaline developer. Pattern edges may not be jagged and sharp. If the blending ratio of component (B) is more than 90/10, the proportion of photoreactive functional groups in the resin is too small to form a sufficient crosslinked structure, and the acid value of the resin component is too high. As a result, there is a risk that the solubility in the alkaline developer in the exposed portion will increase, so there is a risk that the formed pattern will be thinner than the target line width, or that the pattern will be more likely to be missing. .

<(D) Light-shielding component containing carbon black as a light-shielding material>
The (D) light shielding component in the photosensitive resin composition for a light shielding film of the present invention essentially contains untreated or oxidized carbon black. Here, "untreated" means that no special surface treatment such as oxidation treatment or resin coating treatment is performed, and "oxidation treatment" means that the surface of carbon black is treated with some oxidizing agent before the dispersing step. Since such untreated or oxidized carbon black has many acidic functional groups on its surface, it reacts with the glycidyl groups of the component (A) during heat curing to obtain a light-shielding film. By doing so, it is important to allow a large amount of the component (A) to exist in the vicinity of the carbon black. Furthermore, when carbon black is used to increase the resistance of the light-shielding film, surface-coated carbon black in which the carbon black surface is coated with a dye, pigment, resin, or the like may be used. However, it is preferable to mix 80% by mass or more of carbon black in the component (D). As the light-shielding component other than carbon black, a light-shielding component selected from a black organic pigment, a mixed color organic pigment, or a light-shielding material can be used, and the light-shielding component preferably has excellent heat resistance, light resistance, solvent resistance, and the like. Examples of black organic pigments include perylene black, aniline black, cyanine black, and lactam black. Examples of mixed-color organic pigments include pseudo-black pigments obtained by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta, and the like. Examples of the light shielding material include chromium oxide, iron oxide, and titanium black. Two or more of these other light-shielding components can be appropriately selected and used.

Further, the light-shielding component is preferably dispersed in the solvent (F) together with the dispersant in advance to form a light-shielding dispersion liquid, and then blended as the photosensitive resin composition for the light-shielding film. Here, since the solvent to be dispersed is part of the component (F) described later, it can be used as long as it is listed as the component (F) above. For example, propylene glycol monomethyl ether acetate, 3-methoxybutyl Acetate and the like are preferably used. The blending ratio of the component (D) forming the light-shielding dispersion liquid is preferably in the range of 40 to 70% by mass based on the total solid content of the photosensitive resin composition for light-shielding films of the present invention. A range of up to 60% by weight is particularly preferred.

As the dispersant, known dispersants such as various polymer dispersants can be used. Examples of the dispersant include known compounds conventionally used for dispersing pigments (compounds commercially available under the names of dispersants, dispersion wetting agents, dispersion accelerators, etc.) can be used without particular limitation. , for example, cationic polymeric dispersants, anionic polymeric dispersants, nonionic polymeric dispersants, pigment derivative dispersants (dispersion aids), and the like. In particular, it has a cationic functional group such as an imidazolyl group, pyrrolyl group, pyridyl group, primary, secondary or tertiary amino group as an adsorption point to the pigment, and has an amine value of 1 to 100 mgKOH/g and a number average molecular weight. A cationic polymeric dispersant having a is in the range of 1,000 to 100,000 is preferred. The content of the dispersant is preferably 1 to 30% by mass relative to (D) the light-shielding component.

<(E) Photoinitiator>
Examples of the (E) photopolymerization initiator in the photosensitive resin composition for a light-shielding film of the present invention include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, Acetophenones such as trichloroacetophenone, p-tert-butylacetophenone, and benzyldimethylketal; benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdimethylaminobenzophenone (Michler's ketone), 4- benzophenones such as phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, and 4,4'-diethylaminobenzophenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-( o-Chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole imidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5 Biimidazole compounds such as '-tetraphenyl-1,2-biimidazole; 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(trichloro methyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6 -bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl) Halomethyl-s-triazine compounds such as -1,3,5-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), 1-( 4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O-acetate, 1- (4-methylsulfanylphenyl)butan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-bicycloheptyl-1-one oxime-O -acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-( 2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl] -tetrahydrofuranylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethan-1-one oxime-O-acetate , 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2 -methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl] - Morophonylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethan-1-one oxime-O -acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethane-1-one oxime-O-bicycloheptanecarboxylate, 1-[9-ethyl-6- (2-methyl benzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-tricyclodecanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl ]-ethane-1-one oxime-O-adamantanecarboxylate, 1-[4-(phenylsulfanyl)phenyl]octane-1,2-dione=2-O-benzoyloxime, 1-[9-ethyl-6- (2-methylbenzoyl)carbazol-3-yl]ethanone-O-acetyloxime, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyloxime, ethanone, 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]-1-(o-acetyloxime), ethanone, 1-(-9,9-dibutyl-7- Nitro-9H-fluoren-2-yl)-1-O-acetyloxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O -Acyloxime) and other O-acyloxime compounds; sulfur compounds such as 2,4-dichlorothioxanthone and 1-chloro-4-propoxythioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone and 2,3-diphenylanthraquinone; azobisisobutyl Organic peroxides such as nitrile, benzoyl peroxide, and cumene peroxide; 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, β-mercaptopropionic acid, 2-ethylhexyl-3-mercaptopropionate , n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), tris-[(3- mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate) captopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), 3,3'-thiodipropionic acid, dithiodipropionic acid, laurylthio thiol compounds such as propionic acid; Among these, O-acyloxime compounds are preferably used from the viewpoint of easily obtaining a highly sensitive photosensitive resin composition for a light shielding film. Two or more kinds of these photopolymerization initiators can also be used. In addition, the photoinitiator as used in the field of this invention is used in the meaning containing a sensitizer.

In addition, a compound that does not act as a photopolymerization initiator or sensitizer by itself but can be used in combination with the above-mentioned compounds to increase the ability of the photopolymerization initiator or sensitizer can be added. good. Examples of such compounds include amine-based compounds that are effective when used in combination with benzophenone. Examples of the above amine compounds include triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2- dimethylaminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylp-toluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'- bis(ethylmethylamino)benzophenone and the like.

The amount of component (E) to be blended is preferably 2 to 40 parts by mass, more preferably 3 to 30 parts by mass, per 100 parts by mass of components (B) and (C) combined.

<(F) Solvent>
Examples of the (F) solvent in the photosensitive resin composition for a light-shielding film of the present invention include methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, alcohols such as 3-hydroxy-2-butanone and diacetone alcohol; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone and N-methyl-2-pyrrolidone; toluene, xylene, Aromatic hydrocarbons such as tetramethylbenzene; methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether , dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, glycol ethers such as triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. and the like, and by dissolving and mixing them, a uniform solution composition can be obtained.

<Other ingredients>
Further, the photosensitive resin composition for a light-shielding film of the present invention may optionally contain a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a coupling agent, and a surfactant. , and viscosity modifiers. Thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butyl catechol, phenothiazine, hindered phenol compounds, and the like. Plasticizers include dibutyl phthalate, dioctyl phthalate, phosphorus Examples of fillers include glass fiber, silica, mica, and alumina. Examples of antifoaming agents and leveling agents include silicone-, fluorine-, and acrylic-based compounds. be able to. Examples of surfactants include anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether sulfate; cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride; Amphoteric surfactants such as methylhydroxyethylimidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate, and silicone surfactants with polydimethylsiloxane as the main skeleton. agents, fluorine-based surfactants, and the like. Examples of coupling agents include silane coupling agents such as 3-(glycidyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.

<Solid content>
The photosensitive resin composition for a light-shielding film of the present invention contains the above components (A) to (F) as main components. In the solid content excluding the solvent (the solid content includes monomers that become solid content after curing), the total amount of components (A) to (E) is preferably 70% by mass, more preferably 80% by mass or more, and further Preferably, it is contained in an amount of 90% by mass or more. The amount of the solvent (F) varies depending on the target viscosity, but it is preferable that the solvent is contained in the range of 60 to 90% by weight in the photosensitive resin composition for light-shielding films of the present invention.

<Method for Forming Light-Shielding Film>
The photosensitive resin composition for a light-shielding film in the present invention is excellent as, for example, a photosensitive resin composition for forming a color filter light-shielding film, and the method for forming the light-shielding film includes the following photolithography methods. First, a photosensitive resin composition is applied onto a transparent substrate, then the solvent is dried (pre-baking), a photomask is placed on the film thus obtained, and ultraviolet rays are irradiated to expose the exposed area. A method of curing, further performing development using an alkaline aqueous solution to elute the unexposed portions to form a pattern, and further performing post-baking (thermal baking) as post-drying can be used.

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

The exposure performed after prebaking is performed by an ultraviolet exposure device, and by exposing through a photomask, only the portions of the resist corresponding to the pattern are exposed. The exposure apparatus and its exposure irradiation conditions are appropriately selected, and 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 deep ultraviolet lamp to photocure the photosensitive resin composition in the coating film.

Alkaline development after exposure is performed for the purpose of removing the resist from the unexposed portions, and a desired pattern is formed by this development. Examples of the developer suitable for this alkaline development include aqueous solutions of carbonates of alkali metals and alkaline earth metals, and aqueous solutions of hydroxides of alkali metals, particularly sodium carbonate, potassium carbonate and lithium carbonate. It is preferable to develop at a temperature of 23 to 28° C. using a weakly alkaline aqueous solution containing 0.05 to 3% by mass of carbonate such as, and fine images are formed using a commercially available developing machine, an ultrasonic cleaner, or the like. It can be formed precisely.

After 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 improving the adhesion between the patterned light shielding film and the substrate. This is done by heating with an oven, hot plate or the like, similar to pre-baking. The patterned light-shielding film of the present invention is formed through each step of the photolithographic method described above.

As described above, the photosensitive resin composition for light-shielding films of the present invention is suitable for forming fine patterns by operations such as exposure and alkali development. In addition, the photosensitive resin composition for a light-shielding film 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 imaging devices. 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.

The highly light-shielding and high-resistance light-shielding film obtained by the present invention can secure a volume resistivity of 1×10 ⁸ Ω·cm or more at an applied voltage of 10 V at an OD of 3.9/μm or more. Furthermore, the photosensitive resin composition of the present invention is suitable for forming a light-shielding film pattern that exhibits excellent development adhesion even when fine lines of 3 to 8 μm are formed.

Hereinafter, embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to these.

First, a synthesis example of a polymerizable unsaturated group-containing alkali-soluble resin corresponding to the component (B) of the present invention will be described. Evaluation of resins in Synthesis Examples was performed as follows.

[Solid content concentration]
A glass filter [mass: W ₀ (g)] was impregnated with 1 g of the resin solution obtained in the synthesis example, weighed [W ₁ (g)], and heated at 160 ° C. for ₂ hours. g)] from the following formula.
Solid content concentration (mass%) = 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 [manufactured by Hiranuma Seisakusho Co., Ltd., trade name COM-1600].

[Molecular weight]
Gel permeation chromatography (GPC) [manufactured by Tosoh Corporation, trade name HLC-8220GPC, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuper- Measured with H5000 (1 piece) [manufactured by Tosoh Corporation], temperature: 40 ° C., speed: 0.6 ml / min], and converted to standard polystyrene [PS-oligomer kit manufactured by Tosoh Corporation] weight average molecular weight ( Mw).

[Epoxy equivalent]
After dissolving the epoxy compound to be measured in dioxane, an acetic acid solution of tetraethylammonium bromide is added, and a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) is used with a 1/10N-perchloric acid solution. It was determined by titration.

Abbreviations used in Synthesis Examples are as follows.
AA: acrylic acid
BPFE: A reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane. A compound of general formula (I) wherein A is a fluorene-9,9-diyl group and R ₁ to R ₄ are hydrogen atoms.
BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride
THPA: 1,2,3,6-tetrahydrophthalic anhydride
TPP: Triphenylphosphine
PGMEA: Propylene glycol monomethyl ether acetate
TEAB: Tetraethylammonium bromide

[Synthesis Example 1]
114.4 g (0.23 mol) of BPFE, 33.2 g (0.46 mol) of AA, 157 g of PGMEA and 0.48 g of TEAB were placed in a 500 ml four-necked flask equipped with a reflux condenser and heated at 100-105°C. The mixture was stirred for 20 hours to react. Then, 35.3 g (0.12 mol) of BPDA and 18.3 g (0.12 mol) of THPA were charged into the flask and stirred under heating at 120 to 125 ° C. for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin. A solution was obtained. The resulting resin solution had a solid content concentration of 56.5% by mass, an acid value (in terms of solid content) of 103 mgKOH/g, and an Mw of 3,600 by GPC analysis.

[Preparation of photosensitive resin composition for light shielding film]
Compositions shown in Tables 1 to 4 were blended to prepare photosensitive resin compositions of Examples 1 to 34, Comparative Examples 1 to 9, and Reference Comparative Examples 1 to 5. Each component used for blending is as follows, and all numerical values in the table are parts by mass.

(A) epoxy compound:
(A)-1: Bisphenol fluorene type epoxy compound [ESF-300C manufactured by Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent 240, number of aromatic rings with respect to number of glycidyl groups: 2.09]
(A)-2: 1,6-naphthalenediol aralkyl type epoxy compound [compound represented by the above formula (2), epoxy equivalent 167, number of aromatic rings to number of glycidyl groups: 1.30]
(A)-3: 1-naphthol aralkyl type epoxy compound [compound represented by the above formula (3), epoxy equivalent 317, number of aromatic rings to number of glycidyl groups: 3.13]
(A)-4: Phenol novolak-type epoxy compound [YDPN-6300 manufactured by Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent 175, number of aromatic rings per number of glycidyl groups: 1]
(A)-5: Alicyclic epoxy compound [ZX-1658GS manufactured by Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent 132, number of aromatic rings to number of glycidyl groups: 0]

(B) Polymerizable unsaturated group-containing alkali-soluble resin:
Polymerizable unsaturated group-containing alkali-soluble resin solution obtained in Synthesis Example 1

(C) Photopolymerizable monomer:
A mixture of dipentaerythritol pentaacrylate and hexaacrylate [DPHA manufactured by Nippon Kayaku Co., Ltd., acrylic equivalent 96 to 115]

(D) Pigment dispersion containing a light-shielding component:
(D)-1: Pigment dispersion in propylene glycol monomethyl ether acetate solvent containing 25.0% by mass of carbon black, 5.0% by mass of dispersion resin, and 3.5% by mass of polymeric dispersant (D)-2: Carbon black Pigment dispersion in propylene glycol monomethyl ether acetate solvent containing 25.0% by mass and 6.3% by mass of polymer dispersant (D)-3: 16.0% by mass of organic black pigment and 4.8% by mass of polymer dispersant Pigment Dispersion in Propylene Glycol Monomethyl Ether Acetate Solvent (D)-4: Pigment Dispersion in Propylene Glycol Monomethyl Ether Acetate Solvent Containing 15.0% by Mass of Titanium Black and 4.0% by Mass of Polymer Dispersant (D)-5 : 25.0% by mass of dye-coated carbon black, 8.1% by mass of dispersing resin (alkali-soluble resin (using component (B) above)), 2.0% of polymer dispersing agent, propylene glycol monomethyl ether acetate solvent pigment dispersion

(E) Photoinitiator:
Oxime ester photopolymerization initiator [NCI-831 manufactured by ADEKA Corporation]

(F) Solvent:
(F)-1: Propylene glycol monomethyl ether acetate (F)-2: Diethylene glycol dimethyl ether (F)-3: Diethylene glycol ethyl methyl ether (F)-4: Diethylene glycol dibutyl ether

(G) Silane coupling agent: Shin-Etsu Chemical Co., Ltd. KBM-803

(H) Surfactant: BYK-330 manufactured by BYK-Chemie Japan Co., Ltd.

[evaluation]
Using the photosensitive resin compositions of Examples 1 to 34, Comparative Examples 1 to 9, and Reference Comparative Examples 1 to 5, the following evaluations were performed. These evaluation results are shown in Tables 5-8.

<Evaluation of OD/μm>
Each photosensitive resin composition obtained above was coated on a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.0 µm, and Pre-baked for 1 minute. Thereafter, without covering with a negative type photomask, the film was irradiated with ultraviolet rays of 40 mJ/cm ² from an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW/cm ² to carry out a photocuring reaction.

Next, the exposed coated plate was developed at 23° C. with a 0.04% potassium hydroxide aqueous solution at a shower pressure of 1 kgf/cm ² for 80 seconds, then washed with a spray of 5 kgf/cm ² pressure, followed by hot air. Heat post-baking was performed at 230° C. for 30 minutes using a dryer. The OD value of this coated plate was evaluated using a transmission densitometer. Also, the film thickness of the light shielding film formed on the coated plate was measured, and the value obtained by dividing the OD value by the film thickness was defined as OD/μm.

<Evaluation of residual film rate after thermosetting>
Each of the photosensitive resin compositions obtained above was coated on a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 3.0 µm, and the coating was carried out at 90°C. After pre-baking for 1 minute, the film thickness of the light-shielding film formed on the coated plate was measured. Then, after thermal post-baking at 230° C. for 180 minutes using a hot air dryer, the film thickness of the light-shielding film formed on the coated plate was measured again, and the film thickness before and after post-baking was calculated based on the following formula.
Remaining film thickness (%) = 100 × film thickness after post-baking (μm)/film thickness before post-baking (μm)

<Evaluation of increase in volume resistivity>
Each of the photosensitive resin compositions obtained above was coated on a 100 mm × 100 mm chrome-deposited glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 3.0 µm. °C for 1 minute. Then, after heat post-baking at 230 ° C. for 180 minutes using a hot air dryer, using an electrometer (manufactured by Keithley Co., Ltd., "6517A model"), under the condition that the voltage is held for 60 seconds at each applied voltage in 1 V steps, The volume resistivity was measured at an applied voltage of 1V to 10V. With respect to the volume resistivity when 10 V is applied, the degree of increase in Examples 1 to 11 and Comparative Examples 1 to 3 when the reference Comparative Example 1 that does not use the (A) component is used as the reference, and the (A) component is used. The degree of increase in Examples 12 to 24 when based on the reference comparative example 2 without the component (A), the degree of increase in the comparative examples 4 to 6 when based on the reference comparative example 3 without the component (A), (A ) The degree of increase in Comparative Examples 7 to 9 when the reference comparative example 4 that does not use the component (A) is used as the reference, and the degree of increase in Examples 25 to 33 when the reference comparative example 5 that does not use the (A) component is used as the reference were calculated based on the following formulas. In addition, what was used as a reference is written as "Ref." in the following tables.
Degree of increase = each volume resistivity (Ω cm) of the example or comparative example/each volume resistivity (Ω cm) of the reference comparative example
Based on the calculated increase in volume resistance, the increase in volume resistance was determined based on the following criteria.
○: 100 ≤ volume resistivity increase △: 10 ≤ volume resistance increase < 100
×: Increase in volume resistance <10

<Evaluation of development characteristics (minimum resolution line width)>
Each of the photosensitive resin compositions obtained above was coated on a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.2 µm, and the coating was carried out at 90°C. Pre-baked for 1 minute. After that, a negative photomask having a line pattern with an opening width of 1 to 20 μm is adhered to the dry coating film, and an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW/cm ² is used to irradiate ultraviolet rays of 40 mJ/cm ² , A photo-curing reaction of the photosensitive area was performed.

Next, the exposed coated plate was developed in a 0.04% potassium hydroxide aqueous solution at 23° C. under a shower development pressure of 1 kgf/cm ² for +60 seconds from the development time (break time=BT) at which the pattern begins to appear. After that, it was washed with water by spraying at 5 kgf/cm ² pressure to remove the unexposed part of the coating film to form a line pattern on the glass substrate, and then thermally post-baked at 230° C. for 30 minutes using a hot air dryer. In the line pattern obtained later, the minimum opening line in which pattern separation did not occur was defined as the minimum resolution line width.
◎: 2 μm or more and less than 5 μm ○: 5 μm or more and less than 9 μm △: 9 μm or more and less than 11 μm ×: 11 μm or more

<Evaluation of Volume Resistivity Reduction Rate (Heat Resistance)>
Each of the photosensitive resin compositions obtained in Examples 15 to 17 and 34 and Reference Comparative Example 2 was post-baked onto a 100 mm × 100 mm chromium-deposited glass substrate (Corning 1737) using a spin coater. It was applied to a thickness of 3.0 μm and prebaked at 90° C. for 1 minute. Then, after heat post-baking at 230 ° C. for 180 minutes using a hot air dryer, using an electrometer (manufactured by Keithley Co., Ltd., "6517A model"), under the condition that the voltage is held for 60 seconds at each applied voltage in 1 V steps, The volume resistivity was measured at an applied voltage of 1V to 10V. Separately from these, the temperature of the thermal post-baking was changed to 270° C., and the same procedure was carried out for each of the photosensitive resin compositions of Examples 15 to 17 and 34 and Reference Comparative Example 2. Then, the volume resistivity was measured.
Regarding the volume resistivity when 10 V was applied, the decrease rate (absolute value) of the volume resistivity when the thermal post-baking temperature was changed from 230° C. to 270° C. was calculated based on the following formula. Further, when the reduction rate in the case of Reference Comparative Example 2 is regarded as 1, each relative value [relative value of reduction rate (x)] of Examples 15 to 17 and 34 with respect to Reference Comparative Example 2 is calculated as follows. Calculated based on the formula. Reference Comparative Example 2 is indicated as "Ref." in the subsequent tables.
Decrease rate (absolute value) = 100 x (logA-logB)/logB
(where A is the measured volume resistivity (Ω cm) when the thermal post-bake is 270° C., and B is the measured volume resistivity (Ω cm) when the thermal post-bake is 230° C. ) is)
Relative value of decrease rate (x)=each decrease rate of Example 15, 16, 17 or 34/decrease rate of reference comparative example 2 Regarding the calculated relative value of the decrease rate, this is taken as heat resistance, and the following criteria are used. determined based on
◎: 0 ≤ x < 0.5
○: 0.5 ≤ x < 0.8
△: 0.8≦x<1.0
x: 1.0≤x

From the results of Examples 1 to 34, Comparative Examples 1 to 9, and Reference Comparative Examples 1 to 5, an epoxy compound as component (A) was added to a photosensitive resin composition containing a light shielding component using carbon black as a light shielding material. It is clear that the volume resistivity is improved by doing so. Among them, particularly Examples 15 to 17, Examples 21 to 24, and Examples 28 to 30 had a very high increase in volume resistivity, and the minimum resolution line width was thin, so the development adhesion was also excellent. It is a photosensitive resin composition for a light-shielding film that achieves both high light-shielding/high resistance and high definition. In addition, it was found that Examples 15 to 17 using the epoxy compounds (A)-1 to (A)-3 of the component (A) were excellent in the heat resistance. )-1 and (A)-2 were found to be more excellent in heat resistance.

Claims (5)

Components (A) to (F) below,
(A) an epoxy compound,
(B) a polymerizable unsaturated group-containing alkali-soluble resin,
(C) a photopolymerizable monomer having at least one ethylenically unsaturated bond;
(D) a light-shielding component containing carbon black as a light-shielding material;
(E) a photopolymerization initiator, and (F) a photosensitive resin composition for a light-shielding film containing a solvent as essential components,
The component (A) has an aromatic ring in its main chain, the number of aromatic rings relative to the number of glycidyl groups in the component (A) is 0.5 to 10, and the epoxy equivalent is 100 to 400 g/eq. A photosensitive resin composition for a light shielding film characterized by: The mass ratio (B)/(C) of the component (B) and the component (C) is 50/50 to 90/10, and the component (A) is 0.5 to 0.5 parts per 100 parts by mass of the component (D). The photosensitive resin for a light-shielding film according to claim 1, containing 15 parts by mass, and containing 40 to 70% by mass of the component (D) in the solid content of the photosensitive resin composition for a light-shielding film. Composition. A light-shielding film formed by curing the photosensitive resin composition for a light-shielding film according to claim 1 or 2. A color filter comprising the light shielding film according to claim 3 . A display device comprising the color filter according to claim 4 .