TW202303283A - Photosensitive resin composition for light shielding film, and light shielding film, colorfilter and display device with the same - Google Patents

Abstract

The invention provides a photosensitive resin composition for a light-shielding film, and a light-shielding film, a color filter and a display device using the same. The photosensitive resin composition for the light-shielding film can obtain a light-shielding film which can achieve both high light shielding and high resistance and is excellent in developing adhesion under the condition that a thin wire is formed. The invention also provides a light-shielding film, a color filter and a display device using the light-shielding film. A photosensitive resin composition for a light-shielding film, comprising (A) an epoxy compound, (B) an alkali-soluble resin containing a polymerizable unsaturated group, (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 solvent as essential components, the photosensitive resin composition for a light-shielding film is characterized in that the component (A) has an aromatic ring in the main chain, the number of aromatic rings relative to the number of glycidyl groups in the component (A) is 0.5-10, and the epoxy equivalent is 100-400 g/eq.

Description

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

The present invention relates to a photosensitive resin composition for a light-shielding film suitable for forming a black matrix with a high light-shielding and high-resistance thin line pattern.

Color filters are one of the important components that affect the visibility of liquid crystal display devices. In order to improve visibility, that is, to obtain clear images, it is necessary to adjust the red (R), green (G), and blue ( B) The color purity of the pixels is higher than before, and high light-shielding is achieved in the black matrix. For this reason, it is necessary to add a larger amount of colorant to the photosensitive resin composition than before.

Carbon black is generally known as a light-shielding material for resin black matrices, but carbon black is excellent in light-shielding properties and low in electrical resistance, so it may cause malfunction of a display device. Therefore, as a method of using carbon black to increase the resistance of the black matrix, it has been proposed to reduce the ratio of conductive carbon black or to apply a material that has been coated with a resin on the surface of carbon black in advance. The shading that can be achieved on the basis of chemical properties is limited, and it is difficult to achieve the required high shading.

In addition, accepting the prior art as described above, the applicant of the present application proposed a method of formulating an alkali-soluble resin containing a polymerizable unsaturated group having a specific structure and acid value as a method of maintaining the optical density OD and volume resistivity and A photosensitive resin composition for a light-shielding film that is excellent in development adhesion even when thin lines such as 10 μm or less are formed, and can sufficiently secure adhesion to a glass substrate (see Patent Document 1). However, in this method, the characteristics required for the black matrix are becoming higher and higher as the performance of the display device is increased, so there is room for further improvement in the coexistence of high light-shielding and high resistance. [Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-200881 [Patent Document 2] Japanese Patent Laid-Open No. 2014-145821 [Patent Document 3] Japanese Patent Laid-Open No. 2019-070720

[Problem to be Solved by the Invention]

Therefore, the inventors of the present application received the above-mentioned conventional attempts and further studied a photosensitive resin composition for a light-shielding film that can achieve both high light-shielding and high resistance, and obtained the following idea. That is, it was obtained that although a large amount of carbon black as a light-shielding material is blended in order to achieve high light-shielding, it is possible to achieve high resistance without reducing the amount. It is meaningful to realize the idea of avoiding contact between carbon blacks by suppressing thermal shrinkage during heat curing of the light-shielding film, and it is also found that untreated or oxidized normal carbon black has a large number of acidic functional groups on its surface. The idea is to make such other resins or the like exist near the surface of the carbon black by preparing other compounds or the like having functional groups that can preferentially react with the light-shielding film during the thermal curing process.

Furthermore, with regard to this idea, efforts have been made to study compounds having high heat resistance capable of suppressing heat shrinkage during thermosetting and having a functional group that preferentially reacts with acidic functional groups of carbon black during thermosetting, and as a result, it was newly found that: By blending a predetermined amount of a predetermined epoxy compound into the photosensitive resin composition, a combination of high light-shielding and high resistance can be achieved, and it can be developed and adhered when thin lines such as 3 μm to 8 μm are formed. The above-mentioned predetermined epoxy compound has an aromatic ring in the main chain and has a rigid skeleton, and has a glycidyl group that can react with an acidic functional group of carbon black during thermal curing.

In addition, the applicants of the present application have also proposed a technique for blending an epoxy compound into a photosensitive resin composition (see Patent Document 2 and Patent Document 3), and the technique described in Patent Document 2 relates to a touch panel application In particular, the black photosensitive resin composition is disclosed to contain a relatively large amount of epoxy compound in order to meet the requirement of high chemical resistance to chemicals used in the processing process. In addition, Patent Document 3 is characterized in that in order to form a resin film pattern on a plastic substrate with a high heat resistance of 140°C, it is necessary to mix a curing agent and/or a curing accelerator in the photosensitive resin composition, and combine them with The total amount of the epoxy compound is set within a specific range, but it is only disclosed that it is an essential component especially for the purpose of low-temperature curing. That is, in the compositions described in Patent Document 2 and Patent Document 3, the above-mentioned formulation must be performed, and it is difficult to satisfy all of high light shielding, high resistance, and thinning.

Therefore, the present invention was invented based on the above findings, and an object of the present invention is to provide a photosensitive resin composition for a light-shielding film that can form a high light-shielding film and a high resistance at the same time, and can be developed densely when thin lines are formed. A hardened product (shading film) that is also excellent in compatibility.

In addition, another object of the present application is to provide a light-shielding film, which is formed by curing the photosensitive resin composition for the light-shielding film, and further, to provide a color filter including the light-shielding film and a color filter including the color filter. Filter display device.

[Means to solve the problem] That is, the gist of the present invention is as follows. [1] A photosensitive resin composition for a light-shielding film, comprising the following components (A) to (F) as essential components, (A) epoxy compound, (B) Alkali-soluble resins containing polymerizable unsaturated groups, (C) a photopolymerizable monomer having at least one ethylenically unsaturated bond, (D) Light-shielding components containing carbon black as a light-shielding material, (E) photopolymerization initiator, and (F) a solvent, and the photosensitive resin composition for a light-shielding film is characterized by: The component (A) has an aromatic ring in the main chain, and 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 g/eq ~400 g/eq. [2] The photosensitive resin composition for a light-shielding film according to [1], wherein the mass ratio (B)/(C) of the component (B) to the component (C) is 50/50 to 90/10 , containing 0.5 to 15 parts by mass of component (A) with respect to 100 parts by mass of component (D), and containing 40 to 70% by mass of (D) in the solid content of the photosensitive resin composition for light-shielding films )Element. [3] A light-shielding film formed by curing the photosensitive resin composition for light-shielding film according to [1] or [2]. [4] A color filter comprising the light-shielding film according to [3]. [5] A display device comprising the color filter according to [4].

[Effect of the invention] According to the present invention, it is possible to provide a photosensitive resin composition for a light-shielding film, which can achieve both high light-shielding and high resistance, and also has good adhesion to development even when thin lines of, for example, 3 μm to 8 μm are formed. Excellent cured product (shading film).

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

＜(A) Epoxy compound＞ (A) The epoxy compound in the photosensitive resin composition for light-shielding films of this invention needs to have an aromatic ring in a main chain. By having an aromatic ring in the main chain, it has excellent heat resistance and mechanical properties, and can suppress thermal shrinkage that occurs when the photosensitive resin composition for light-shielding film of the present invention using it is heat-hardened to form a light-shielding film , which is better in this respect. Here, "having in the main chain" means having at least one aromatic ring in the structure of the skeleton of a molecule having the largest carbon number, as commonly used in this technical field. In addition, the aromatic ring includes a benzene ring, a naphthalene ring, a biphenyl ring, a bisphenol ring, and the like, and these structures may not be substituted, or may each independently have one or more substituents. The substituent may be an alkyl group or aryl group having 1 to 10 carbon atoms, and is not particularly limited as long as it is within the scope of the present invention.

Here, as the (A) component, it is preferable to use an epoxy equivalent of 100 g/eq to 400 g/eq, preferably 120 g/eq to 380 g/eq, more preferably 150 g/eq to 360 g The composition of /eq. When the epoxy equivalent is less than 100 g/eq, it may react with the acidic functional group contained in the (B) component responsible for the solubility of the development, and the developability may be reduced. On the contrary, if it exceeds 400 g/eq In the case of , there is a concern that the control of the distance between carbon blacks is lacking, and an increase in resistance cannot be expected.

In addition, regarding the (A) component, the number of aromatic rings relative to the number of glycidyl groups is 0.5-10, preferably 1.1-4, and more preferably 1.3. ~4, especially preferably 2~4. The number of aromatic rings mentioned here refers to the number of benzene rings, for example, if it is a naphthalene ring, it is 2, if it is a biphenyl ring, it is 2, if it is an anthracycline, it is 3, if it is a bisphenol fluorene ring, it is 4. The aromatic ring is preferably a bulky (large number of aromatic rings) aromatic ring, more preferably an aromatic ring having a condensed ring structure such as a bisphenol fluorene ring or a naphthalene ring. When the number of aromatic rings/number of glycidyl groups is less than 0.5, there are concerns about a decrease in electrical resistance due to a decrease in heat resistance due to a small number of aromatic rings, or a decrease in electrical resistance due to a large number of glycidyl groups due to a large number of glycidyl groups. The acidic functional group responsible for the solubility of the development reacts, thereby reducing the developability. On the contrary, when the number of aromatic rings/the number of glycidyl groups exceeds 10, there is a concern that the control of the distance between carbon blacks is lacking due to the small number of glycidyl groups, and an increase in electrical resistance cannot be expected.

在所述式（1）的情況下，芳香環數/縮水甘油基數=（4m ₁+4）/2，例如，在m ₁=1的情況下為4。此時，環氧當量為435。同樣地，m ₁=2時的芳香環數/縮水甘油基數為6，環氧當量為638。根據所述關係而成為（環氧當量）=102×（芳香環數/縮水甘油基數）+28，因此可根據環氧當量來算出芳香環數/縮水甘油基數。 Here, regarding the number of aromatic rings/glycidyl group, it can be known that, as shown below, it can be based on the ratio relationship between the number of aromatic rings/glycidyl group and the epoxy equivalent in consideration of the repeating unit of the epoxy compound, and according to the ring Calculate the oxygen equivalent. That is, although the number of aromatic rings or the number of glycidyl groups varies depending on the chemical structure or repeating unit of each epoxy compound, as described above, the number of aromatic rings and the number of glycidyl groups can be determined in advance by fitting several repeating units specifically. The relational formula of oxygen equivalent, and calculate the aromatic ring number/glycidyl group number according to the measured value of epoxy equivalent. Here, as a specific example thereof, the compounds listed in the following chemical formula (1) to chemical formula (4) are shown as examples, and epoxy compounds other than these can also be obtained in the same manner. · Bisphenol fluorene type epoxy compound [Chemical 1]

In the case of the formula (1), number of aromatic rings/number of glycidyl groups=(4m ₁ +4)/2, for example, 4 when m ₁ =1. At this time, the epoxy equivalent was 435. Similarly, when m ₁ =2, the number of aromatic rings/glycidyl group is 6, and the epoxy equivalent is 638. From the relationship described above, (epoxy equivalent)=102×(number of aromatic rings/number of glycidyl groups)+28, and thus the number of aromatic rings/number of glycidyl groups can be calculated from the epoxy equivalent.

在所述式（2）的情況下，芳香環數/縮水甘油基數=（3m ₂+2）/（2m ₂+2），例如，在m ₂=1的情況下為1.25。此時，環氧當量為162。同樣地，m ₂=2時的芳香環數/縮水甘油基數為1.33，環氧當量為170。根據所述關係而成為（環氧當量）=102×（芳香環數/縮水甘油基數）+34。 ·1,6-Naphthalene diol aralkyl epoxy compound [Chem. 2]

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

在所述式（3）的情況下，芳香環數/縮水甘油基數=（3m ₃+2）/（m ₃+1），例如，在m ₃=1的情況下為2.5。此時，環氧當量為252。同樣地，m ₃=2時的芳香環數/縮水甘油基數為2.67，環氧當量為269。根據所述關係而成為（環氧當量）=102×（芳香環數/縮水甘油基數）-3。 ·1-Naphthol aralkyl type epoxy compound [Chem. 3]

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

在所述式（4）的情況下，芳香環數/縮水甘油基數=（m ₄+2）/（m ₄+2），與環氧當量無關地成為（芳香環數/縮水甘油基數）=1。 · Phenol novolac type epoxy compound [Chem. 4]

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

It is preferable to use the component whose weight average molecular weight is 300-10000 about the said (A) component.

As such (A) epoxy compound, it will not specifically limit if it is an epoxy compound which has an aromatic ring in a main chain, For example, bisphenol A type epoxy compound, bisphenol F type epoxy compound, Bisphenol fluorene type epoxy compound, bisnaphthol fluorene type epoxy compound, diphenyl fluorene type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, phenol aralkyl type epoxy compound Compounds, phenol novolac compounds containing a naphthalene skeleton (such as NC-7000L manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compounds, trisphenol methane type epoxy compounds, tetraphenol ethane type epoxy compounds, Glycidyl ethers of polyhydric alcohols, glycidyl esters of polycarboxylic acids, and copolymers of methacrylic acid and glycidyl methacrylate, which contain glycidyl (meth)acrylate as units and have a (meth)acrylic group. Copolymers of monomers, epoxy compounds with a silicone skeleton, etc. Among them, it is preferable to use a polycyclic aromatic epoxy compound from the viewpoint of good affinity with carbon black. Moreover, the said (A) component may use only 1 type of compound, and may use multiple types together.

Furthermore, the compounding quantity of the said (A) component is preferably 1 mass part - 25 mass parts with respect to the total 100 mass parts of (B) component and (C) component mentioned later, More preferably, it is 1 mass part -18 parts by mass, more preferably 1.5 -16 parts by mass. Since favorable patterning characteristics can be acquired by setting the said compounding quantity with respect to (B) component and (C)component, it is preferable. Furthermore, it is preferable to mix|blend the said (A) component so that it may be 0.5-15 mass parts with respect to 100 mass parts of (D) components mentioned later, More preferably, it shall be 1-13 mass parts, Furthermore, it is more preferable to set it as 1.0 mass part - 9.0 mass parts. By rationalizing the quantity with respect to carbon black as mentioned above, since good affinity with carbon black can be maintained, and sufficient light-shielding property and coexistence of electric resistance are achieved, it is preferable.

<(B) Alkali-soluble resin containing a polymerizable unsaturated group> In the photosensitive resin composition for a light-shielding film of the present invention (B) the alkali-soluble resin containing a polymerizable unsaturated group has a polymerizable unsaturated group in the molecule. The resin of saturated group and acidic group can be used without special limitation. The first example that can be preferably applied is epoxy (meth)acrylate acid adduct, and described epoxy (meth)acrylate acid The adduct is to react a compound having two or more epoxy groups with (meth)acrylic acid (which refers to acrylic acid and/or methacrylic acid), and to make (a) dicarboxylic acid or tricarboxylic acid or its It is obtained by reacting an acid monoanhydride and/or (b) tetracarboxylic acid or its acid dianhydride with the obtained epoxy (meth)acrylate compound which has a hydroxyl group. A bisphenol-type epoxy compound or a novolak-type epoxy compound can be illustrated as a compound which has two or more epoxy groups derivatized into an epoxy (meth)acrylate acid adduct. Specifically, bisphenol-type epoxy compounds represented by the following general formula (I) are suitably mentioned. [chemical 5]

In the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbons, a halogen atom or a phenyl group, and A represents -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, fluorene-9,9-diyl or direct bond . l is an integer of 0-10. Preferred R ₁ , R ₂ , R ₃ , and R ₄ are hydrogen atoms, and preferred A is fluorene-9,9-diyl. In addition, about 1, a plurality of values are usually mixed, so the average value is 0-10 (not limited to an integer), and the preferable average value of 1 is 0-3.

The bisphenol-type epoxy compound is an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols and epichlorohydrin. During the reaction, the oligomerization of the glycidyl ether compound is usually accompanied, Therefore, epoxy compounds containing two or more bisphenol skeletons are contained. Examples of bisphenols used in the reaction include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxy-3 ,5-Dichlorophenyl) Ketone, Bis(4-Hydroxyphenyl) Phenyl, Bis(4-Hydroxy-3,5-Dimethylphenyl) Phenyl, Bis(4-Hydroxy-3,5-Dichloro Phenyl) Phenyl, Bis(4-Hydroxyphenyl) Hexafluoropropane, Bis(4-Hydroxy-3,5-Dimethylphenyl) Hexafluoropropane, Bis(4-Hydroxy-3,5-Dichlorobenzene base) 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-dibromobenzene base) 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'-bisphenol, 3,3'-bisphenol wait. Among these, bisphenols having a fluorene-9,9-diyl group can be particularly preferably used.

As (a) acid monoanhydride of dicarboxylic acid or tricarboxylic acid to react with epoxy (meth)acrylate, acid monoanhydride of chain hydrocarbon dicarboxylic acid or tricarboxylic acid or alicyclic dicarboxylic acid can be used acid or tricarboxylic acid monoanhydride, aromatic dicarboxylic acid or tricarboxylic acid monoanhydride. Here, 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, citramalic acid, Acid monoanhydrides such as malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, etc., which may further introduce optional substituents Anhydrides of dicarboxylic or tricarboxylic acids. In addition, examples of acid monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids include cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyl Acid monoanhydrides such as tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorbacteric acid, hexahydrotrimellitic acid, norbornane dicarboxylic acid, etc., can further introduce arbitrary substitutions Acid monoanhydrides of dicarboxylic or tricarboxylic acids. Furthermore, examples of acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids include phthalic acid, isophthalic acid, trimellitic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid Acid monoanhydrides, such as acid, may further be an acid monoanhydride of a dicarboxylic acid or a tricarboxylic acid into which an arbitrary substituent is introduced.

In addition, as the (b) acid dianhydride of tetracarboxylic acid reacted with epoxy (meth)acrylate, acid dianhydride of chain hydrocarbon tetracarboxylic acid or acid dianhydride of alicyclic tetracarboxylic acid, Or the acid dianhydride of aromatic tetracarboxylic acid. Here, the acid dianhydrides of chain hydrocarbon tetracarboxylic acids include, for example, acid dianhydrides such as butane tetracarboxylic acid, pentane tetracarboxylic acid, and hexane tetracarboxylic acid. An acid dianhydride of tetracarboxylic acid. In addition, examples of acid dianhydrides of alicyclic tetracarboxylic acids include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, and norbornane tetracarboxylic acid. etc., the acid dianhydride of the tetracarboxylic acid which introduced the arbitrary substituent further may be used. Furthermore, as an acid dianhydride of an aromatic tetracarboxylic acid, for example, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, diphenyl tetracarboxylic acid, acid dianhydrides such as naphthalene-1,4,5,8-tetracarboxylic acid, naphthalene-2,3,6,7-tetracarboxylic acid, etc., furthermore, it may be an acid of tetracarboxylic acid introduced with an arbitrary substituent Dianhydride.

The molar ratio (a)/(b) of (a) the acid anhydride of dicarboxylic acid or tricarboxylic acid and (b) the acid dianhydride of tetracarboxylic acid reacted with epoxy (meth)acrylate is preferably 0.01～ 10.0, more preferably 0.02 or more and less than 3.0. When the molar ratio (a)/(b) is in the above range, it is easy to obtain the optimum molecular weight for making a photosensitive resin composition having good photopatternability, and the alkali solubility is not impaired. Therefore better.

〔式（II）中，R ₁、R ₂、R ₃及R ₄分別獨立地表示氫原子、碳數1～5的烷基、鹵素原子或苯基，A表示-CO-、-SO ₂-、-C(CF ₃) ₂-、-Si(CH ₃) ₂-、-CH ₂-、-C(CH ₃) ₂-、-O-、芴-9,9-二基或直鍵，X表示四價羧酸殘基，Y ₁及Y ₂分別獨立地表示氫原子或-OC-Z-(COOH) _m（其中，Z表示二價或三價羧酸殘基，m表示1～2的數），n表示1～20的整數〕 The epoxy (meth)acrylate acid adduct can be produced by a known method, for example, the methods described in JP-A-8-278629 or JP-A-2008-9401. First, as a method of reacting (meth)acrylic acid with an epoxy compound, for example, there is a method in which (meth)acrylic acid, which is molar to the epoxy group of the epoxy compound, is added to a solvent, and the catalyst (three In the presence of ethylbenzyl ammonium chloride, 2,6-diisobutylphenol, etc.), heating and stirring at 90° C. to 120° C. were performed while air was blown in, and the reaction was carried out. Next, as a method of reacting an acid anhydride with a hydroxyl group of an epoxy acrylate compound as a reaction product, there is a method in which a predetermined amount of an epoxy acrylate compound, an acid dianhydride, and an acid monoanhydride are added to a solvent, and the catalyst In the presence of (tetraethylammonium bromide, triphenylphosphine, etc.), it reacts by heating and stirring at 90°C to 130°C. The epoxy acrylate acid adduct obtained by the method has a skeleton of the general formula (II). [chemical 6]

[In formula (II), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbons, a halogen atom or a phenyl group, and A represents -CO-, -SO ₂ - , -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, fluorene-9,9-diyl or direct bond, X Represents a tetravalent carboxylic acid residue, Y ₁ and Y ₂ independently represent a hydrogen atom or -OC-Z-(COOH) _m (wherein, Z represents a divalent or trivalent carboxylic acid residue, m represents 1 to 2 number), n represents an integer from 1 to 20]

As another example of (B) component, the resin which has a (meth)acrylic group and a carboxyl group in copolymers, such as (meth)acrylic acid and (meth)acrylate, is mentioned. For example, it is an alkali-soluble resin containing a polymerizable unsaturated group obtained by copolymerizing (meth)acrylic acid esters containing glycidyl (meth)acrylate in a solvent as a first step to obtain a copolymerized As a second step, (meth)acrylic acid is reacted with the obtained copolymer, and in a third step, an anhydride of a dicarboxylic acid or a tricarboxylic acid is reacted.

As yet another example of the component (B), 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, A urethane compound obtained by reacting the diisocyanate compound of the third component. As the resin of the above-mentioned system, the resin disclosed in Japanese Patent Laid-Open No. 2017-76071 can be referred to.

The polymerizable unsaturated group-containing alkali-soluble resin of the component (B) is preferably blended in an amount of 10% by mass to 40% by mass, more preferably 20% by mass, in the solid content of the photosensitive resin composition for a light-shielding film of the present invention. ~40% by mass is suitable. In addition, the weight average molecular weight (Mw) is usually 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 during development cannot be maintained, and pattern peeling will occur. In addition, if the weight average molecular weight (Mw) exceeds 10,000, development residues or residual films on unexposed parts will easily remain. . Furthermore, the component (B) preferably has an acid value in the range of 30 KOHmg/g to 200 KOHmg/g. The reason is that if the value is less than 30 KOHmg/g, alkali development may not be carried out smoothly or special development conditions such as strong alkali are required. In addition, if it exceeds 200 KOHmg/g, the penetration of the alkali developing solution may be reduced. Too fast, easy to produce peeling development. Moreover, the polymerizable unsaturated group containing alkali-soluble resin of (B) component may use only 1 type, and may use the mixture of 2 or more types.

<(C) Photopolymerizable monomer having at least one ethylenically unsaturated bond> Examples of the (C) 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, (meth) ) 2-hydroxypropyl acrylate, 2-hydroxyhexyl (meth)acrylate and other (meth)acrylates with hydroxyl groups, or ethylene glycol di(meth)acrylate, diethylene glycol di(methyl) ) acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate ester, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate Acrylates, glycerol (meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta( Meth)acrylate, or dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide modified hexa(meth)acrylate of phosphazene, caprolactone (Meth)acrylates such as modified dipentaerythritol hexa(meth)acrylate, dendrimers having (meth)acryl groups, etc., one or more of these can be used. As a dendrimer having a (meth)acryl group, for example, a multifunctional mercapto group added to a part of the carbon-carbon double bond in the (meth)acryl group of a polyfunctional (meth)acrylate compound can be exemplified Known dendrimers obtained from thiol groups in compounds.

The component (C) functions to cross-link the molecules of the alkali-soluble resin. In order to exhibit this function, it is preferable to use a component having two or more ethylenically unsaturated bonds. Moreover, the acrylic acid equivalent obtained by dividing the molecular weight of a monomer by the number of (meth)acryloyl groups in one molecule should just be 50-300.

Regarding the blending amount of the (C) component, as the blending ratio with the above-mentioned (B) component, the mass ratio (B)/(C) is 50/50 to 90/10, preferably 60/40 to 80/ 20. If the compounding ratio of (B) component is less than 50/50, there is a concern that the cured product after photocuring becomes brittle, and the acid value of the coating film in the unexposed part is low, so the solubility to the alkali developing solution may be feared. Lowered, pattern edges are jagged and not sharp. In addition, if the compounding ratio of the (B) component is more than 90/10, the proportion of the photoreactive functional group in the resin is small, the formation of the crosslinked structure is insufficient, and the acid value of the resin component is too high On the other hand, there is a possibility that the solubility of the exposed portion to an alkali developer may become high, and therefore there may be a problem that the formed pattern becomes thinner than the target line width, or the pattern may be easily peeled off.

<(D) Light-shielding component containing carbon black as a light-shielding material> The (D) light-shielding component in the photosensitive resin composition for light-shielding films of this invention must contain unprocessed or oxidation-processed 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 an oxidizing agent before the dispersion step. Such untreated or oxidized carbon black has a large number of acidic functional groups on the surface, so it is important to react with the glycidyl group of the (A) component during heat curing to obtain a light-shielding film. A large amount of (A) component exists near carbon black. Furthermore, when carbon black is used and the resistance value of a light-shielding film is desired to be further increased, surface-coated carbon black which coat|covers the surface of carbon black with a dye, a pigment, resin, etc. can be used. Among them, it is preferable to mix 80% by mass or more of carbon black in the component (D). As light-shielding components other than carbon black, those selected from black organic pigments, mixed-color organic pigments, and light-shielding materials can be used, and components excellent in heat resistance, light resistance, and solvent resistance are preferred. Here, as a black organic pigment, perylene black, aniline black, cyanine black, lactam black etc. are mentioned, for example. Examples of the mixed-color organic pigment include organic pigments obtained by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta, and the like and turning them into black. Examples of the light-shielding material include chromium oxide, iron oxide, titanium black, and the like. Two or more of these other light-shielding components can also be selected suitably and used.

In addition, the light-shielding component is preferably formulated as a light-shielding film photosensitive resin composition after being previously dispersed in the (F) solvent together with a dispersant to prepare a light-shielding dispersion liquid. Here, the dispersed solvent is part of the (F) component described later, so any solvent listed in the (F) component can be used, for example, propylene glycol monomethyl ether acetate, acetic acid 3- Methoxybutyl Etc. Regarding the compounding ratio of the (D) component which forms the light-shielding dispersion liquid, it is preferable to use it in the range of 40 mass % - 70 mass % with respect to the total solid content of the photosensitive resin composition for light-shielding films of this invention, and it is especially preferable. It is the range of 40 mass % - 60 mass %.

In addition, known dispersants such as various polymer dispersants can be used as the dispersant. As an example of a dispersant, known compounds previously used for pigment dispersion (compounds commercially available under the name of dispersant, dispersion wetting agent, dispersion accelerator, etc., etc.) can be used without particular limitation. For example, cationic Polymer dispersant, anionic polymer dispersant, nonionic polymer dispersant, pigment derivative type dispersant (dispersion aid), etc. Particularly suitable is a cationic polymer system dispersant, which has cationic functional groups such as imidazolyl, pyrrolyl, pyridyl, primary amine, secondary amine or tertiary amine as adsorption points for pigments, and The amine value is 1 mgKOH/g to 100 mgKOH/g, and the number average molecular weight is in the range of 1,000 to 100,000. It is preferable that the compounding quantity of the said dispersing agent is 1 mass % - 30 mass % with respect to (D) light-shielding component.

＜(E) Photopolymerization initiator＞ 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, and p-dimethylacetophenone. , p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, benzyl dimethyl ketal and other acetophenones; benzophenone, 2- Chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdimethylaminobenzophenone (Michler's ketone), 4-phenylbenzophenone Ketone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4,4'-diethylaminobenzophenone and other benzophenones; benzoyl, benzoin, benzoin methyl ether , benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers; 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methyl Oxyphenyl) biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2, 4,5-triarylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-biimidazole and other biimidazole compounds; 2-Trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyano-styryl)-1,3,4-oxadiazole , 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole and other halomethyldiazole compounds; 2,4,6-tri(trichloromethyl )-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloro Methyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methyl Oxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl) -1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4 ,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis (Trichloromethyl)-1,3,5-triazine and other halomethyl-s-triazine compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyl oxime), 1-(4-phenylmercaptophenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4 -Methylmercaptophenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylmercaptophenyl)butane-1-ketoxime- O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-dicycloheptyl-1-ketoxime-O-ethyl Ester, 1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethane-1-ketoxime-O-benzoate , 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethane-1-ketoxime-O-acetate, 1- [9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofurylmethane-1-ketoxime-O-benzoate, 1-[9- Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofurylmethane-1-ketoxime-O-acetate, 1-[9-ethyl-6 -(2-Methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethane-1-ketoxime-O-benzoate, 1-[9-ethyl-6-( 2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methyl ylbenzoyl)-9H-carbazol-3-yl]-morpholinylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzene Formyl)-9H-carbazol-3-yl]-morpholinylmethane-1-ketoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl )-9H-carbazol-3-yl]-ethane-1-ketoxime-O-dicycloheptanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl) -9H-carbazol-3-yl]-ethane-1-ketoxime-O-tricyclodecane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)- 9H-carbazol-3-yl]-ethane-1-ketoxime-O-adamantanecarboxylate, 1-[4-(phenylmercapto)phenyl]octane-1,2-dione =2-O-benzoyl oxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethanone-O-acetyl oxime, (2 -Methylphenyl)(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyl oxime, ethyl ketone, 1-[7-(2-methylbenzoyl base)-9,9-dipropyl-9H-fluoren-2-yl]-1-(O-acetyl oxime), ethyl ketone, 1-(9,9-dibutyl-7-nitro- 9H-fluoren-2-yl)-1-O-acetyl oxime, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl ]-,1-(O-acetyl oxime) and other O-acyl oxime compounds; thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, Sulfur compounds such as 1-chloro-4-propoxythioxanthone; anthracene such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, etc. Quinones; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and cumene peroxide; 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole , β-mercapto propionate, 2-ethylhexyl-3-mercapto propionate, n-octyl-3-mercapto propionate, methoxybutyl-3-mercapto propionate, stearyl propionate -3-Mercaptoester, trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercapto butyrate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), 3,3'-thiobis Thiol compounds such as propionic acid, dithiodipropionic acid, laurylthiopropionic acid, etc. Among them, it is preferable to use O-acyl oxime compounds from the viewpoint of easily obtaining a highly sensitive photosensitive resin composition for a light-shielding film. In addition, two or more of these photopolymerization initiators may also be used. In addition, the photopolymerization initiator described in this invention is used in the meaning of including a sensitizer.

In addition, it does not function as a photopolymerization initiator or a sensitizer by itself, and a compound capable of increasing the ability of a photopolymerization initiator or a sensitizer may be added by using it in combination with the above-mentioned compounds. Examples of such compounds include amine compounds that are effective when used in combination with benzophenone. Examples of the amine compounds include: triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate Esters, Isoamyl 4-Dimethylaminobenzoate, 2-Dimethylaminoethyl Benzoate, 2-Ethylhexyl 4-Dimethylaminobenzoate, N,N-Dimethylaminobenzoate p-toluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylamino)benzophenone Amino) benzophenone, etc.

The compounding quantity of (E) component is preferably 2-40 mass parts with respect to the total 100 mass parts of said (B) component and (C) component, More preferably, it is 3-30 mass parts .

<(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, and 3-methoxy-1-butyl alcohol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, diacetone alcohol and other alcohols; α-terpineol or β-terpineol and other terpenes; acetone, methyl ethyl ketone, Cyclohexanone, N-methyl-2-pyrrolidone and other ketones; toluene, xylene, tetramethylbenzene and other aromatic hydrocarbons; methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl Base carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, three Glycol ethers such as ethylene glycol monoethyl ether; ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy acetate -3-Methyl-1-butyl ester, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, Esters such as butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; by using these and dissolving and mixing them, a homogeneous solution-like composition can be prepared.

＜Other ingredients＞ In addition, the photosensitive resin composition for light-shielding film of the present invention may be formulated with thermal polymerization inhibitors, antioxidants, plasticizers, fillers, leveling agents, defoamers, coupling agents, surfactants, and viscosity modifiers as needed. and other additives. Examples of thermal polymerization inhibitors and antioxidants include: hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenolic compounds, etc. Plasticizers include: dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc., as fillers, include: glass fiber, silicon dioxide, mica, alumina, etc., as disinfectants Foaming agents or leveling agents include silicone-based, fluorine-based, and acrylic-based compounds. In addition, examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether sulfate, and cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride. Amphoteric surfactants, lauryl dimethylamine oxide, lauryl carboxymethyl hydroxyethyl imidazolium betaine and other amphoteric surfactants, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate Non-ionic surfactants such as polydimethylsiloxane and other silicone-based surfactants, fluorine-based surfactants, etc. Examples of coupling agents include silane coupling agents such as 3-(glycidyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane. mixture.

＜Solid content＞ The photosensitive resin composition for light-shielding films of this invention contains the said (A) component - (F) component as a main component. In the solid content excluding the solvent (the solid content includes monomers that become solid content after hardening), the total of components (A) to (E) is preferably 70% by mass, more preferably 80% by mass or more , More preferably, it is suitable to contain 90 mass % or more. (F) Although the amount of the solvent changes depending on the target viscosity, it is preferably included in the range of 60% by mass to 90% by mass in the photosensitive resin composition for light-shielding films of the present invention.

＜Method of forming light-shielding film＞ The photosensitive resin composition for a light-shielding film of the present invention is excellent, for example, as a photosensitive resin composition for forming a light-shielding film of a color filter. As a method for forming a light-shielding film, there is a photolithography method as described below. The following methods can be mentioned: First, the photosensitive resin composition is coated on a transparent substrate, and then the solvent is dried (pre-baked), and a photomask is placed on the film obtained in the above way, and ultraviolet rays are irradiated to expose The part is hardened, and then the unexposed part is developed by using an aqueous alkali solution to elute the unexposed part to form a pattern, and post-baking (heat sintering) is performed as post-drying.

As a transparent substrate on which a photosensitive resin composition is applied, in addition to a glass substrate, vapor deposition or patterned oxidation on a transparent film (for example, polycarbonate, polyethylene terephthalate, polyethersulfone, etc.) can also be exemplified. Substrates made of transparent electrodes such as indium tin oxide (ITO) or gold. As a method of coating the solution of the photosensitive resin composition on the transparent substrate, in addition to the known solution dipping method and spray method, roll coater, land coater machine (land coater machine), slit coater, etc. can also be used. Either method such as machine or rotary machine method. After coating to a desired thickness by these methods, the solvent is removed (prebaked) to form a film. Prebaking is performed by heating with an oven, a hot plate, or the like. The heating temperature and heating time in the prebaking are appropriately selected according to the solvent to be used, for example, at a temperature of 60° C. to 110° C. for 1 minute to 3 minutes.

Exposure after the prebaking is performed using an ultraviolet exposure device, and exposure is performed through a photomask to sensitize only a portion of the resist corresponding to the pattern. The photosensitive resin composition in the coating film is photohardened by appropriately selecting an exposure device and its exposure irradiation conditions and exposing using a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, or an extreme ultraviolet lamp.

Alkali development after exposure is performed for the purpose of removing the resist in unexposed parts, and a desired pattern is formed by this development. As a developing solution suitable for the above-mentioned alkali development, for example, aqueous solutions of carbonates of alkali metals or alkaline earth metals, aqueous solutions of hydroxides of alkali metals, etc., are particularly preferably used. , Potassium Carbonate, Lithium Carbonate and other weakly alkaline aqueous solutions of carbonates are developed at a temperature of 23°C to 28°C, and fine images can be precisely formed using commercially available developing machines or ultrasonic cleaners.

After image development, heat processing (post-baking) is preferably performed at a temperature of 180° C. to 250° C. and on conditions of 20 minutes to 60 minutes. The post-baking is performed for the purpose of improving the adhesion between the patterned light-shielding film and the substrate. This is performed by heating with an oven, a hot plate, etc. similarly to prebaking. The patterned light-shielding film of the present invention is formed through the above steps of photolithography.

As mentioned above, the photosensitive resin composition for light-shielding films of this invention is suitable for forming a fine pattern 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, especially as an ink for a color filter used in a liquid crystal display device or an imaging element. The film is useful as a color filter, a black matrix for liquid crystal projection, a light-shielding film, a light-shielding film for a touch panel, and the like.

The high light-shielding and high-resistance light-shielding film obtained in the present invention can ensure a volume resistivity of 1×10 ⁸ Ω·cm or more under an applied voltage of 10 V when the OD is 3.9/μm or more. Furthermore, the photosensitive resin composition of the present invention is suitable for forming a light-shielding film pattern having excellent development adhesion even when thin lines of, for example, 3 μm 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 thereto.

First, a synthesis example of a polymerizable unsaturated group-containing alkali-soluble resin corresponding to (B) component of the present invention is shown. The evaluation of the resin in the synthesis example was performed as follows.

[Concentration of solid content] 1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [mass: W ₀ (g)] and weighed [W ₁ (g)], and heated at 160°C for 2 The mass [W ₂ (g)] after hr was obtained by 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 it was determined by titrating with a 1/10 N-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 Co., Ltd., solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2 pieces) + TSKgelSuperH-3000 (1 root) + TSKgelSuperH-4000 (1 piece) + TSKgelSuper-H5000 (1 piece) [Tosoh Co., Ltd.], temperature: 40°C, speed: 0.6 ml/min] as a standard polystyrene The weight average molecular weight (Mw) was calculated from the converted value of [PS-Oligomer Kit manufactured by Tosoh Co., Ltd.].

[epoxy equivalent] After dissolving the epoxy compound to be measured in dioxane, add an acetic acid solution of tetraethylammonium bromide, and use a potentiometric titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to utilize 1/10 N - Calculated by titrating a perchloric acid solution.

In addition, the abbreviations used in the synthesis example are as follows. AA: acrylic acid (acrylic acid) BPFE: a reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane. Among the compounds of the general formula (I), A is a fluorene-9,9-diyl group, and R ₁ to R ₄ are hydrogen atoms. BPDA: 3,3',4,4'-biphenyl tetracarboxylic dianhydride (3,3',4,4'-biphenyl tetracarboxylic dianhydride) THPA: 1,2,3,6-tetrahydrophthalic acid dianhydride Anhydride (1,2,3,6-tetra hydrophthalic anhydride) TPP: triphenylphosphine PGMEA: propylene glycol monomethyl ether acetate TEAB: tetraethylammonium bromide ammonium bromide)

[Synthesis Example 1] Put 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 into a 500 ml four-necked flask with a reflux cooler, and stir while heating at 100°C to 105°C 20 hr for the reaction. Next, 35.3 g (0.12 mol) of BPDA and 18.3 g (0.12 mol) of THPA were put into the flask, and stirred while heating at 120°C to 125°C for 6 hours to obtain an alkali-soluble resin solution containing a polymerizable unsaturated group . The solid content concentration of the obtained resin solution was 56.1 mass %, the acid value (solid content conversion) was 103 mgKOH/g, and the Mw obtained by GPC analysis was 3600.

[Preparation of Photosensitive Resin Composition for Light-shielding Film] Preparation was carried out according to the composition shown in Table 1-Table 4, and the photosensitive resin composition of Example 1-Example 34, Comparative Example 1-Comparative Example 9, and Standard Comparative Example 1-Basic Comparative Example 5 were prepared. Each component used for preparation is as follows, and the numerical values in a table|surface are all 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 to the number of glycidyl groups: 2.09] (A)-2: 1,6-naphthalenediol aralkyl-type epoxy compound [the compound represented by the above-mentioned formula (2), epoxy equivalent 167, number of aromatic rings relative to the number of glycidyl groups: 1.30] (A)-3: 1-naphthol aralkyl type epoxy compound [the compound represented by the above-mentioned formula (3), epoxy equivalent 317, number of aromatic rings relative to the 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 to the 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 relative to the number of glycidyl groups: 0]

(B) Alkali-soluble resins containing polymerizable unsaturated groups: The alkali-soluble resin solution containing the polymerizable unsaturated group obtained in the synthesis example 1

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

(D) Pigment dispersions containing opacifying ingredients: (D)-1: Pigment dispersion in propylene glycol monomethyl ether acetate solvent of 25.0% by mass of carbon black, 5.0% by mass of dispersing resin, and 3.5% by mass of polymer dispersant (D)-2: Pigment dispersion of propylene glycol monomethyl ether acetate solvent with 25.0% by mass of carbon black and 6.3% by mass of polymer dispersant (D)-3: Pigment dispersion of propylene glycol monomethyl ether acetate solvent with 16.0% by mass of organic black pigment and 4.8% by mass of polymer dispersant (D)-4: Pigment dispersion of propylene glycol monomethyl ether acetate solvent with 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 the above-mentioned (B) component)) 8.1% by mass, and 2.0% of polymer dispersant, propylene glycol monomethyl ether acetate solvent pigment Dispersions

(E) Photopolymerization initiator: Oxime ester-based photopolymerization initiator [NCI-831 manufactured by ADEKA Co., Ltd.]

(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: KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd.

(H) Surfactant: BYK-330 manufactured by BYK-Chemie Japan (stock)

[Table 1] Blending ingredients Example Example Example Example Example Example Example Example Example Example Example comparative example comparative example comparative example Benchmark comparison example 1 2 3 4 5 6 7 8 9 10 11 1 2 3 1 (A)-1 0.71 3.50 5.00 (A)-2 0.71 3.50 5.00 (A)-3 0.71 3.50 5.00 (A)-4 0.71 5.00 (A)-5 0.71 3.50 5.00 (B) 31.3 31.3 31.3 31.3 27.9 27.9 27.9 26.0 26.0 26.0 26.0 31.3 27.9 26.0 32.2 (C) 9.36 9.36 9.36 9.36 8.71 8.71 8.71 8.36 8.36 8.36 8.36 9.36 8.71 8.36 9.50 (D)-1 208 208 208 208 208 208 208 208 208 208 208 208 208 208 208 (D)-2 (D)-3 (D)-4 (E) 2.64 2.64 2.64 2.64 2.43 2.43 2.43 2.36 2.36 2.36 2.36 2.64 2.43 2.36 2.64 (F)-1 155 155 155 155 156 156 156 157 157 157 157 155 156 157 155 (F)-2 184 184 184 184 184 184 184 184 184 184 184 184 184 184 184 (F)-3 104 104 104 104 104 104 104 104 104 104 104 104 104 104 104 (F)-4 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 (G) 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 (H) 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04

[Table 2] Blending ingredients Example Example Example Example Example Example Example Example Example Example Example Example Example Benchmark comparison example 12 13 14 15 16 17 18 19 20 twenty one twenty two twenty three twenty four 2 (A)-1 0.64 3.00 4.29 1.50 1.50 1.00 (A)-2 0.64 3.00 4.29 1.50 1.50 1.00 (A)-3 0.64 3.00 4.29 1.50 1.50 1.00 (A)-4 (A)-5 (B) 42.3 42.3 42.3 39.4 39.4 39.4 37.8 37.8 37.8 39.4 39.4 39.4 39.4 43.1 (C) 7.93 7.93 7.93 7.43 7.43 7.43 7.14 7.14 7.14 7.43 7.43 7.43 7.43 8.07 (D)-1 (D)-2 208 208 208 208 208 208 208 208 208 208 208 208 208 208 (D)-3 (D)-4 (E) 2.21 2.21 2.21 2.07 2.07 2.07 2.00 2.00 2.00 2.07 2.07 2.07 2.07 2.29 (F)-1 146 146 146 147 147 147 148 148 148 147 147 147 147 146 (F)-2 184 184 184 184 184 184 184 184 184 184 184 184 184 184 (F)-3 104 104 104 104 104 104 104 104 104 104 104 104 104 104 (F)-4 18 18 18 18 18 18 18 18 18 18 18 18 18 18 (G) 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.18 (H) 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04

[table 3] Blending ingredients comparative example comparative example comparative example Benchmark comparison example comparative example comparative example comparative example Benchmark comparison example 4 5 6 3 7 8 9 4 (A)-1 2.79 2.93 (A)-2 2.79 2.93 (A)-3 2.79 2.93 (A)-4 (A)-5 (B) 36.57 36.57 36.57 39.93 38.50 38.50 38.50 42.14 (C) 6.86 6.86 6.86 7.50 7.29 7.29 7.29 7.93 (D)-1 (D)-2 (D)-3 325 325 325 325 (D)-4 347 347 347 347 (E) 1.93 1.93 1.93 2.14 2.00 2.00 2.00 2.21 (F)-1 34 34 34 32 10 10 10 8 (F)-2 184 184 184 184 184 184 184 184 (F)-3 104 104 104 104 104 104 104 104 (F)-4 18 18 18 18 18 18 18 18 (G) 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 (H) 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04

[Table 4] Blending ingredients Example Example Example Example Example Example Example Example Example Example Benchmark comparison example 25 26 27 28 29 30 31 32 33 34 5 (A)-1 0.79 3.71 5.36 (A)-2 0.79 3.71 5.36 (A)-3 0.79 3.71 5.36 (A)-4 3.00 (A)-5 (B) 23.0 23.0 23.0 19.4 19.4 19.4 17.4 17.4 17.4 39.4 24.0 (C) 10.00 10.00 10.00 9.29 9.29 9.29 8.93 8.93 8.93 7.43 10.14 (D)-1 (D)-2 208 (D)-3 (D)-4 (D)-5 208 208 208 208 208 208 208 208 208 208 (E) 2.79 2.79 2.79 2.57 2.57 2.57 2.50 2.50 2.50 2.07 2.86 (F)-1 162 162 162 164 164 164 165 165 165 147 162 (F)-2 184 184 184 184 184 184 184 184 184 184 184 (F)-3 104 104 104 104 104 104 104 104 104 104 104 (F)-4 18 18 18 18 18 18 18 18 18 18 18 (G) 0.21 0.21 0.21 0.21 0.21 0.21 0.18 0.18 0.18 0.14 0.21 (H) 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04

[evaluate] 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 Table 5-Table 8.

<Evaluation of OD/μm> Each photosensitive resin composition obtained above was coated on a 125 mm×125 mm glass substrate (Corning 1737 ) and pre-bake at 90°C for 1 min. Thereafter, the photocuring reaction was performed by irradiating ultraviolet rays of 40 mJ/cm ² with an ultra-high pressure mercury lamp with i-ray illuminance of 30 mW/cm ² without covering the negative photomask.

Next, for the above-mentioned exposed coated plate, use 0.04% potassium hydroxide aqueous solution at 23°C, after developing for 80 seconds with a spray pressure of 1 kgf/cm ² , carry out spray water washing with a pressure of 5 kgf/cm ² , Thereafter, post-baking was performed at 230° C. for 30 minutes using a hot air dryer. The OD value of the coated plate was evaluated using a permeation densitometer. Moreover, the film thickness of the light-shielding film formed on the coated board was measured, and the value obtained by dividing the OD value by the film thickness was made into OD/micrometer.

＜Evaluation of residual film rate after thermosetting＞ Each photosensitive resin composition obtained above was coated on a 125 mm×125 mm glass substrate (Corning 1737) with a film thickness of 3.0 μm after post-baking using a spin coater, and heated at 90° C. After pre-baking for 1 minute, the film thickness of the light-shielding film formed on the coated panel was measured. Thereafter, after 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 panel was measured again, and calculated from the film thickness before and after post-baking based on the following calculation formula. Residual film rate (%)=100×film thickness after post-baking (μm)/film thickness before post-baking (μm)

<Evaluation of volume resistivity increase> Each photosensitive resin composition obtained above was coated on a 100 mm×100 mm chrome-deposited glass substrate (Corning 1737) so that the film thickness after post-baking was 3.0 μm using a spin coater, and Prebake at 90°C for 1 minute. Thereafter, after post-baking at 230°C for 180 minutes using a hot air dryer, using an electrometer (manufactured by Keithley, "Type 6517A"), a voltage was applied in steps of 1 V at each The volume resistivity at an applied voltage of 1 V to 10 V was measured while maintaining the lower voltage for 60 seconds each. For the volume resistivity when 10 V is applied, the increases in Examples 1 to 11 and Comparative Examples 1 to 3 were calculated based on the following calculation formulas based on the standard Comparative Example 1 that does not use the component (A) degree, the degree of increase of Example 12 to Example 24 based on the standard comparative example 2 not using the (A) component, and the comparative example 4 to the comparative example 3 based on the standard comparative example 3 not using the (A) component The degree of rise of Example 6, the degree of rise of Comparative Examples 7 to 9 based on the standard Comparative Example 4 that does not use the (A) component, and the implementation of the standard Comparative Example 5 that does not use the (A) component Example 25-Example 33 rise degree. In addition, what is used as a reference is expressed as "Ref." in the following table. Degree of rise = each volume resistivity (Ω·cm) of the example or comparative example/each volume resistivity (Ω·cm) of the reference comparative example Regarding the calculated increase in volume resistivity, the increase in volume resistivity was determined based on the following determination criteria. 〇: 100≦Volume resistivity increase degree Δ: 10≦Volume resistivity increase degree<100 ×: volume resistivity increase <10

<Evaluation of development characteristics (minimum resolution line width)> Each photosensitive resin composition obtained above was coated on a 125 mm×125 mm glass substrate ( Corning (Corning) 1737) and prebake at 90°C for 1 minute. Thereafter, a negative photomask having a line pattern with an opening width of 1 μm to 20 μm is closely bonded to the dry coating film, and 40 mJ/cm ² of ultraviolet rays are irradiated with an ultra-high pressure mercury lamp with an i-ray illuminance of 30 mW/cm ² , to carry out the photohardening reaction of the photosensitive part.

Next, with respect to the coated plate whose exposure was finished, the developing time from the beginning of pattern appearance was carried out at 23° C. in 0.04% potassium hydroxide aqueous solution with a shower developing pressure of 1 kgf/cm ² (breaktime = After developing for +60 seconds from BT), spray water washing with a pressure of 5 kgf/cm ² is carried out to remove the unexposed part of the coating film and form a line pattern on the glass substrate. After that, use a hot air dryer at 230°C for 30 Baking after heating for 1 minute, and then obtaining a line pattern, the smallest opening line without pattern peeling in the obtained line pattern was taken as the minimum resolution line width. ◎: 2 μm or more and less than 5 μm ○: 5 μm or more and less than 9 μm Δ: 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, Example 34, and Reference Comparative Example 2 was coated on a surface of 100 mm× A 100 mm chrome-evaporated glass substrate (Corning 1737) was prebaked at 90 °C for 1 min. Thereafter, after post-baking at 230°C for 180 minutes using a hot air dryer, using an electrometer (manufactured by Keithley, "Type 6517A"), a voltage was applied in steps of 1 V at each The volume resistivity at an applied voltage of 1 V to 10 V was measured while maintaining the lower voltage for 60 seconds each. In addition, differently from these, the temperature of the thermal post-baking was changed to 270° C., and the same procedure was implemented for each photosensitive resin composition of Examples 15 to 17, Example 34, and Reference Comparative Example 2 in the same manner. to measure volume resistivity. Regarding the volume resistivity when 10 V was applied, the decrease rate (absolute value) of the volume resistivity when the temperature of the post-baking was changed from 230° C. to 270° C. was calculated based on the following calculation formula. In addition, when the reduction rate in the reference comparative example 2 was regarded as 1, each relative value of Examples 15 to 17 and Example 34 with respect to the reference comparative example 2 was calculated based on the following calculation formula [reduction rate relative value (x)]. In addition, about the standard comparative example 2, it expresses as "Ref." in the following table|surface. Reduction rate (absolute value)=100×(logA-logB)/logB (Here, A is the measured value of volume resistivity (Ω·cm) at 270°C after heat-baking, and B is the measured value (Ω·cm) of volume resistivity at 230°C after heat-baking) Relative value of reduction rate (x) = each reduction rate of Example 15, Example 16, Example 17, or Example 34/reduction rate of Reference Comparative Example 2 The relative value of the calculated decrease rate was determined based on the following determination criteria as heat resistance. ◎: 0≦x<0.5 〇: 0.5≦x<0.8 Δ: 0.8≦x<1.0 ×: 1.0≦x

[table 5] Example Example Example Example Example Example Example Example Example Example Example comparative example comparative example comparative example Benchmark comparison example 1 2 3 4 5 6 7 8 9 10 11 1 2 3 1 OD (/μm) 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 3.9 4.0 4.0 4.0 4.0 4.0 4.0 Residual film rate after thermal hardening (%) 91.8 92.5 92.5 92.1 92.0 93.0 92.8 92.2 93.4 92.6 93.1 91.9 91.1 90.4 92.0 volume resistivity increase Δ 〇 Δ 〇 〇 〇 〇 〇 〇 〇 〇 x x x Ref. Minimum resolution line width (μm) ◎ ◎ ◎ 〇 〇 〇 〇 Δ Δ Δ Δ ◎ 〇 Δ ◎

[Table 6] Example Example Example Example Example Example Example Example Example Example Example Example Example Benchmark comparison example 12 13 14 15 16 17 18 19 20 twenty one twenty two twenty three twenty four 2 OD (/μm) 4.0 4.0 4.0 4.0 4.0 4.0 3.9 4.0 3.9 4.0 4.0 4.0 4.0 4.0 Residual film rate after thermal hardening (%) 91.0 92.0 91.5 92.1 92.3 91.3 92.8 92.5 91.8 91.1 90.4 90.7 90.5 91.0 volume resistivity increase Δ 〇 Δ 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Ref. Minimum resolution line width (μm) ◎ ◎ ◎ ◎ ◎ ◎ 〇 〇 〇 ◎ ◎ ◎ ◎ ◎ heat resistance - - - ◎ ◎ 〇 - - - - - - - Ref.

[Table 7] comparative example comparative example comparative example Benchmark comparison example comparative example comparative example comparative example Benchmark comparison example 4 5 6 3 7 8 9 4 OD (/μm) 2.2 2.2 2.2 2.2 4.2 4.2 4.2 4.2 Residual film rate after thermal hardening (%) 91.8 92.1 91.8 91.7 87.9 88.7 87.6 88.0 volume resistivity increase x x x Ref. x x x Ref. Minimum resolution line width (μm) 〇 〇 Δ 〇 ◎ ◎ 〇 ◎

[Table 8] Example Example Example Example Example Example Example Example Example Example Benchmark comparison example 25 26 27 28 29 30 31 32 33 34 5 OD (/μm) 3.9 4.0 4.0 3.9 4.0 4.0 3.9 4.0 3.9 4.0 4.0 Residual film rate after thermal hardening (%) 88.9 89.5 89.2 89.1 89.8 89.7 89.4 89.9 90.2 - 88.2 volume resistivity increase Δ Δ Δ 〇 〇 〇 〇 〇 〇 〇 Ref. Minimum resolution line width (μm) ◎ ◎ ◎ ◎ ◎ ◎ 〇 〇 〇 - ◎ heat resistance - - - - - - - - - Δ -

According to the results of Examples 1 to 34, Comparative Examples 1 to 9, and Reference Comparative Examples 1 to 5, it is clear that by adding carbon black to the photosensitive resin composition containing the light-shielding component of the light-shielding material Adding an epoxy compound as the component (A) improves the volume resistivity. Among them, especially in Examples 15 to 17, Examples 21 to 24, and Examples 28 to 30, the increase in volume resistivity is very high and the minimum resolution line width is thin, so the development adhesion is also good. It is an excellent photosensitive resin composition for light-shielding film that combines high light-shielding, high-resistance, and high-definition. In addition, in the case of Examples 15 to 17 using the epoxy compounds of (A)-1 to (A)-3 in the (A) component, it was found that the heat resistance was excellent, and it was found that especially in (A) )-1 and (A)-2, the heat resistance was more excellent.

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Claims (5)

A photosensitive resin composition for a light-shielding film, characterized by comprising the following components (A) to (F) as essential components, (A) epoxy compound, (B) Alkali-soluble resins containing polymerizable unsaturated groups, (C) a photopolymerizable monomer having at least one ethylenically unsaturated bond, (D) Light-shielding components containing carbon black as a light-shielding material, (E) photopolymerization initiator, and (F) solvent, The component (A) has an aromatic ring in the main chain, and 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 g/eq ~400 g/eq. The photosensitive resin composition for a light-shielding film according to Claim 1, wherein the mass ratio (B)/(C) of component (B) to component (C) is 50/50 to 90/10, relative to (D) 100 mass parts of components contain 0.5-15 mass parts of (A) components, and 40-70 mass % of (D) components are contained in the solid content of the photosensitive resin composition for light-shielding films. A light-shielding film formed by curing the photosensitive resin composition for a light-shielding film according to Claim 1 or Claim 2. A color filter, characterized by comprising the light-shielding film according to claim 3. A display device having the color filter according to Claim 4.