KR102639912B1 - Photosensitive resin composition for light-shielding film with the role of spacer, light-shielding film thereof, lcd with that film, and manufacturing process for them - Google Patents

Abstract

(Problem) It is possible to form a light-shielding film that has high light-shielding and insulating properties and has excellent compression ratio, elastic recovery rate, and fracture strength. Additionally, when forming a light-shielding film with a spacer function, it is possible to form a step of ΔH, creating a pattern shape that is closer to vertical. A photosensitive resin composition capable of forming a is provided.
(Solution) The present invention is a photosensitive resin composition for a light-shielding film, characterized in that it contains components (A) to (E) as essential components.
(A) It contains a unit derived from a (meth)acrylic acid ester compound and a unit having a (meth)acryloyl group and a di- or tricarboxylic acid residue, and has a weight average molecular weight of 3,000 to 50,000 and an acid value of 30 to 200 mg/KOH. Alkali-soluble resin containing a polymerizable unsaturated group, which is a polymer,
(B) Photopolymerizable monomer having at least two ethylenically unsaturated bonds
(C) Photopolymerization initiator
(D) Light-blocking component that is a black organic pigment, mixed-color organic pigment, or light-blocking material.
(E) Solvent

Description

Photosensitive resin composition for light-shielding film, light-shielding film, liquid crystal display device, manufacturing method of light-shielding film with spacer function, and manufacturing method of liquid crystal display device {PHOTOSENSITIVE RESIN COMPOSITION FOR LIGHT-SHIELDING FILM WITH THE ROLE OF SPACER, LIGHT-SHIELDING FILM THEREOF, LCD WITH THAT FILM, AND MANUFACTURING PROCESS FOR THEM}

The present invention relates to a photosensitive resin composition for a light-shielding film and a light-shielding film cured thereof, and specifically, to a black matrix of a liquid crystal display device, or a black column spacer having both a spacer function and a black matrix function in a liquid crystal display device, by photolithography. It relates to a photosensitive resin composition that can be formed and a cured film thereof. The present invention also relates to a liquid crystal display device using the black matrix or black column spacer obtained by curing the above. The present invention also relates to a method of manufacturing a light-shielding film and a liquid crystal display device using the photosensitive resin composition.

In recent years, color liquid crystal displays (LCDs) have been used in all fields, including liquid crystal televisions, liquid crystal monitors, and color liquid crystal mobile phones. Among these, improvements aimed at improving characteristics such as viewing angle, contrast, and response speed are actively being made to improve the performance of LCDs, and various panel structures have been developed for thin-film transistor (TFT)-LCDs, which are currently widely used. For TFT-LCD, the method of manufacturing an array substrate and a color filter substrate on which a conventional TFT is formed separately and bonding the two substrates while keeping them at a constant distance using a spacer has been mainly adopted. However, this method has been adopted to reduce costs and improve yield. Targeted LCD manufacturing processes have also been developed. For example, a manufacturing process has been developed that forms a color filter directly on the TFT of the array substrate and bonds a glass substrate as the opposing substrate. The structure formed in this way is called color filter-on TFT (COT), etc. In this COT as well, there is a method of forming a black matrix that serves as the boundary of each pixel, such as red (R), green (G), and blue (B) of the color filter layer formed on the TFT, before forming the RGB pixel. Various LCD panel structures are being studied, such as a method of forming the LCD panel after forming the LCD panel, or a method of forming the LCD panel on an opposing glass substrate.

As for the spacer, which is responsible for maintaining the thickness of the liquid crystal layer constant (in the conventional method, the gap between the array substrate and the color filter (CF) substrate), which is a factor affecting the performance of LCD, conventionally, balls of a certain particle size are used. The method of inserting a spacer was taken. However, this method has a problem in that the dispersion state of the ball spacers becomes non-uniform, so the amount of light transmitted for each pixel becomes inconsistent. For this problem, a method of forming a column spacer by photolithography is adopted. However, many column spacers formed by photolithography are transparent, and these column spacers have a problem in that light incident from an oblique direction affects the electrical characteristics of the TFT and deteriorates display quality. In response to this problem, an LCD panel structure using a light-shielding column spacer, which is a light-shielding film with a spacer function formed by a photolithography method, has been proposed (Patent Document 1). Also in COT, a method of forming a so-called black column spacer (BCS), in which the column spacer is formed of the same material as the black matrix, has also been studied (for example, patent document 2).

Since this light-shielding column spacer functions as a spacer, a film thickness of about 2 to 7 μm is required. In addition, it is necessary that light-shielding column spacers with different heights can be formed simultaneously at the location where the TFT is formed and at other locations. In addition, light-shielding column spacers are also required to have appropriate ranges of elastic modulus, deformation amount, elastic recovery rate, etc. as spacer functions (Patent Document 3). In addition, light-shielding column spacers are also required to improve the reduction of curable components by adding a light-shielding component (colorant) to the spacer and the loss of electrical properties due to the influence of impurities in the colorant (Patent Document 4) ).

Additionally, when an LCD panel manufacturer actually wants to apply BCS, there are various BCS shapes required depending on the design of the panel. For example, there is a design using a BCS whose cross-sectional shape is a trapezoid or rectangle (Patent Document 5), and a design using a BCS whose cross-sectional shape is a combination of trapezoids or rectangles with different base lengths (Patent Document 6). There are also others. The reason for the combined shape is to collectively form a part that only functions as a light shield and a part that also functions as a spacer. There is also a demand for a photosensitive resin composition for a light-shielding film that is used to collectively form such cross-sectional shapes.

Japanese Patent Publication No. 08-234212 US Patent Application Publication No. 2009/0303407 Specification Japanese Patent Publication No. 2009-031778 International Publication No. 2013/062011 Korean Patent Application Publication No. 10-2013-62123 Korean Patent Application Publication No. 10-2008-34545

Although mixed-color organic pigments are used in Patent Document 4, the optical density of the light-shielding column spacer is not indicated. Mixed organic pigments are more effective in lowering dielectric constant than inorganic pigments such as carbon black, but many have low light blocking properties. In addition, because it is necessary to form spacers of different heights at the same time, light-shielding column spacers are also required to have mechanical properties such as compression ratio, elastic recovery ratio, and fracture strength. Since the shape and mechanical properties of these spacers are greatly influenced by the light-shielding component, it is difficult to design a photosensitive resin composition for a light-shielding film. Therefore, the shape and mechanical properties of spacers using carbon black or mixed-color organic pigments cannot yet be said to be sufficient, and further improvements are needed.

Additionally, as described above, the light-shielding column spacer is manufactured with a film thickness of approximately 1 to 7 μm. With the recent miniaturization of liquid crystal display devices, it is desired to be able to form fine spacer shapes in light-shielding column spacers even if the film thickness is about 1 to 7 μm. In addition, with the functions of a black matrix and a spacer, two substrates (an array substrate and a CF substrate, a COT substrate and a glass substrate with a light-shielding spacer, and a COT with a light-shielding spacer) sandwiching the liquid crystal layer. In order to accurately bond (there are various combinations of substrates and glass substrates, etc.), that is, to increase alignment precision, it is necessary to form two types of light-shielding spacer heights (forming a step of ΔH), and also to form a glass substrate (or COT substrate). ), there are many requirements for patterning characteristics such as forming a light-shielding spacer that stands as vertically as possible, and it is difficult to satisfy all the required characteristics.

The present invention was made in consideration of the above problems, and enables the formation of a light-shielding film that has high light-shielding and insulating properties and has excellent compression ratio, elastic recovery rate, and fracture strength, and also forms a step of ΔH when forming a light-shielding film having a spacer function. The object is to provide a photosensitive resin composition capable of forming a pattern shape closer to vertical, a light-shielding film formed using the same, and a liquid crystal display device containing the light-shielding film as a component.

Furthermore, a photosensitive resin composition capable of collectively forming a BCS whose cross-sectional shape is a combination of trapezoids or rectangles with different base lengths, a light-shielding film formed using the same, and a liquid crystal display device containing the light-shielding film as a component are provided. It's in the thing.

As a result of studying to solve the problems in the photosensitive resin composition for a light-shielding film as described above, the present inventors discovered that a specific colorant was suitable as a light-shielding component of the desired photosensitive resin composition for a light-shielding film, and completed the present invention.

(1) The present invention is a photosensitive resin composition for a light-shielding film, characterized in that it contains components (A) to (E) as essential components.

(A) Contains 5 to 90 mol% of the unit represented by the general formula (1) and 10 to 95 mol% of the unit represented by the general formula (2) (the unit represented by the general formula (1) and the general formula ( 2) An alkali-soluble resin containing a polymerizable unsaturated group, which is a polymer with a weight average molecular weight of 3,000 to 50,000 and an acid value of 30 to 200 mg/KOH,

[However, R ₁ , R ₃ and R ₄ independently represent a hydrogen atom or a methyl group. R ₂ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain an ether bond, an ester bond, or a urethane bond therein. In addition, 40 mol% or more of R ₂ in the units represented by the general formula (1) is a dicyclopentanyl group or a dicyclopentenyl group. R ₅ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. p represents the number 0 or 1. X represents a hydrogen atom or -OC-Y-(COOH) _q (where Y represents a divalent or trivalent carboxylic acid residue, and q represents a number from 1 to 2). In addition, two or more types of X are contained in one polymer molecule.]

(B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds,

(C) photopolymerization initiator,

(D) at least one light-shielding component selected from the group consisting of black organic pigments, mixed-color organic pigments, and light-shielding materials, and

(E) Solvent

(2) The present invention further provides that the alkali-soluble resin containing a polymerizable unsaturated group of component (A) is a unit derived from styrene, which may have a substituent on the phenyl group in addition to the units of general formula (1) and (2). and/or the photosensitive resin composition according to (1), which is a copolymer containing a unit derived from a monomaleimide compound.

(3) The present invention further includes (D) a black organic pigment and/or a mixed-color organic pigment as a light-shielding component, and the average secondary particle diameter of the black organic pigment and/or the mixed-color organic pigment is 20 to 500 nm. , (1) or (2), the photosensitive resin composition.

(4) The present invention further provides the component (B) in an amount of 5 to 400 parts by mass based on 100 parts by mass of the component (A), and the component (C) in an amount of 0.1 to 400 parts by mass based on the total amount of the component (A) and (B). 30 parts by mass, when the component (B) that becomes solid after photocuring is included and the component (E) is considered solid, the component (D) is included in an amount of 5 to 80% by mass out of the total solid content. The photosensitive resin composition according to any one of (1) to (3).

(5) The present invention also provides a light-shielding film having an optical density (OD) of 0.5/μm or more and 3/μm or less, a volume resistivity of 1×10 ⁹ Ω·cm or more when a voltage of 10 V is applied, and a dielectric constant of 2 to 10. The photosensitive resin composition according to any one of (1) to (4), characterized in that it can be formed.

(6) The present invention is further characterized in that it is possible to form a light-shielding film that satisfies at least one of the following (i) to (iii) in a load-unload test by a microhardness tester, (1) to (5) It is a photosensitive resin composition according to any one of the above.

(i) Having a breaking strength of 200 mN or more

(ii) Elastic recovery rate of 30% or more

(iii) Compression ratio of 40% or less

(7) The present invention is also a light-shielding film characterized in that it is a cured product of the photosensitive resin composition according to any one of (1) to (6).

(8) The present invention is also a liquid crystal display device characterized by having the light-shielding film described in (7) as a black column spacer (BCS).

(9) The present invention is the liquid crystal display device according to (8), further comprising a thin film transistor (TFT).

(10) The present invention is also a liquid crystal display device characterized by having a cured product of the photosensitive resin composition according to any one of (1) to (6) as a black matrix.

(11) The present invention further has a thin film transistor (TFT), and the black matrix is disposed between the liquid crystal and a substrate facing the array substrate on which the thin film transistor (TFT) is formed. It is a display device.

(12) The present invention is the liquid crystal display device according to (10), further comprising a thin film transistor (TFT), and the black matrix is disposed between the liquid crystal and an array substrate on which the thin film transistor (TFT) is formed.

(13) The present invention is also a method for producing a light-shielding film formed on a substrate by applying the photosensitive resin composition according to any one of (1) to (6) to the substrate and curing the photosensitive resin composition by light irradiation, the light-shielding film Regarding the film thickness (H1) to keep the optical density from 0.5/㎛ to less than 3/㎛ and the film thickness (H2) of the light-shielding film that functions as a spacer, when H2 is 1 to 7㎛, ΔH = H2-H1 This is a method of manufacturing a light-shielding film with a spacer function, characterized by simultaneously forming a light-shielding film with a film thickness (H1) and a film thickness (H2) of 0.1 to 6.9.

(14) The present invention further provides a method for manufacturing a light-shielding film according to (13), wherein a light-shielding film including a portion having the film thickness (H1) and a portion having the film thickness (H2) is formed in a single light-shielding film through one exposure. am.

(15) The present invention is also a method of manufacturing a liquid crystal display device, characterized in that the light-shielding film manufactured by the method described in (13) or (14) is used as a black column spacer (BCS).

(16) The present invention is also the manufacturing method according to (15), wherein the liquid crystal display device has a thin film transistor (TFT).

The photosensitive resin composition for a light-shielding film according to the present invention can obtain a cured product excellent in compression rate, elastic recovery rate, and breaking strength while maintaining light-shielding properties and insulating properties. In addition, the photosensitive resin composition for a light-shielding film according to the present invention can form a fine spacer shape even when the film thickness is about 1 to 7 μm.

1 is a height profile of a pattern formed using the photosensitive resin composition of Example 8.
Figure 2 is a height profile of a pattern formed using the photosensitive resin composition of Example 9.
Figure 3 is a height profile of a pattern formed using the photosensitive resin composition of Comparative Example 3.
Figure 4 is a height profile of a pattern formed using the photosensitive resin composition of Comparative Example 4.

Hereinafter, the present invention will be described in detail.

One embodiment of the present invention includes (A) an alkali-soluble resin containing a polymerizable unsaturated group, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D) a light-shielding component, and (E) a solvent as essential components, each of which is described in detail below. It relates to a photosensitive resin composition comprising:

The polymerizable unsaturated group-containing alkali-soluble resin of component (A) is a polymer containing a unit represented by general formula (1) and a unit represented by general formula (2).

In general formulas (1) and (2), R ₁ , R ₃ and R ₄ independently represent a hydrogen atom or a methyl group. R ₂ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain an ether bond, an ester bond, or a urethane bond therein. In addition, 40 mol% or more of R ₂ in the units represented by the general formula (1) is a dicyclopentanyl group or a dicyclopentenyl group.

R ₅ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. p represents the number 0 or 1. _Where or more included).

Hydrocarbon groups represented by R ₂ include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, and neopentyl group. , saturated linear groups such as tert-pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, etc. Unsaturated linear hydrocarbon groups such as hydrocarbon groups, vinyl groups, allyl groups, and ethynyl groups, cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, 2-methylcyclohexyl groups, 4-methylcyclohexyl groups, and dicyclofentanyl groups. , dicyclopentenyl group, dicyclohexyl group, norbornyl group, isobornyl group, adamantyl group, a substituent represented by the following general formula (3) (* indicates a bonding portion with the ester moiety of general formula (1) ), aromatic rings such as cyclic aliphatic hydrocarbon groups, phenyl group, tolyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, benzyl group, 2-phenylethyl group, 2-phenylvinyl group, decahydronaphthyl group, etc. and aliphatic ethers such as hydrocarbon groups, methoxyethyl groups, 2-(methoxyethoxy)ethyl groups, and isoamyl groups, and aliphatic urethanes such as 2-(ethoxycarbonylamino)ethyl groups. In the present invention, it is essential that the hydrocarbon group represented by R ₂ contains a dicyclopentanyl group or a dicyclopentenyl group. The unit represented by General Formula (1) may include a plurality of units with different R ₂ .

Examples of the hydrocarbon group represented by R ₅ include ethylene group, 1,2-propylene group, 1,4-butylene group, and 1,6-hexamethylene group. The hydrocarbon group represented by R ₅ is preferably an ethylene group, 1,2-propylene group, or 1,4-butylene group. The unit represented by General Formula (2) may include a plurality of units with different R ₅ .

The structure _of where , is formed by reacting divalent carboxylic acid, trivalent carboxylic acid, or their acid monoanhydride. The divalent or trivalent carboxylic acid residue refers to the portion excluding the COOH group in a carboxylic acid compound in which two or three COOH groups are bonded. Examples of the divalent or trivalent carboxylic acids used here include divalent or trivalent carboxylic acids such as maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, chlorendic acid, and trimellitic acid. Examples include boxylic acids, and their acid monoanhydrides can also be preferably used. More preferably, it is tetrahydrophthalic anhydride, succinic anhydride, or trimellitic anhydride.

The ratio of the unit represented by formula (1) and the unit represented by formula (2) is when the sum of the unit represented by formula (1) and the unit represented by formula (2) is 100 mol%. , the unit represented by the general formula (1) may be 5 to 90 mol%, preferably 20 to 70 mol%. Additionally, the amount of the unit represented by the general formula (2) may be 10 to 95 mol%, preferably 30 to 80 mol%.

The polymerizable unsaturated group-containing alkali-soluble resin of component (A) may contain other units in addition to the unit represented by the general formula (1) and the unit shown by the general formula (2). For example, the alkali-soluble resin containing a polymerizable unsaturated group as component (A) may further contain a unit derived from styrene or monomaleimide, which may have a substituent on the phenyl group. Substituents that styrene may have on the phenyl group include an alkyl group having 1 to 10 carbon atoms. Examples of monomaleimide include N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide.

Among these, styrene and N-phenylmaleimide are preferred.

The ratio of the other units mentioned above can be 20 to 50 mol%, assuming that the entire polymer is 100 mol%.

Additionally, only one type of alkali-soluble resin containing a polymerizable unsaturated group (A) may be used, or a mixture of two or more types of polymers having different polymerization ratios may be used.

The method for producing the alkali-soluble resin containing a polymerizable unsaturated group of component (A) is not particularly limited. For example, in the first step, (meth)acrylic acid esters having the functional group described above as R ₂ and (meth)acrylic acid ester compounds having a glycidyl group such as glycidyl (meth)acrylate are radically copolymerized in a solvent. After obtaining the copolymer, as a second step, a monocarboxylic acid compound such as (meth)acrylic acid (including alkylene oxide modified ones) is reacted with the glycidyl group in the copolymer, and then as a third step. There is a method of reacting the hydroxyl group produced in step 2 with a dicarboxylic acid compound, a tricarboxylic acid compound, or an acid monoanhydride of these carboxylic acid compounds.

As (meth)acrylic acid esters that become units of the general formula (1) used in the first step, first, (meth)acrylic acid esters for introducing a dicyclopentanyl group or dicyclopentenyl group, which is essential in the present invention as R ₂ As, dicyclofentanyl (meth)acrylate of formula (4), dicyclopentenyl (meth)acrylate of formula (5), ethylene glycol-modified dicyclofentanyl (meth)acrylate of formula (6), formula Examples include ethylene glycol-modified dicyclopentenyl (meth)acrylate (7), and two or more of these may be used in combination.

In addition, R ₁ in general formulas (4) to (7) represents a hydrogen atom or a methyl group like R ₁ in general formula (1).

Other (meth)acrylic acid esters that form units of general formula (1) include methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic acid-n-propyl, (meth)acrylic acid-iso-propyl, and (meth)acrylic acid. ) acrylic acid-n-butyl, (meth)acrylic acid-sec-butyl, (meth)acrylic acid-tert-butyl, (meth)acrylic acid pentyl, (meth)acrylic acid neopentyl, (meth)acrylic acid isoamyl, (meth)acrylic acid hexyl , (meth)acrylic acid 2-ethylhexyl, (meth)acrylic acid dodecyl, (meth)acrylic acid cyclopentyl, (meth)acrylic acid cyclohexyl, (meth)acrylic acid 2-methylcyclohexyl, (meth)acrylic acid dicyclohexyl, ( Isobornyl (meth)acrylate, adamantyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, anthracenyl (meth)acrylate, benzyl (meth)acrylate, ( (meth)acrylic acid esters having a hydrocarbon group of 1 to 20 carbon atoms, such as phenethyl (meth)acrylate, cresyl (meth)acrylate, triphenylmethyl (meth)acrylate, and cumyl (meth)acrylate, and two or more types thereof. Can also be used together.

The amount of (meth)acrylic acid ester used may be adjusted so that the amount of (meth)acrylic acid ester for introducing a dicyclopentanyl group or dicyclopentenyl group is 40 mol% or more based on the total of (meth)acrylic acid esters.

In addition, the amount of the (meth)acrylic acid ester and the (meth)acrylic acid ester compound having a glycidyl group used is 5 to 90 mol% of units derived from (meth)acrylic acid ester in the copolymer, and the (meth)acrylic acid ester compound having a glycidyl group is 5 to 90 mol%. ) It may be adjusted so that the unit derived from the acrylic acid ester compound is 10 to 95 mol%.

Examples of dicarboxylic acid compounds, tricarboxylic acid compounds, or acid monoanhydrides of these carboxylic acid compounds used in the third step include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and chlorendic acid. , trimellitic acid, and their acid monoanhydrides, and two or more types can be used in combination. Among these, tetrahydrophthalic anhydride, succinic anhydride, and trimellitic anhydride can be preferably used.

In the radical polymerization of the first step, known radical polymerization initiators such as azo compounds and peroxides can be used, and the degree of polymerization may be controlled using known chain transfer agents, polymerization inhibitors, etc. The reaction temperature can be set appropriately in consideration of the half-life temperature of the radical polymerization initiator used.

The addition reaction in the second step is performed by heating and stirring to 90 to 120°C while blowing air in the presence of a catalyst such as, for example, triethylbenzylammonium chloride, 2,6-isobutylphenol, and trisdimethylaminomethylphenol. There is a way to react.

The third step includes, for example, a method of reacting by heating and stirring at 90 to 130°C in the presence of a catalyst such as triethylamine, tetraethylammonium bromide, or triphenylphosphine.

As another method for producing an alkali-soluble resin containing a polymerizable unsaturated group of component (A), as a first step, a monocarboxylic acid compound containing a polymerizable unsaturated group such as the above-mentioned (meth)acrylic acid esters and (meth)acrylic acid is added. It is radically copolymerized in a solvent, and as a second step, a (meth)acrylic acid ester having a glycidyl group such as glycidyl (meth)acrylate is reacted with the carboxyl group in the copolymer, and as a third step, the product produced in the second step is There is also a method of reacting the hydroxyl group with the above-mentioned dicarboxylic acid compound, tricarboxylic acid compound, or acid monoanhydride of these carboxylic acid compounds.

Additionally, when the alkali-soluble resin containing a polymerizable unsaturated group as component (A) has other units such as the above-mentioned styrene or monomaleimide, the styrene or monomaleimide may be copolymerized in the first step in any method. .

The weight average molecular weight (M _w ) of the alkali-soluble resin of (A) in terms of polystyrene as measured by gel permeation chromatography (GPC) is usually 3,000 to 50,000, and is preferably 4,000 to 20,000. In the case of the alkali-soluble resin containing a polymerizable unsaturated group in the unit configuration of the present invention, if the weight average molecular weight is less than 3000, there is a risk that the pattern adhesion during alkali development may decrease, and if the weight average molecular weight exceeds 50000, the developability may be reduced. There is a risk that this will decrease significantly.

Additionally, the preferred range of the acid value of the alkali-soluble resin (A) is 30 to 200 mgKOH/g, and more preferably 50 to 150 mgKOH/g. In the case of the alkali-soluble resin containing a polymerizable unsaturated group in the unit configuration of the present invention, if this value is less than 30 mgKOH/g, residue is likely to remain during alkali development, and if it exceeds 200 mgKOH/g, penetration of the alkaline developer is too rapid, resulting in peeling phenomenon. Because this happens, it is not desirable at all. The acid value can be adjusted by the amount of carboxyl group present in X in the unit represented by general formula (2).

In the present invention, the weight average molecular weight of (A) was determined by Tosho Inc. by dissolving the sampled solution in tetrahydrofuran. Molecular weight distribution is measured using HLC-8220GPC, and the weight average molecular weight calculated in terms of standard polystyrene is used. Additionally, the acid value of component A is determined by dissolving the sampled solution in dioxane, neutralizing and titrating it with 0.1 N aqueous potassium hydroxide solution, and calculating the acid value in terms of solid content of the sample solution from the equivalence point.

Next, (B) photopolymerizable monomers having at least two ethylenically unsaturated bonds include, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate. Latex, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate , Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol (meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate ) Acrylate, or dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide modified hexa(meth)acrylate of phosphagen, caprolactone modified dipentaerythritol hexa(meth)acrylate, etc. (meth)acrylic acid esters, polyhydric alcohols such as pentaerythritol and dipentaerythritol, vinyl benzyl ether compounds of polyhydric phenols such as phenol novolak, and addition polymers of divinyl compounds such as divinylbenzene. These (B) photopolymerizable monomers having at least two ethylenically unsaturated bonds may be used as one type of compound or may be used in combination of multiple compounds. Additionally, (B) the photopolymerizable monomer having at least two ethylenically unsaturated bonds does not have a free carboxyl group. Trifunctional or more is more preferable.

The mixing ratio of component (B) is preferably 5 to 400 parts by mass, and preferably 10 to 150 parts by mass, per 100 parts by mass of component (A). If the mixing ratio of component (B) is more than 400 parts by mass with respect to 100 parts by mass of component (A), the cured product after photocuring becomes brittle, and the acid value of the coating film in the unexposed area is low, so its solubility in alkaline developer solution. As this decreases, a problem arises in that the pattern edges become jagged and do not become sharp. On the other hand, if the mixing ratio of component (B) is less than 5 parts by mass with respect to 100 parts by mass of component (A), the proportion of photoreactive functional groups in the resin is small and the formation of a crosslinked structure is not sufficient, and furthermore, in the resin component. Since the acid value of is high, the solubility in the alkaline developer in the exposed area increases, so there is a risk that the formed pattern may become thinner than the target line width or that defects in the pattern may easily occur.

In addition, as the photopolymerization initiator of component (C), for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p Acetophenones such as -tert-butylacetophenone, benzophenones such as benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin iso Benzoin ethers such as propyl 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, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2, Biimidazole-based compounds such as 4,5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p- Halomethyldiazole compounds such as cyanostyryl)-1,3,4-oxadiazole and 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl- 4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2 -(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl) -1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5- Trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1 , Halomethyl-s-triazine compounds such as 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, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl] -,1-(0-acetyloxime), methanone,(9-ethyl-6-nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy)-2- Methylphenyl]-, O-acetyloxime, methanone, (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)-, O-acyloxime compounds such as 1-O-acetyloxime, benzyldimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-di Sulfur compounds such as ethylthioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenyl anthra Anthraquinones such as quinone, organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, etc. Thiol compounds, etc. can be mentioned. Among these, it is preferable to use O-acyloxime-based compounds from the viewpoint of making it easy to obtain a highly sensitive photosensitive resin composition for a light-shielding film. These (C) photopolymerization reagents may be used alone or in combination of multiple compounds. In addition, the photopolymerization initiator referred to in the present invention is used in the sense including a sensitizer.

These photopolymerization initiators and sensitizers can be used individually or in combination of two or more. Additionally, compounds that do not act as photopolymerization initiators or sensitizers by themselves but can increase the ability of the photopolymerization initiators or sensitizers when used in combination can also be added. Examples of such compounds include tertiary amines such as triethanolamine and triethylamine, which are effective when used in combination with benzophenone.

The amount of the photopolymerization initiator of component (C) used is preferably 0.1 to 30 parts by mass, preferably 1 to 25 parts by mass, based on a total of 100 parts by mass of component (A) and component (B). If the mixing ratio of component (C) is less than 0.1 parts by mass, the speed of photopolymerization slows down and the sensitivity decreases. On the other hand, if it exceeds 30 parts by mass, the sensitivity becomes too strong and the pattern line width becomes thicker than that of the pattern mask. , there is a risk that a problem may arise such that the line width cannot be faithfully reproduced on the mask or the pattern edges may be jagged and not sharp.

Component (D) is a light-shielding component selected from black organic pigments, mixed-color organic pigments, and light-shielding materials, and preferably has excellent insulation, heat resistance, light resistance, and solvent resistance. Here, examples of black organic pigments include perylene black, aniline black, cyanine black, and lactam black. Examples of mixed-color organic pigments include those made by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta, etc., thereby producing a pseudo-black color. Light-shielding materials include chromium oxide, iron oxide, and titanium black. As for these (D) light-shielding components, only one type of compound may be used, or a plurality of compounds may be used in combination.

As the organic pigment used in the present invention, known compounds can be used without particular restrictions, but those with a specific surface area of 50 m2/g or more as determined by the BET method with atomization processing are preferred. Specifically, azo pigment, condensed azo pigment, azomethine pigment, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, isoindoline pigment, dioxazine pigment, trene pigment, perylene pigment, perinone pigment, and quinacridone pigment. Nophthalone pigment, diketopyrrolopyrrole pigment, thioindigo pigment, etc. are mentioned, and specifically, the following C.I compounds are mentioned, but are not limited to these.

C. I. Pigment Red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262 , 264, 266, 272, 279, etc.;

C.I.Pigment/Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.;

C. I. Pigment yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214 etc. ;

C.I.Pigment Green 7, 36, 58, etc.;

C. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc.;

C．I．Pigment Violet 19, 23, 37, etc.

Additionally, solvents for component (E) include, for example, methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, and 3-hydroxy-2. -Alcohols such as 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, Aromatic hydrocarbons such as xylene and tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether , glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butylcarbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Examples include esters such as ethyl ether acetate, and these can be used to dissolve and mix to form a uniform solution composition. Two or more types of these solvents may be used to obtain necessary properties such as coating properties.

In addition, the light-shielding component (D) is preferably dispersed in advance in a solvent together with the dispersant (F) to form a light-shielding dispersion, and then blended as a photosensitive resin composition for a light-shielding film. Here, since the dispersing solvent becomes part of component (E), any solvent listed as component (E) above can be used. For example, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc. are suitable. It is used.

The mixing ratio of the light-shielding component (D) forming the light-shielding dispersion is preferably in the range of 5 to 80% by mass based on the total solid content of the photosensitive resin composition for a light-shielding film of the present invention. In addition, the solid content means components other than component (E) in the composition. The solid content also includes component (B), which becomes solid after photocuring. If it is less than 5% by mass, the desired light-shielding property cannot be set. If it exceeds 80% by mass, the content of the photosensitive resin, which serves as the original binder, decreases, causing the undesirable problem of impairing the development characteristics and impairing the film forming ability.

It is desirable that the average particle diameter (hereinafter referred to as “average secondary particle diameter”) of the light-shielding component in this light-shielding dispersion measured with a laser diffraction/scattering particle diameter distribution meter is as follows. When using black organic pigments and/or mixed-color organic pigments and/or single-color organic pigments, the average secondary particle diameter of the dispersed particles is preferably 20 to 500 nm. Also, in the photosensitive resin composition for a light-shielding film prepared by mixing these light-shielding dispersions, it is preferable that these light-shielding components have the same average secondary particle size.

In addition, a dispersant (F) is used in the light-shielding dispersion to stably disperse the light-shielding component, but known dispersants such as various polymer dispersants can be used for this purpose. Examples of dispersants include known compounds conventionally used in pigment dispersion (compounds commercially available under the names of dispersants, dispersion wetting agents, dispersion accelerators, etc.) without particular restrictions, but examples include cationic polymer dispersants and anionic polymers. Dispersants based on dispersants, nonionic polymer-based dispersants, pigment derivative-type dispersants (dispersing aids), etc. can be listed. 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 polymer dispersant in the range of 1,000 to 100,000 is suitable. The blending amount of the dispersant (F) is preferably 1 to 30% by mass, preferably 2 to 25% by mass, relative to the light-shielding component.

In addition, when preparing a light-shielding dispersion, by codispersing a part of the alkali-soluble resin containing a polymerizable unsaturated group of component (A) in addition to the dispersant (F) above, when used as a photosensitive resin composition for a light-shielding film, exposure sensitivity can be increased to high sensitivity. It can be made into a photosensitive resin composition that is easy to maintain, has good adhesion during development, and is unlikely to cause residue problems. The compounding amount of component (A) is preferably 2 to 20% by mass, and more preferably 5 to 15% by mass, in the light-shielding dispersion liquid. If the component (A) is less than 2% by mass, the codispersed effects such as improved sensitivity, improved adhesion, and reduced residue cannot be obtained. In addition, if it is 20% by mass or more, especially when the content of the light-shielding material is large, the viscosity of the light-shielding dispersion is high, and dispersing it uniformly becomes difficult or very time-consuming, making it difficult to obtain a coating film in which the light-shielding component is evenly dispersed. It becomes difficult to obtain a photosensitive resin composition.

The light-shielding dispersion obtained in this way contains component (A) (if component (A) is codispersed when preparing the light-shielding dispersion, the remaining component (A), component (B), component (C), and the remaining component (E) ) It can be made into a photosensitive resin composition for a light-shielding film by mixing it with the component.

Additionally, (H) additives such as a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a solvent, a leveling agent, an antifoaming agent, a coupling agent, and a surfactant may be added to the photosensitive resin composition of the present invention as needed. . Thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and hindered phenolic compounds, and plasticizers include dibutyl phthalate and dioctyl phthalate. , tricresyl phosphate, etc., fillers include glass fiber, silica, mica, alumina, etc., and examples of defoaming agents and leveling agents include silicon-based, fluorine-based, and acrylic-based compounds. In addition, surfactants include fluorine-based surfactants and silicone-based surfactants, and coupling agents include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-isocyane. Silane coupling agents such as itopropyltriethoxysilane and 3-ureidopropyltriethoxysilane can be mentioned.

The photosensitive resin composition of the present invention may be used in combination with other resin components that polymerize or harden by heat. As other resin components, (G) epoxy resins or epoxy compounds having two or more epoxy groups are preferable, such as 3,3',5,5'-tetramethyl-4,4'-biphenol type epoxy resin and bisphenol A type epoxy. Resin, bisphenol fluorene type epoxy resin, phenol novolac type epoxy resin, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate, 2,2-bis(hydroxymethyl)- Examples include 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 1-butanol, epoxy silicone resin, etc. As for these additional components, only one type of compound may be used, or a plurality of compounds may be used in combination.

The photosensitive resin composition of the present invention contains the above components (A) to (E) as main components. It is preferable that the solid content contains a total of 70% by mass of components (A) to (D), preferably 80% by mass or more. (E) The amount of solvent varies depending on the target viscosity, but is preferably contained in the range of 60 to 90% by mass in the photosensitive resin composition.

The photosensitive resin composition for a light-shielding film in the present invention is excellent as a photosensitive resin composition for forming, for example, a light-shielding film with a spacer function. A method of forming a light-shielding film having a spacer function includes the following photolithography method. First, the photosensitive resin composition for a light-shielding film according to the present invention is applied onto a substrate, the solvent is then dried (prebaking), a photomask is placed on the film thus obtained, and ultraviolet rays are irradiated to cure the exposed area, and then A method of forming a pattern by performing development to elute the unexposed area using an aqueous alkaline solution and further performing post-baking (thermal baking) as post-drying is an example.

The substrate may be a transparent substrate, or may be a substrate other than a transparent substrate, such as an alignment film formed on a pixel or on a planarization film on a pixel or on a flattening film on a pixel after forming RGB pixels. Additionally, the substrate may be an array substrate on which TFTs are formed.

The type of substrate on which the light-shielding film with a spacer function is formed depends on the design of the liquid crystal display device. For example, when the light shielding film is BCS and an area functioning as a black matrix is provided on the TFT, an array substrate may be used as the substrate. Additionally, when the area functioning as the black matrix is installed on a substrate opposite to the substrate on which the TFT is formed in a liquid crystal display device, or when manufacturing a liquid crystal display device without a TFT, a transparent substrate such as glass can be used as the substrate. there is.

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

Exposure performed after prebaking is performed using an ultraviolet exposure device, and only the portion of the resist corresponding to the pattern is exposed through a photomask. The exposure apparatus and its exposure irradiation conditions are appropriately selected, exposure is performed using a light source such as an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a deep ultraviolet ray lamp, and the photosensitive resin composition in the coating film is photocured. At this time, by forming areas with different exposure amounts using a halftone mask or the like, areas with different heights (such as an area with a film thickness H1 and an area with a film thickness H2, which will be described later) can be formed simultaneously.

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

After development, heat treatment (post-baking) is preferably performed at a temperature of 180 to 250°C and for 20 to 60 minutes. This post-baking is performed for purposes such as improving the adhesion between the patterned light-shielding film and the substrate. Similar to prebaking, this is done by heating using an oven, hot plate, etc. The patterned light-shielding film of the present invention is formed through each process using the above photolithography method.

According to the above method, a light-shielding film with an optical density of 0.5/μm to 3/μm, preferably 1.5/μm to 2.5/μm, can be formed. Additionally, according to the above method, a light-shielding film having a volume resistivity of 1×10 ⁹ Ω·cm or more when a voltage of 10 V is applied, preferably 1×10 ¹² Ω·cm or more, can be formed. Furthermore, according to the above method, a light-shielding film having a dielectric constant of 2 to 10, preferably 2 to 8, and more preferably 3 to 6 can be formed. In addition, according to the above method, in a mechanical property test, it is possible to form a light-shielding film that satisfies the breaking strength of 200 mN or more, and/or the elastic recovery rate of 30% or more, and/or the compression ratio of 40% or less. The light-shielding film formed by the above method can be used as a column spacer in a liquid crystal display device, and is preferably used as a black column spacer.

The substrate on which the light-shielding film or cured film is formed can be used as a liquid crystal display (LCD) by bonding it to another substrate with a liquid crystal layer in between. At this time, the light shielding film or cured film is formed on the array substrate on which the TFT is formed, and color resists such as red (R), green (G), and blue (B) are applied, exposed, developed, and baked to add color filters of each color. By bonding the formed product to a transparent substrate, COT can also be used as a BOA (Black Matrix on Array) liquid crystal display device. Additionally, a COT liquid crystal display can be obtained by forming the light-shielding film or cured film on a transparent substrate and bonding it to a COT substrate on which a color filter is formed on a TFT. Alternatively, the light-shielding film or cured film and color filter may be formed on a transparent substrate and bonded to the TFT substrate. Among these, the light-shielding film or cured film having a low dielectric constant can be preferably used in a BOA liquid crystal display device.

In addition, according to the above method, H2 is 1 to 7 μm with respect to the film thickness (H1) for adjusting the optical density as a light-shielding film to 0.5/μm or more and less than 3/μm and the film thickness (H2) of the light-shielding film that functions as a spacer. When ΔH=H2-H1 is 0.1 to 6.9, a light-shielding film with a film thickness (H1) and a light-shielding film with a film thickness (H2) can be formed simultaneously. A more preferable range is 2 to 5 μm for H2 and ΔH is 0.1 to 4.9, and a more preferable range is 2 to 4 μm for H2 and 0.1 to 2.9 for ΔH. The cured film formed by the above method can be used as a column spacer in a liquid crystal display device, and is preferably used as a black column spacer. According to the cured film in which ΔH is in the above range, black column spacers with different heights can be formed at once from the same material, so the manufacture of the liquid crystal display device can be performed more efficiently. At this time, for example, the cured film with a film thickness (H2) can function as a spacer, and the cured film with a film thickness (H1) can function as a black matrix.

In addition, according to the above method, the cross-sectional shape is a combination of trapezoids or rectangles with different base lengths, and the upper side of the trapezoid or rectangle with a larger width and the lower side of the trapezoid or rectangle with a smaller width are shorter than the upper side. Since the black column spacer having a step portion so that its long lower sides are in contact can be formed at once from the same material, the liquid crystal display device can be manufactured more efficiently. In other words, according to the above method, among the same black column spacers, the black column spacer is also made of the same material at once with one exposure so that the portion with the film thickness H1 and the portion with the film thickness H2 are contained simultaneously in the same light-shielding film. Since it can be formed, liquid crystal display devices can be manufactured more efficiently. In addition, the above combination shape may be as long as the shape of the part higher than the cut surface when cut at a certain height from the bottom of the black column spacer is "a combination of trapezoids or rectangles with different base lengths in cross-sectional shape", and the actual bottom is not. When the surface of the TFT has steps or depressions, it may be shaped to cover the steps or fill the depressions without gaps in accordance with the surface shape of the TFT.

In addition, when forming a black column spacer with different heights or a black column spacer with a cross-sectional shape of a combination of trapezoids or rectangles with different base lengths, it is preferable to use a black organic pigment as a light-shielding component, especially the solid content. It is more preferable to use 20 to 50% by mass of a black organic pigment. In addition, it is possible to collectively form a black column spacer with higher optical density using an inorganic black pigment such as carbon black as a part of the black organic pigment, but the ratio of the inorganic black pigment in this case is that of the black organic pigment and the inorganic black pigment. A range of 10 to 20% by mass of the total amount is preferable. The carbon black used at this time is preferably carbon black coated with resin from the viewpoint of increasing the insulation of the black column spacer and lowering the dielectric constant when added in the same amount.

The liquid crystal display device having the light-shielding film or cured film is preferably a TFT-LCD equipped with a thin film transistor.

The liquid crystal display device having the light-shielding film or cured film has high light-shielding and insulating properties, and also has a spacer function with excellent compression rate, elastic recovery rate, and fracture strength, and can form a fine spacer shape even when the film thickness is about 1 to 7 μm. .

Example

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 the alkali-soluble resin containing a polymerizable unsaturated group (A) of the present invention is shown. Evaluation of the resin in the synthesis example was performed as follows.

[Solids concentration]

1 g of the resin solution obtained in the synthesis example was impregnated with a glass filter [weight: W ₀ (g)] and weighed [W ₁ (g)], and the weight [W ₂ (g)] after heating at 160°C for 2 hours was obtained by the following formula: saved from

Solids concentration (% by weight) = 100×(W ₂ -W ₀ )/(W ₁ -W ₀ ).

[Sanga]

The resin solution was dissolved in dioxane and used in a potentiometric titration device [Hiranuma Sangyo Co Ltd. It was obtained by titration with a 1/10 N-KOH aqueous solution using [#199, product name COM-1600].

[Molecular Weight]

Gel permeation chromatography (GPC) [Tosho Inc. Second, product name HLC-8220GPC, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2 units) + TSKgelSuperH-3000 (1 unit) + TSKgelSuperH-4000 (1 unit) + TSKgelSuper-H5000 (1 unit) [Tosho Inc. 1], temperature: 40°C, speed: 0.6ml/min], and standard polystyrene [Tosho Inc. 1, PS-oligomer kit] The weight average molecular weight (M _w ) was obtained as a conversion value.

[Measurement of average secondary particle size]

The light-shielding dispersion was diluted with a solvent (PGMEA in this example), and a solution with a light-shielding component concentration of about 0.1% by mass was measured using a laser diffraction/scattering method particle size distribution meter (Micro Trac MT-, manufactured by Nikkiso Co., Ltd.). 3000), the average secondary particle size was measured.

In addition, the symbols used in synthesis examples and comparative synthesis examples are as follows.

BzMA: Benzyl methacrylate

DCPMA: dicyclofentanyl methacrylate

GMA: Glycidyl methacrylate

St: Styrene

MMA: Methyl methacrylate

MAA: methacrylic acid

AA: Acrylic acid

THPA: tetrahydrophthalic anhydride

SA: Succinic anhydride

AIBN: Azobisisobutyronitrile

TDMAMP: Trisdimethylaminomethylphenol

HQ: hydroquinone

TPP: Triphenylphenol

DTBPC: 2,6-di-tert-butyl-p-cresol

TEA: triethylamine

PGMEA: propylene glycol monomethyl ether acetate

[Synthesis Example 1]

300 g of PGMEA was placed in a 1L four-necked flask equipped with a reflux condenser, and the inside of the flask system was purged with nitrogen and the temperature was raised to 120°C. A monomer mixture (a mixture of 52.9 g (0.30 mol) of BzMA, 77.1 g (0.35 mol) of DCPMA, 49.8 g (0.35 mol) of GMA, and 10 g of AIBN) was added dropwise from a dropping funnel over 2 hours and cooled at 120°C. After stirring for 2 hours, a copolymer solution was obtained.

Next, after replacing the flask system with air, 24.0 g of AA (95% of glycidyl groups), 0.8 g of TDMAMP, and 0.15 g of HQ were added to the obtained copolymer solution, and stirred for 6 hours under heating at 120°C to polymerize. A copolymer solution containing a sexually unsaturated group was obtained. Additionally, 45.7 g of THPA (90% of the number of moles of AA added) and 0.5 g of TEA were added to the obtained copolymer solution containing a polymerizable unsaturated group and reacted at 120°C for 4 hours to obtain an alkali-soluble copolymer resin solution containing a polymerizable unsaturated group. (A)-1 was obtained. The solid concentration of the resin solution was 47 mass%, the acid value (converted to solid content) was 62 mgKOH/g, and M _w by GPC analysis was 8200.

[Synthesis Example 2]

300 g of PGMEA was placed in a 1L four-necked flask equipped with a reflux condenser, and the inside of the flask system was purged with nitrogen and the temperature was raised to 120°C. In this flask, a monomer mixture (a mixture of 35.2 g (0.20 mol) of BzMA, 77.1 g (0.35 mol) of DCPMA, 49.8 g (0.35 mol) of GMA, and 10 g (0.10 mol) of St dissolved in 10 g of AIBN) was placed in the dropping funnel for 2 hours. It was added dropwise and stirred at 120°C for 2 hours to obtain a copolymer solution.

Next, after replacing the flask system with air, 24.0 g of AA (95% of glycidyl groups), 0.8 g of TDMAMP, and 0.15 g of HQ were added to the obtained copolymer solution, and stirred for 6 hours under heating at 120°C to polymerize. A copolymer solution containing a sexually unsaturated group was obtained.

Additionally, 45.7 g of THPA (90% of the number of moles of AA added) and 0.5 g of TEA were added to the obtained copolymer solution containing a polymerizable unsaturated group and reacted at 120°C for 4 hours to obtain an alkali-soluble copolymer resin solution containing a polymerizable unsaturated group ( A) I got -2. The solid concentration of the resin solution was 46 mass%, the acid value (converted to solid content) was 68 mgKOH/g, and M _w according to GPC analysis was 7900.

[Synthesis Example 3]

300 g of PGMEA was placed in a 1L four-necked flask equipped with a reflux condenser, and the inside of the flask system was purged with nitrogen and the temperature was raised to 120°C. A monomer mixture (a mixture of 77.1 g (0.35 mol) of DCPMA, 49.8 g (0.35 mol) of GMA, and 31.2 g (0.30 mol) of St dissolved in 10 g of AIBN) was added dropwise from a dropping funnel over 2 hours, and the mixture was heated at 120°C. After stirring for 2 hours, a copolymer solution was obtained.

Next, after replacing the flask system with air, 24.0 g of AA (95% of glycidyl groups), 0.8 g of TDMAMP, and 0.15 g of HQ were added to the obtained copolymer solution, and stirred for 6 hours under heating at 120°C to polymerize. A copolymer solution containing a sexually unsaturated group was obtained.

Additionally, 30.0 g of SA (90% of the number of moles of AA added) and 0.5 g of TEA were added to the obtained copolymer solution containing a polymerizable unsaturated group and reacted at 120°C for 4 hours to obtain an alkali-soluble copolymer resin solution containing a polymerizable unsaturated group ( A) I got -3. The solid concentration of the resin solution was 46 mass%, the acid value (converted to solid content) was 76 mgKOH/g, and M _w according to GPC analysis was 5300.

[Comparative Synthesis Example 1]

370 g of PGMEA was placed in a 1 L four-necked flask equipped with a reflux condenser, and the inside of the flask system was purged with nitrogen and the temperature was raised to 90°C. A monomer mixture (a mixture of 38.8 g (0.22 mol) of BzMA, 38.4 g (0.38 mol) of MMA, and 51.7 g (0.60 mol) of MAA and 6 g of AIBN) was added dropwise from a dropping funnel over 2 hours, and the mixture was heated to 90°C. was stirred for 8 hours to obtain a copolymer solution.

Next, after replacing the flask system with air, 39.2 g of GMA (50% of the carboxyl group), 1.4 g of TPP, and 0.06 g of DTBPC were added to the obtained copolymer solution, and stirred for 6 hours under heating at 90° C. to obtain polymerizable unsaturation. A group-containing alkali-soluble copolymer resin solution (A)-4 was obtained. The solid concentration of the resin solution was 32% by mass, the acid value (converted to solid content) was 110 mgKOH/g, and M _w according to GPC analysis was 18100.

(Alkali-soluble resin containing polymerizable unsaturated group)

(A)-1 Component: Alkali-soluble resin solution obtained in Synthesis Example 1 above

(A)-2 Component: Alkali-soluble resin solution obtained in Synthesis Example 2 above

(A)-3 Component: Alkali-soluble resin solution obtained in Synthesis Example 3 above

(A)-4 Component: Alkali-soluble resin solution obtained in Comparative Synthesis Example 1 above

(Photopolymerizable monomer)

(B): A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., brand name DPHA)

(Photopolymerization initiator)

(C): Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(0-acetyl oxime) (manufactured by BASF Japan Ltd., product name) Irgacure OXE02)

(Light-blocking disperse pigment)

(D)-1: PGMEA dispersion (solid content 19.5%, average secondary particle size of black pigment 241 nm) containing 15.0 mass% of black pigment (lactam black Irgaphor S0100CF manufactured by BASF Corp.) and 4.5 mass% of polymer dispersant.

(D)-2: C.I.Pigment Orange 64 (manufactured by BASF Corp.) 7.0 mass%, C.I.Pigment Violet 23 (manufactured by Clariant) 3.0 mass%, C.I.Pigment Blue 15:6 (manufactured by Clariant) 7.0 mass%, polymer dispersant concentration 4.0 mass%, 2.0 mass% sulfonated azo dispersant, 2.0 mass% benzyl methacrylate/methacrylic acid copolymer, PGMEA dispersion (solid content 25.0%)

(D)-3: PGMEA dispersion of 20.0% by mass of carbon black and 5.0% by mass of polymer dispersant (solid content 25.0%, average secondary particle size of carbon black 162nm)

(D)-4: PGMEA dispersion of 25.0% by mass of resin-coated carbon black and 5.0% by mass of polymer dispersant (solid content 30.0%, average secondary particle size of carbon black 90nm)

(solvent)

(E)-1: PGMEA

(E)-2: 3-methoxy-3-methylbutylacetate

(Surfactants)

(H): PGMEA solution (solid content 1.0%) of BYK-330 (manufactured by BYK-Chemie GmbH)

The above-mentioned ingredients were mixed in the ratios shown in Table 1 to prepare photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 2. In addition, the values in Table 1 all represent the compounding amount (g). In addition, (E)-1 in the solvent compartment is PGMEA (same as (E)-1) in the unsaturated group-containing resin solution (alkali-soluble resin solution containing polymerizable unsaturated group), and PGMEA ((E)) in the light-shielding dispersion. It is a quantity that does not include (same as -1).

[evaluation]

The evaluation described below was performed using the photosensitive resin composition for light shielding films of Examples 1 to 7 and Comparative Examples 1 to 2. The results of these evaluations are shown in Table 2.

<Phenomena characteristics>

Each of the photosensitive resin compositions obtained above was applied onto a glass substrate with a thickness of 1.2 mm using a spin coater so that the film thickness after heat curing was 3.0 μm, and prebaked at 90°C for 1 minute. After that, the photomask was brought into close contact, and ultraviolet rays of 100 mJ/cm 2 were irradiated with an ultra-high pressure mercury lamp with a wavelength of 365 nm and an illuminance of 30 mW/cm 2 to perform a photocuring reaction of the photosensitive portion.

Next, the exposed glass substrate was developed for 60 seconds at 24°C and a pressure of 0.1 MPa using a 0.05% potassium hydroxide aqueous solution to remove the unexposed portion of the coating film. After that, heat curing was performed at 230°C for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition. The formation of fine lines in the obtained cured film pattern was confirmed with an optical microscope and evaluated in the following three steps. The results are shown in Table 2.

○: A pattern with L/S of 10㎛/10㎛ or more is formed without residue.

△: A pattern with L/S of 30㎛/30㎛ or more is formed without residue.

×: A pattern with an L/S of less than 50㎛/50㎛ is not formed, or the trailing or residue of the pattern is prominent.

<Optical density>

Each of the photosensitive resin compositions obtained above was applied onto a glass substrate with a thickness of 1.2 mm using a spin coater so that the film thickness after heat curing was 1.1 μm, and prebaked at 90°C for 1 minute. After that, heat curing was performed at 230°C for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition. Next, the optical density of the obtained cured film was measured using a Macbeth transmission densitometer and evaluated as optical density per unit film thickness.

<Volume resistivity>

Each of the photosensitive resin compositions obtained above was applied to the portion excluding the electrode on the Cr-deposited glass substrate with a thickness of 1.2 mm using a spin coater so that the film thickness after heat curing was 3.5 ㎛, and prebaked at 90°C for 1 minute. . After that, heat curing was performed at 230°C for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition. After that, an aluminum electrode was formed on the cured film to create a substrate for measuring volume resistivity. Next, the volume resistivity was measured at an applied voltage of 1 V to 10 V using an electrometer (Keithley Instruments, Inc., “Type 6517A”). Measurements were made under the condition of maintaining the voltage for 60 seconds at each applied voltage in 1V steps, and the volume resistivity when 10V is applied is shown in Table 2.

<Dielectric constant>

Each of the photosensitive resin compositions obtained above was applied to the portion excluding the electrode on the Cr-deposited glass substrate with a thickness of 1.2 mm using a spin coater so that the film thickness after heat curing was 3.5 ㎛, and prebaked at 90°C for 1 minute. . After that, heat curing was performed at 230°C for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition. After that, an aluminum electrode was formed on the cured film to create a substrate for dielectric constant measurement. Next, the electric capacitance at a frequency of 1 Hz to 100000 Hz was measured using an electrometer (Keithley Instruments, Inc., “Type 6517A”), and the dielectric constant was calculated from the electric capacitance. The calculated dielectric constants are shown in Table 2.

<Halftone (HT) characteristics of spacer>

Each of the photosensitive resin compositions obtained above was applied onto a glass substrate with a thickness of 1.2 mm using a spin coater so that the film thickness after heat curing was 3.0 μm, and prebaked at 90°C for 1 minute. After that, a photomask with a dot pattern was placed in close contact, and ultraviolet rays of 5 mJ/cm 2 or 100 mJ/cm 2 were irradiated with an ultra-high pressure mercury lamp with a wavelength of 365 nm and an illuminance of 30 mW/cm 2 to perform a photocuring reaction of the photosensitive portion.

Next, the exposed glass substrate was developed for 60 seconds at 24°C and a pressure of 0.1 MPa using a 0.05% potassium hydroxide aqueous solution to remove the unexposed portion of the coating film. After that, heat curing was performed at 230°C for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition.

The halftone characteristics of the spacer calculate the difference (ΔH) between the film thickness of the light-shielding film (H1) at an exposure dose of 5 mJ/cm2 and the film thickness (H2) of the spacer at an exposure dose of 100 mJ/cm2, using the following four steps. It was evaluated as The results are shown in Table 2.

○: When ΔH is 1.0㎛∼2.0㎛

△: When ΔH is 0.1㎛∼2.9㎛

×: When ΔH is less than 0.1㎛ or greater than 2.9㎛

<Compression rate, elastic recovery rate, and breaking strength of spacer>

Each of the photosensitive resin compositions obtained above was applied onto a glass substrate with a thickness of 1.2 mm using a spin coater so that the film thickness after heat curing was 3.0 μm, and prebaked at 90°C for 1 minute. After that, a photomask with a dot pattern was placed in close contact, and ultraviolet rays of 100 mJ/cm 2 were irradiated with an ultra-high pressure mercury lamp with a wavelength of 365 nm and an illuminance of 30 mW/cm 2 to perform a photocuring reaction of the photosensitive portion.

Next, the exposed glass substrate was developed for 60 seconds at 24°C and a pressure of 0.1 MPa using a 0.05% potassium hydroxide aqueous solution to remove the unexposed portion of the coating film. After that, heat curing was performed at 230°C for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition.

The spacer properties of the obtained cured film pattern were evaluated using an ultra-micro hardness tester (Fisher Scope HM2000Xyp, manufactured by Fisher Instruments). A 100 μm x 100 μm flat indenter was press-fitted at a loading rate of 5.0 mN/sec, a load of up to 50 mN was applied, and then unloaded at an unloading rate of 5.0 mN/sec to create a displacement curve. The compression ratio was calculated from the following equation, with the displacement at a load of 50 mN at the time of load being L1.

Compression rate (%) = L1/height of spacer × 100

The elastic recovery rate was calculated from the following equation, with the displacement at a load of 50 mN at the time of load being L1 and the displacement at the time of unloading being L2.

Elastic recovery rate (%) = (L1-L2)/L1 ×100

The breaking strength was evaluated using an ultramicro hardness meter (Fisher Scope HM2000Xyp, manufactured by Fisher Instruments). A 100 μm x 100 μm flat indenter was pressed in at a load speed of 5.0 mN/sec, and a load of up to 300 mN was applied to measure the load when the spacer was destroyed, and evaluated in the following four steps. The results are shown in Table 2.

○: When the breaking strength is 300mN or more

△: When the breaking strength is 200mN or less

×: When the breaking strength is 100 mN or less

<Shape of spacer>

Each of the photosensitive resin compositions obtained above was applied onto a glass substrate with a thickness of 1.2 mm using a spin coater so that the film thickness after heat curing was 3.0 μm, and prebaked at 90°C for 1 minute. After that, a photomask with a dot pattern was placed in close contact, and ultraviolet rays of 100 mJ/cm 2 were irradiated with an ultra-high pressure mercury lamp with a wavelength of 365 nm and an illuminance of 30 mW/cm 2 to perform a photocuring reaction of the photosensitive portion.

Next, the exposed glass substrate was developed for 60 seconds at 24°C and a pressure of 0.1 MPa using a 0.05% potassium hydroxide aqueous solution to remove the unexposed portion of the coating film. After that, heat curing was performed at 230°C for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition.

The shape of the spacer was evaluated by the internal angle (taper angle) of the end of the spacer using a scanning electron microscope. When the taper angle was 70° or more and 90° or less, it was designated as ◎, when it was 50° or more and less than 70°, it was designated as ○, when it was 50° or less, it was designated as △, and when it was 90° or more, it was designated as ×.

From the results of Examples 1 to 7 and Comparative Examples 1 to 2, the cured product of the photosensitive resin composition of the present invention, when used as a black column spacer, has high light blocking properties (optical density) and insulation (volume resistivity), and has high compressibility and elastic recovery rate. , it is possible to form a light-shielding film with a spacer function and excellent breaking strength, and it is also possible to form a step of ΔH, thereby forming a pattern shape that is closer to vertical.

Next, in order to confirm whether it is possible to form a pattern by exposure and development so that the cross-sectional shape is a combination of trapezoids or rectangles with different base lengths, the photosensitive resins of Examples 8 and 9 and Comparative Examples 3 and 4 were used. The composition was mixed as shown in Table 3 to obtain a photosensitive resin composition.

Except for the photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 and 2 and the shape of the spacer, the same evaluation was performed using the photosensitive resin compositions of Examples 8 and 9 and Comparative Examples 3 and 4, and the evaluation results are shown in Table 4. Organized. And, regarding the shape of the spacer, the detailed cross-sectional shape of the formed pattern was observed using a separate evaluation method shown below.

<Detailed cross-sectional shape of spacer>

Each photosensitive resin composition obtained in Examples 8 and 9 and Comparative Examples 3 and 4 was applied to a 1.2 mm thick glass substrate using a spin coater so that the film thickness after heat curing was 3.0 ㎛, and incubated at 90°C for 1 minute. It was pre-baked. Afterwards, photomasks (halftone masks) with different line patterns with a total light transmittance of 20% and 100% were fixed at a distance of 200㎛ from the film surface, and illuminated with an ultra-high pressure mercury lamp with a wavelength of 365nm and an illuminance of 30mW/cm2. UV rays of 100 mJ/cm2 were irradiated to perform a photocuring reaction of the photosensitive portion. The photomask was a halftone mask in which the area 25 μm to the left and right from the center of the mask opening had a total line transmittance of 100%, and the area outside the mask opening 25 μm to 100 μm from the center had a total line transmittance of 20%.

Next, the exposed glass substrate was developed for 180 seconds at 24°C and a pressure of 0.1 MPa using a 0.05% potassium hydroxide aqueous solution to remove the unexposed portion of the coating film. After that, heat curing was performed at 230°C for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition.

The cross-sectional shape of the spacer was obtained by obtaining the height profile of the pattern in white vertical scanning interferometry (VSI) using a three-dimensional white light interference optical microscope (Contour GT-K, manufactured by Bruker Corp.), and then plotting it in two dimensions. This was obtained as a cross-sectional shape. 1 to 4 show the two-dimensional plotted cross-sectional shape. Figure 1 is a height profile of a pattern formed using the photosensitive resin composition of Example 8, Figure 2 is a height profile of a pattern formed using the photosensitive resin composition of Example 9, and Figure 3 is a height profile of a pattern formed using the photosensitive resin composition of Example 3. This is the height profile of a pattern formed using the resin composition, and Figure 4 is the height profile of the pattern formed using the photosensitive resin composition of Comparative Example 4. 1 to 4 show the distance from the mask opening on the horizontal axis, and the film thickness on the vertical axis. Additionally, the line indicated by M represents the center of the mask opening. The line indicated by R represents the central part of the area with a total line transmittance of 20%. The line indicated by R appears on both sides with respect to the center of the mask opening, but only one side is shown in FIGS. 1 to 4.

As shown in Figures 1 and 2, by using the photosensitive resin composition of the present invention and performing exposure development using a halftone mask, the cross-sectional shape is trapezoidal with different base lengths, as shown in Figures 1 and 2. Alternatively, it was possible to form BCS in a rectangular combination shape in batches.

As shown in Figures 3 and 4, in Comparative Examples 3 and 4 using a resin other than the alkali-soluble resin containing a polymerizable unsaturated group of the present invention, the cross-sectional shape of the BCS is a combination of trapezoids or rectangles with different base lengths. could not be formed in batches, and only patterns with a trapezoidal or rectangular cross-sectional shape or patterns with a semicircular cross-sectional shape were obtained.

Claims (16)

Contains components (A) to (E) as essential ingredients,
(A) Contains 5 to 90 mol% of the unit represented by the general formula (1) and 10 to 95 mol% of the unit represented by the general formula (2) (the unit represented by the general formula (1) and the general formula ( 2) An alkali-soluble resin containing a polymerizable unsaturated group (represented by the general formula ( (excluding those containing residues from the compound),


[However, R ₁ , R ₃ and R ₄ independently represent a hydrogen atom or a methyl group. R ₂ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain an ether bond, an ester bond, or a urethane bond therein. In addition, 40 mol% or more of R ₂ in the units represented by the general formula (1) is a dicyclopentanyl group or a dicyclopentenyl group. R ₅ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. p represents the number 0 or 1. _Where Includes more than one species.]

[In the formula, Ra to Re each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a substituent.]
(B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds,
(C) photopolymerization initiator,
(D) at least one light-shielding component selected from the group consisting of black organic pigments, mixed-color organic pigments, and light-shielding materials, and
(E) solvent;
10 to 150 parts by mass of component (B) based on 100 parts by mass of component (A), and 0.1 to 30 parts by mass of component (C) based on 100 parts by mass of the total amount of component (A) and component (B), after photocuring. When the components including component (B) and excluding component (E) are referred to as solid components, component (D) is included in 5 to 80% by mass of the total amount of solid content, and (A) to (D) are included in the solid content. A photosensitive resin composition for a light-shielding film, characterized in that it contains 80% by mass or more of components in total. According to claim 1,
The alkali-soluble resin containing a polymerizable unsaturated group as the component (A) is a unit and/or a monomaleimide compound derived from styrene, which may have a substituent on the phenyl group in addition to the units of the general formula (1) and (2). A photosensitive resin composition that is a copolymer containing units derived from. The method of claim 1 or 2,
(D) A photosensitive resin composition comprising, as a light-shielding component, a black organic pigment and/or a mixed-color organic pigment, wherein the black organic pigment and/or the mixed-color organic pigment have an average secondary particle size of 20 to 500 nm. delete The method of claim 1 or 2,
It is a light-shielding film with an optical density (OD) of 0.5/㎛ or more and 3/㎛ or less, and is characterized by being able to form a light-shielding film with a volume resistivity of 1×10 ⁹ Ω·cm or more when a voltage of 10 V is applied and a dielectric constant of 2 to 10. A photosensitive resin composition. The method of claim 1 or 2,
A photosensitive resin composition capable of forming a light-shielding film that satisfies at least one of the following (i) to (iii) in a load-unload test using a microhardness meter.
(i) Having a breaking strength of 200 mN or more
(ii) Elastic recovery rate of 30% or more
(iii) Compression ratio of 40% or less A light-shielding film, characterized in that it is a cured product of the photosensitive resin composition according to claim 1 or 2. A liquid crystal display device comprising the light-shielding film according to claim 7 as a black column spacer (BCS). According to claim 8,
A liquid crystal display device further comprising a thin film transistor (TFT). A liquid crystal display device comprising a cured product of the photosensitive resin composition according to claim 1 or 2 as a black matrix. According to claim 10,
A liquid crystal display device further comprising a thin film transistor (TFT), wherein the black matrix is disposed between the liquid crystal and a substrate facing the array substrate on which the thin film transistor (TFT) is formed. According to claim 10,
A liquid crystal display device further comprising a thin film transistor (TFT), wherein the black matrix is disposed between the liquid crystal and an array substrate on which the thin film transistor (TFT) is formed. A method for manufacturing a light-shielding film formed on a substrate by applying the photosensitive resin composition according to claim 1 or 2 to the substrate and curing the photosensitive resin composition by light irradiation, wherein the optical density as the light-shielding film is 0.5/μm or more. Regarding the film thickness (H1) to be less than ㎛ and the film thickness (H2) of the light-shielding film that functions as a spacer, when H2 is 1 to 7㎛, the film thickness (H1) is ΔH = H2-H1 of 0.1 to 6.9. A method of manufacturing a light-shielding film with a spacer function, characterized in that a light-shielding film with a film thickness (H2) is simultaneously formed. According to claim 13,
A method of manufacturing a light-shielding film in which a light-shielding film including a portion having the film thickness (H1) and a portion having the film thickness (H2) is formed in a single light-shielding film through one exposure. A method of manufacturing a liquid crystal display device, characterized in that the light-shielding film manufactured by the method according to claim 13 is used as a black column spacer (BCS). According to claim 15,
A method of manufacturing a liquid crystal display device, characterized in that the liquid crystal display device has a thin film transistor (TFT).