CN115145114A

CN115145114A - Photosensitive resin composition for light-shielding film, and light-shielding film, color filter and display device using same

Info

Publication number: CN115145114A
Application number: CN202210292718.7A
Authority: CN
Inventors: 原口健太郎; 小野悠树
Original assignee: Nippon Steel and Sumikin Chemical Co Ltd
Current assignee: Nippon Steel Chemical and Materials Co Ltd
Priority date: 2021-03-31
Filing date: 2022-03-23
Publication date: 2022-10-04
Also published as: TW202303283A; KR20220136171A

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, which can obtain the light-shielding film capable of achieving both high light-shielding and high resistance and having excellent development adhesion when a thin line is formed. 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, characterized in that: 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 to 400g/eq.

Description

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

Technical Field

The present invention relates to a photosensitive resin composition for a light-shielding film suitable for forming a black matrix (black matrix) having a high light-shielding and high-resistance fine line pattern, and a light-shielding film, a color filter and a display device using the same.

Background

A color filter is one of important members affecting visibility of a liquid crystal display device, and in order to improve visibility, that is, to obtain a clear image, it is necessary to achieve higher color purity of pixels such as red (R), green (G), and blue (B) constituting the color filter than before and to achieve high light shielding in a black matrix, and therefore, it is necessary to add a larger amount of a colorant than before to a photosensitive resin composition.

Carbon black is generally known as a light-shielding material for a resin black matrix, but carbon black is excellent in light-shielding properties, and on the other hand, has low electric resistance, and thus may cause malfunction of a display device. Therefore, as a method of increasing the resistance of the black matrix by using carbon black, a method of reducing the ratio of carbon black having conductivity or a method of applying a material in which a resin is coated on the surface of carbon black in advance has been proposed, but the light-shielding degree achievable while sufficiently maintaining the patterning property is limited, and it is difficult to achieve the required high light-shielding property.

Further, the applicant of the present application has proposed the following method, accepting the prior art as described above: an alkali-soluble resin having a specific structure and acid value and containing a polymerizable unsaturated group is blended so as to maintain the optical density OD and the volume resistivity and to form a layer having a thickness of 10 [ mu ] m or less and the like, and also has excellent development adhesion even in the case of thin lines, and can sufficiently ensure adhesion to a glass substrate (see patent document 1). However, in the above method, the characteristics required for the black matrix are also increasing with the increase in performance of the display device, and therefore, there is room for further improvement in both high light shielding and high resistance.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent laid-open No. 2015-200881 publication

[ patent document 2] Japanese patent laid-open No. 2014-145821

[ patent document 3] Japanese patent laid-open publication No. 2019-070720

Disclosure of Invention

[ problems to be solved by the invention ]

Therefore, the inventors of the present application have received the above-described previous attempts and further studied a photosensitive resin composition for a light-shielding film which can achieve both high light shielding and high resistance, and then have obtained the following idea.

Namely, there are obtained: in order to achieve high light shielding, a large amount of carbon black as a light shielding material is blended, but a method of achieving high resistance without reducing the amount thereof is proposed, in which the probability of contact between carbon blacks, that is, the idea of preventing contact between carbon blacks by suppressing thermal shrinkage at the time of thermal curing of a light shielding film is reduced, and in addition, it is known that a general carbon black which is not treated or subjected to oxidation treatment has a large amount of acidic functional groups on the surface thereof, and it is significant to blend another compound having a functional group which can react preferentially with the carbon black during thermal curing of the light shielding film, and the like, so that such another resin or the like is present in the vicinity of the surface of the carbon black.

Further, with respect to such an idea, a compound having high heat resistance which can suppress thermal shrinkage at the time of thermal curing and having a functional group which can react preferentially with an acidic functional group of carbon black at the time of thermal curing has been studied in an effort, and as a result, it has been newly found that: by blending a predetermined amount of a predetermined epoxy compound in a photosensitive resin composition, a cured product (light-shielding film) which can achieve both high light-shielding and high resistance and which is excellent in development adhesion even when a thin line of, for example, 3 to 8 μm is formed, the predetermined epoxy compound has an aromatic ring in the main chain and a rigid skeleton, and has a glycidyl group capable of reacting with an acidic functional group of carbon black during thermosetting.

Further, as a technique for blending an epoxy compound in a photosensitive resin composition, the present applicant has also proposed (see patent documents 2 and 3), and the technique described in patent document 2 relates to a black photosensitive resin composition for touch panel applications, and discloses that a relatively large amount of an epoxy compound is contained to satisfy a requirement of high chemical resistance against chemicals used in processing. In addition, patent document 3 is characterized in that: in order to form a resin film pattern on a plastic substrate or the like having a high heat resistance of 140 ℃, a curing agent and/or a curing accelerator must be added to the photosensitive resin composition, and the total amount of these and an epoxy compound is set to a specific range.

That is, the compositions described in patent documents 2 and 3 require the above-described formulation, and it is difficult to satisfy all of high light-shielding, high resistance, and fine wiring.

Accordingly, the present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a photosensitive resin composition for a light-shielding film, which can form a cured product (light-shielding film) that can achieve both high light shielding and high electrical resistance and that has excellent development adhesion even when a thin line is formed.

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

[ means for solving problems ]

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) 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) Containing carbon black as a light-shielding component,

(E) Photopolymerization initiator, and

(F) A solvent, and the photosensitive resin composition for a light-shielding film is characterized in that:

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 to 400g/eq.

[ 2] the photosensitive resin composition for a light-shielding film according to [ 1], characterized in that: (B) The mass ratio (B)/(C) of the component (C) to the component (B) is 50/50 to 90/10, the component (A) is contained in an amount of 0.5 to 15 parts by mass per 100 parts by mass of the component (D), and the component (D) is contained in an amount of 40 to 70% by mass in the solid content of the photosensitive resin composition for a light-shielding film.

[ 3] A light-shielding film, characterized in that: the photosensitive resin composition for a light-shielding film according to [ 1] or [ 2] is cured.

[ 4] A color filter, characterized in that: comprising the light-shielding film according to [ 3 ].

A display device having the color filter according to [4 ].

[ Effect of the invention ]

According to the present invention, there can be provided a photosensitive resin composition for a light-shielding film, which can obtain a cured product (light-shielding film) having both high light-shielding and high resistance and excellent development adhesion even when a thin line of, for example, 3 to 8 μm is formed.

Detailed Description

As described above, the photosensitive resin composition for a light-shielding film of the present invention contains at least (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. Hereinafter, these components will be mainly described in detail.

< epoxy Compound (A) >

The epoxy compound (a) in the photosensitive resin composition for a light-shielding film of the present invention needs to have an aromatic ring in the main chain. It is preferable that the photosensitive resin composition for a light-shielding film of the present invention, which contains an aromatic ring in the main chain, has excellent heat resistance and mechanical properties, and can suppress thermal shrinkage that occurs when the light-shielding film is formed by heat curing. Here, having a main chain means that at least one aromatic ring is present in the structure of the skeleton of the molecule having the largest number of carbon atoms as is generally used in the art. The aromatic ring includes a benzene ring, a naphthalene ring, a biphenyl ring, a bisphenol ring, and the like, and the structures thereof may be unsubstituted or each independently have one or more substituents. The substituent may be an alkyl group or an aryl group having 1 to 10 carbon atoms, and is not particularly limited as long as it is within the target range of the present invention.

The component (A) preferably has an epoxy equivalent of 100 to 400g/eq, preferably 120 to 380g/eq, and more preferably 150 to 360 g/eq. When the epoxy equivalent is less than 100g/eq, the component (B) may react with an acidic functional group responsible for development solubility, and the developability may be lowered, whereas when the epoxy equivalent exceeds 400g/eq, the control of the distance between carbon blacks may be insufficient, and the resistance may not be expected to be increased.

In the component (a), the number of aromatic rings per number of glycidyl groups is 0.5 to 10, preferably 1.1 to 4, more preferably 1.3 to 4, and particularly preferably 2 to 4, based on the number of glycidyl groups. The number of aromatic rings mentioned here is the number of benzene rings, and is, for example, 2 in the case of a naphthalene ring, 2 in the case of a biphenyl ring, 3 in the case of an anthracene ring, and 4 in the case of a bisphenol fluorene ring. The aromatic ring is preferably a bulky (having a large number of aromatic rings), and 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 is a concern that: the resistance is lowered due to the lowering of heat resistance caused by the small number of aromatic rings, or the developability is lowered due to the reaction with an acidic functional group responsible for developability contained in the component (B) caused by the large number of glycidyl groups. On the contrary, when the number of aromatic rings/number of glycidyl groups exceeds 10, there is a concern that: since the number of glycidyl groups is small, the control of the distance between carbon blacks is poor, and the improvement of the resistance cannot be expected.

Here, the number of aromatic rings/number of glycidyl groups are known as follows: the epoxy equivalent can be calculated from the epoxy equivalent based on the proportional relationship between the number of aromatic rings/the number of glycidyl groups and the epoxy equivalent in consideration of the repeating unit of the epoxy compound as shown below. That is, although the number of aromatic rings or the number of glycidyl groups varies depending on the chemical structure or the repeating unit of each epoxy compound, the number of aromatic rings/the number of glycidyl groups can be calculated from the measured value of the epoxy equivalent by obtaining a relational expression with respect to the epoxy equivalent in advance by specifically fitting a plurality of repeating units as described above. Here, specific examples thereof are shown by way of example of compounds listed in the following chemical formulae (1) to (4), and epoxy compounds other than these can be similarly obtained.

Bisphenol fluorene type epoxy compound

[ solution 1]

In the case of said formula (1), the number of aromatic rings/number of glycidyl groups = (4 m) ₁ + 4)/2, e.g. at m ₁ And 4 in the case of =1. At this time, the epoxy equivalent was 435. Likewise, m ₁ Number of aromatic rings/number of glycidol groups at =2 is 6, and epoxy equivalent is 638. From the above relationship, (epoxy equivalent) =102 × (aromatic ring number/number of glycidyl groups) +28, and therefore the aromatic ring number/number of glycidyl groups can be calculated from the epoxy equivalent.

1,6 Naphthdiol aralkyl epoxy Compound

[ solution 2]

In the case of said formula (2), the number of aromatic rings/number of glycidyl groups = (3 m) ₂ +2)/(2m ₂ + 2), e.g. at m ₂ 1.25 in the case of =1. At this time, the epoxy equivalent was 162. Likewise, m ₂ The number of aromatic rings/the number of glycidyls in the case of =2 was 1.33, and the epoxy equivalent was 170. According to the above relationship, (epoxy equivalent) =102 × (number of aromatic rings/number of glycidyl groups) +34.

1-Naphthol aralkyl type epoxy compound

[ solution 3]

In the case of said formula (3), the number of aromatic rings/number of glycidyl groups = (3 m) ₃ +2)/(m ₃ + 1), e.g. at m ₃ And 2.5 in the case of =1. At this time, the epoxy equivalent was 252. Likewise, m ₃ The number of aromatic rings/number of glycidyl groups was 2.67 and the epoxy equivalent was 269 in the case of = 2. The epoxy equivalent is (epoxy equivalent) =102 × (aromatic ring number/glycidyl group number) -3 according to the above relationship.

Epoxy compounds of phenol novolak type

[ solution 4]

In the case of said formula (4), the number of aromatic rings/number of glycidyl groups = (m) ₄ +2)/(m ₄ + 2) is (aromatic ring number/glycidyl group number) =1 irrespective of epoxy equivalent.

As the component (A), a component having a weight average molecular weight of 300 to 10000 is preferably used.

The epoxy compound (a) is not particularly limited as long as it is an epoxy compound having an aromatic ring in the main chain, and examples thereof include: bisphenol a type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, bisnaphthol fluorene type epoxy compounds, diphenylfluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (for example, NC-7000L manufactured by japan chemical company), 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, copolymers of monomers containing a (meth) acrylic acid group as a unit represented by copolymers of methacrylic acid and glycidyl methacrylate, epoxy compounds having a silicone skeleton, and the like. Among them, polycyclic aromatic epoxy compounds are preferably used from the viewpoint of good affinity with carbon black.

In addition, the component (a) may be used as a single compound or as a combination of two or more compounds.

The amount of the component (a) to be blended is preferably 1 to 25 parts by mass, more preferably 1 to 18 parts by mass, and still more preferably 1.5 to 16 parts by mass, based on 100 parts by mass of the total of the components (B) and (C) described later. The amount of the component (B) and the component (C) is preferably set to the above amount, because good patterning characteristics can be obtained.

Further, the component (a) is preferably blended in a range of 0.5 to 15 parts by mass, more preferably 1 to 13 parts by mass, and still more preferably 1.0 to 9.0 parts by mass, based on 100 parts by mass of the component (D) described later. By optimizing the amount of carbon black as described above, it is possible to maintain good affinity with carbon black and achieve both sufficient light-shielding properties and resistance, and therefore, it is preferable.

Alkali-soluble resin having polymerizable unsaturated group (B)

The alkali-soluble resin containing a polymerizable unsaturated group (B) in the photosensitive resin composition for a light-shielding film of the present invention can be used without particular limitation if it has a polymerizable unsaturated group and an acid group in the molecule, and a first example which can be preferably used is an epoxy (meth) acrylate adduct obtained by reacting a compound having two or more epoxy groups with (meth) acrylic acid (which means acrylic acid and/or methacrylic acid) and reacting (a) a dicarboxylic acid or tricarboxylic acid or acid monoanhydride thereof and/or (B) a tetracarboxylic acid or acid dianhydride thereof with the obtained epoxy (meth) acrylate compound having a hydroxyl group. Examples of the compound having two or more epoxy groups derived as an epoxy (meth) acrylate acid adduct include bisphenol type epoxy compounds and novolak type epoxy compounds. Specifically, bisphenol type epoxy compounds represented by the following general formula (I) can be suitably exemplified.

[ solution 5]

In the formula of the general formula (I), R ₁ 、R ₂ 、R ₃ And R ₄ Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, 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 a direct bond. 1 is an integer of 0 to 10. Preferred R ₁ 、R ₂ 、R ₃ 、R ₄ As a hydrogen atom, preferred A is fluorene-9,9-diyl. In addition, since a plurality of values are usually mixed in 1, the average value is 0 to 10 (not limited to an integer), and the average value of 1 is preferably 0 to 3.

The bisphenol epoxy compound is an epoxy compound having two glycidyl ether groups obtained by reacting a bisphenol with epichlorohydrin, and generally includes an epoxy compound having two or more bisphenol skeletons, accompanied by oligomerization of the glycidyl ether compound. The 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) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 3535 zxft 7935-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-4284-dimethylphenyl) fluorene, 3525-bis (4-hydroxy-3-methoxyphenyl) fluorene, 3525 zxft 3535-bis (4-hydroxy-3-dichlorophenyl) fluorene, 345756' -bis (345749-hydroxy-3-dichlorophenyl) fluorene, 345756-bisphenol [ 3425-hydroxy-325756-dichlorophenyl ] fluorene, and the like. Of these, bisphenols having a fluorene-9,9-diyl group may be particularly preferably used.

As the acid monoanhydride of the (a) dicarboxylic acid or tricarboxylic acid which is reacted with the epoxy (meth) acrylate, an acid monoanhydride of a chain hydrocarbon dicarboxylic acid or tricarboxylic acid, or an acid monoanhydride of an alicyclic dicarboxylic acid or tricarboxylic acid, an acid monoanhydride of an aromatic dicarboxylic acid or tricarboxylic acid may be used. Examples of the acid monoanhydride of the chain hydrocarbon dicarboxylic acid or tricarboxylic acid include succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and the like, and further, may be an acid monoanhydride of a dicarboxylic acid or tricarboxylic acid to which an arbitrary substituent is introduced. Examples of the acid monoanhydride of the alicyclic dicarboxylic acid or tricarboxylic acid include acid monoanhydrides such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, hexahydrotrimellitic acid, and norbornanedicarboxylic acid, and further, acid monoanhydrides of dicarboxylic acids or tricarboxylic acids having an optional substituent introduced thereinto. Further, examples of the acid monoanhydride of the aromatic dicarboxylic acid or tricarboxylic acid include acid monoanhydrides such as phthalic acid, isophthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid, and 2,3-naphthalenedicarboxylic acid, and further, acid monoanhydrides of dicarboxylic acids or tricarboxylic acids having an arbitrary substituent introduced thereto may be used.

As the acid dianhydride of the tetracarboxylic acid (b) to be reacted with the epoxy (meth) acrylate, an acid dianhydride of a chain hydrocarbon tetracarboxylic acid, an acid dianhydride of an alicyclic tetracarboxylic acid, or an acid dianhydride of an aromatic tetracarboxylic acid can be used. Examples of the acid dianhydride of the chain hydrocarbon tetracarboxylic acid include acid dianhydrides of butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and the like, and further, acid dianhydrides of tetracarboxylic acids having an arbitrary substituent introduced therein may be used. Examples of the acid dianhydride of the alicyclic tetracarboxylic acid include acid dianhydrides of cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, and the like, and further acid dianhydrides of tetracarboxylic acids having an arbitrary substituent introduced therein. Further, as the acid dianhydride of the aromatic tetracarboxylic acid, for example, there can be mentioned acid dianhydrides of pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, biphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, naphthalene-2,3,6,7-tetracarboxylic acid and the like, and further, there can be mentioned acid dianhydrides of tetracarboxylic acids having an arbitrary substituent introduced therein.

The molar ratio (a)/(b) of the acid anhydride of the (a) dicarboxylic acid or tricarboxylic acid reacted with the epoxy (meth) acrylate to the acid dianhydride of the (b) tetracarboxylic acid is preferably 0.01 to 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 preferable because an optimum molecular weight for producing a photosensitive resin composition having a good photo-patterning property can be easily obtained and alkali solubility is not impaired.

The epoxy (meth) acrylate acid adduct can be produced by a known method, for example, a method described in Japanese patent application laid-open No. 8-278629 or Japanese patent application laid-open No. 2008-9401. First, as a method for reacting (meth) acrylic acid with an epoxy compound, for example, there is a method of: (meth) acrylic acid in an amount equivalent to the epoxy group of the epoxy compound is added to a solvent, and the mixture is heated and stirred at 90 to 120 ℃ in the presence of a catalyst (triethylbenzylammonium chloride, 2,6-diisobutylphenol, etc.) while blowing air. 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 of: the epoxy acrylate compound, acid dianhydride and acid monoanhydride are added to a solvent in predetermined amounts, and the mixture is heated and stirred at 90 to 130 ℃ in the presence of a catalyst (tetraethylammonium bromide, triphenylphosphine, or the like) to react. The epoxy acrylate acid adduct obtained by the method has a skeleton of the general formula (II).

[ solution 6]

[ in the formula (II), R ₁ 、R ₂ 、R ₃ And R ₄ Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, 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 a direct bond, X represents a tetravalent carboxylic acid residue, Y ₁ And Y ₂ Each independently represents a hydrogen atom or-OC-Z- (COOH) _m (wherein Z represents a divalent or trivalent carboxylic acid residue, m represents a number of 1 to 2, and n represents an integer of 1 to 20.)

Other examples of the component (B) include resins having a (meth) acrylic group and a carboxyl group in a copolymer such as (meth) acrylic acid and (meth) acrylic ester. For example, the resin is a polymerizable unsaturated group-containing alkali-soluble resin obtained by: in the first step, a copolymer is obtained by copolymerizing (meth) acrylates containing glycidyl (meth) acrylate in a solvent, in the second step, (meth) acrylic acid is reacted with the obtained copolymer, and in the third step, an anhydride of a dicarboxylic acid or tricarboxylic acid is reacted.

As another example of the component (B), there can be mentioned a urethane compound obtained by reacting a polyol compound having an ethylenically unsaturated bond in the molecule as a first component, a diol compound having a carboxyl group in the molecule as a second component, and a diisocyanate compound as a third component. As the resin of the system, a resin shown in Japanese patent laid-open publication No. 2017-76071 can be referred to.

(B) The alkali-soluble resin containing a polymerizable unsaturated group as the component (B) is preferably blended in an amount of 10 to 40% by mass based on the solid content of the photosensitive resin composition for a light-shielding film of the present invention, more preferably, it is 20 to 40% by mass. The weight average molecular weight (Mw) is preferably 2000 to 10000, more preferably 3000 to 7000. If the weight average molecular weight (Mw) is less than 2000, the adhesion of the pattern during development cannot be maintained, pattern peeling occurs, when the weight average molecular weight (Mw) exceeds 10000, development residue or a film residue at unexposed portions tends to remain. Further, it is preferable that the acid value of the component (B) is in the range of 30 to 200 KOHmg/g. The reason is that: if the value is less than 30KOHmg/g, the alkali development may not be smoothly performed or special developing conditions such as strong alkali may be required, and if it exceeds 200KOHmg/g, the penetration of the alkali developing solution becomes too fast, and the peeling development is likely to occur.

In addition, as the alkali-soluble resin containing a polymerizable unsaturated group as the component (B), only one kind thereof may be used, or a mixture of two or more kinds thereof may be used.

[ C ] photopolymerizable monomer having at least one ethylenically unsaturated bond >

The photopolymerizable monomer (C) having at least one ethylenically unsaturated bond in the photosensitive resin composition for a light-shielding film of the invention includes, for example: (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyhexyl (meth) acrylate and the like having a hydroxyl group, or ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, butanediol 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 di (meth) acrylate, glycerol tri (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide-modified hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate and the like, and dendrimers having a (meth) acryloyl group may be used. Examples of the dendritic polymer having a (meth) acryloyl group include known dendritic polymers obtained by adding a thiol group in a polythiol compound to a part of a carbon-carbon double bond in a (meth) acryloyl group in a polyfunctional (meth) acrylate compound.

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

The blending amount of the component (C) is 50/50 to 90/10, preferably 60/40 to 80/20 in terms of the mass ratio (B)/(C) as the blending ratio with the component (B). If the blending ratio of the component (B) is less than 50/50, there is a concern that: the cured product after photo-curing becomes brittle, and the acid value of the coating film in the unexposed portion is low, so that the solubility in an alkali developing solution is lowered, and the edge of the pattern is not sharp with jaggies. When the blending ratio of the component (B) is more than 90/10, the ratio of the photoreactive functional group in the resin is small, the formation of the crosslinked structure is insufficient, and further, the acid value of the resin component is too high and the solubility of the exposed portion in an alkali developing solution may be high, so that the following problems may occur: the formed pattern becomes thinner than the target line width, or the pattern is likely to be peeled off.

< D) light-screening component containing carbon black as light-screening material >

The light-shielding component (D) in the photosensitive resin composition for a light-shielding film of the present invention should contain untreated or oxidized carbon black. Here, the non-treatment means that a special surface treatment such as an oxidation treatment or a resin coating treatment is not performed, and the oxidation treatment means that the surface of carbon black is treated with an oxidizing agent before the dispersion step. Such untreated or oxidation-treated carbon black has a large amount of acidic functional groups on the surface, and therefore it is important that a large amount of the component (a) is present in the vicinity of the carbon black by reacting with the glycidyl group of the component (a) at the time of thermal hardening at the time of obtaining a light-shielding film. Further, when carbon black is used and the resistance value of the light-shielding film is to be further increased, surface-coated carbon black in which the surface of carbon black is coated with a dye, a pigment, a resin, or the like can be used. Among these, it is preferable to add carbon black in an amount of 80 mass% or more to the component (D). As the light-shielding component other than carbon black, a light-shielding component selected from a black organic pigment, a mixed color organic pigment, or a light-shielding material can be used, and a component having excellent heat resistance, light resistance, solvent resistance, and the like is preferable. Here, examples of the black organic pigment include: perylene blacks, aniline blacks, cyanine blacks, lactam blacks, and the like. Examples of the mixed color organic pigment include those prepared by mixing two or more pigments selected from red, blue, green, violet, yellow, cyanine, and magenta to form a pseudo-black color. 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 may be appropriately selected and used.

The light-shielding component is preferably prepared as a light-shielding dispersion by dispersing the light-shielding component in the (F) solvent together with a dispersant in advance, and then the resulting dispersion is used as a light-shielding resin composition for a light-shielding film. Since the solvent to be dispersed is a part of component (F) described later, any solvent listed as the above-mentioned component (F) can be used, and for example, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and the like can be suitably used. The blending ratio of the component (D) forming the light-shielding dispersion is preferably in the range of 40 to 70 mass%, particularly preferably in the range of 40 to 60 mass%, relative to the total solid content of the photosensitive resin composition for a light-shielding film of the present invention.

As the dispersant, known dispersants such as various polymer dispersants can be used. Examples of the dispersant include, but are not limited to, known compounds (commercially available compounds under the names of dispersants, dispersion wetting agents, dispersion accelerators, and the like) which have been used for pigment dispersion in the past, and examples thereof include: a cationic polymer dispersant an anionic polymer dispersant nonionic polymer dispersants, pigment derivative dispersants (dispersing aids), and the like. Particularly preferred is a cationic polymer dispersant having a cationic functional group such as an imidazole group, a pyrrole group, a pyridine group, a primary amino group, a secondary amino group or a tertiary amino group as an adsorption site for a pigment, and having an amine value of 1mgKOH/g to 100mgKOH/g and a number average molecular weight in the range of 1 thousand to 10 ten thousand. The amount of the dispersant to be blended is preferably 1 to 30% by mass relative to the light-shielding component (D).

< E) photopolymerization initiator

Examples of the photopolymerization initiator (E) in the photosensitive resin composition for a light-shielding film of the present invention include: acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropylketone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, benzyl dimethyl ketal, etc.; benzophenones such as benzophenone, 2-chlorobenzophenone, p '-bisdimethylaminobenzophenone, 4,4' -bisdimethylaminobenzophenone (michelson), 4-phenylbenzophenone, 4,4 '-dichlorobenzophenone, hydroxybenzophenone, 4,4' -diethylaminobenzophenone, and the like; benzoin ethers such as benzil, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; biimidazole compounds such as 2- (o-chlorophenyl) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-bis (m-methoxyphenyl) 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; halomethyl oxadiazole compounds such as 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-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 halomethyl-s-triazine compounds such as 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; 1,2-octanedione, 1- [4- (phenylthio) phenyl ] -,2- (O-benzoyloxime), 1- (4-phenylmercaptophenyl) butane-1,2-dione-2-oxime-O-benzoate, 1- (4-methylthiophenyl) butane-1,2-dione-2-oxime-O-acetate, 1- (4-methylthiophenyl) butane-1-ketoxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -bicycloheptyl-1-ketoxime-O-acetate, 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 ] -adamantylmethane-3-yl ] -1-ketoxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -2-oxolane-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-ketoxime-O-acetate, and mixtures thereof 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -morpholinylmethane-1-one oxime-O-benzoate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -morpholinylmethane-1-one oxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethane-1-one oxime-O-bicycloheptane carboxylate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethane-1-one oxime-O-tris Cyclodecane carboxylate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethane-1-ketoxime-O-adamantane carboxylate, 1- [4- (phenylthioyl) 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, ethanone, 1- [7- (2-methylbenzoyl) -9,9-dipropyl-9H-fluoren-2-yl ] -1- (O-acetyl oxime), ethanone, 1- (9,9-dibutyl-7-nitro-9H-fluoren-2-yl) -1-O-acetyl oxime, ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-acetyl-oxime, and the like; sulfur compounds such as thioxanthone, 2-chlorothianthrone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone and 2,3-diphenylanthraquinone; azobisisobutyronitrile, benzoyl peroxide organic peroxides such as cumene peroxide; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, β -mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), tris- [ (3-mercaptopropionyloxy) -ethyl ] -isocyanurate, pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), 3,3' -thiodipropionic acid, dithiodipropionic acid, and laurylthiopropionic acid. Among them, O-acyloxime compounds are preferably used from the viewpoint of easily obtaining a photosensitive resin composition for a light-shielding film with high sensitivity. Two or more of these photopolymerization initiators may also be used. The photopolymerization initiator used in the present invention is intended to include a sensitizer.

Further, it does not act as a photopolymerization initiator or sensitizer by itself, and a compound capable of increasing the capability of the photopolymerization initiator or sensitizer may be added by using it in combination with the above-mentioned compound. Examples of such compounds include amine-based compounds that are effective when used in combination with benzophenone. Examples of the amine-based compound include: triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 4,4' -bis (dimethylamino) benzophenone, 4,4' -bis (diethylamino) benzophenone, 4,4' -bis (ethylmethylamino) benzophenone, and the like.

The blending amount of the component (E) is preferably 2 to 40 parts by mass, more preferably 3 to 30 parts by mass, based on 100 parts by mass of the total of the components (B) and (C).

< solvent (F) >

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

< other ingredients >

The photosensitive resin composition for a light-shielding film of the present invention may optionally contain additives such as a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a coupling agent, a surfactant, and a viscosity modifier. Examples of the thermal polymerization inhibitor and the antioxidant include: hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butyl catechol, phenothiazine, hindered phenol compounds, and the like, and examples of the plasticizer include: dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like, and examples of the filler include: glass fiber, silica, mica, alumina, etc., and examples of the defoaming agent or leveling agent include: silicone, fluorine, and acrylic compounds. In addition, as the surfactant, there can be mentioned: anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether sulfate, cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride, amphoteric surfactants such as lauryldimethylamine oxide and laurylcarboxymethylhydroxyethylimidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and sorbitan monostearate, silicone surfactants having polydimethylsiloxane as a main skeleton, fluorine surfactants, and the like. Examples of coupling agents include: silane coupling agents such as 3- (glycidyloxy) propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.

< solid content >

The photosensitive resin composition for a light-shielding film of the present invention contains the components (A) to (F) as main components. The total amount of the components (a) to (E) is preferably 70% by mass, more preferably 80% by mass or more, and even more preferably 90% by mass or more, of the solid components excluding the solvent (the solid components include the monomer which becomes the solid component after curing). (F) The amount of the solvent varies depending on the target viscosity, and is preferably contained in the range of 60 to 90% by mass in the photosensitive resin composition for a light-shielding film of the present invention.

< method for Forming light-shielding film >

The photosensitive resin composition for a light-shielding film of the present invention is excellent as, for example, a photosensitive resin composition for forming a light-shielding film of a color filter, and a method for forming a light-shielding film includes the following photolithography method. The following methods may be mentioned: first, a photosensitive resin composition is applied onto a transparent substrate, followed by drying with a solvent (prebaking), then a photomask is placed on the coating film obtained in the above manner, ultraviolet rays are irradiated to cure an exposed portion, further, development in which an unexposed portion is eluted is performed using an aqueous alkali solution to form a pattern, and further, post-baking (thermal baking) is performed as post-drying.

Examples of the transparent substrate to which the photosensitive resin composition is applied include a glass substrate, and a substrate in which a transparent electrode such as Indium Tin Oxide (ITO) or gold is deposited or patterned on a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, or the like). As a method for coating the solution of the photosensitive resin composition on the transparent substrate, any method using a roll coater, a disc coater (Land coater machine), a slit coater, a rotary coater, or the like may be used in addition to the known solution dipping method and spraying method. After coating to a desired thickness by these methods, the solvent is removed (prebaked), thereby forming a coating film. The prebaking is performed by heating with an oven, a hot plate, or the like. The heating temperature and the heating time in the prebaking are appropriately selected depending on the solvent used, and are, for example, carried out at a temperature of 60 to 110 ℃ for 1 to 3 minutes.

The exposure after the prebaking is performed by an ultraviolet exposure apparatus, and exposure is performed through a photomask to expose only a portion of the resist corresponding to the pattern. The photosensitive resin composition in the coating film is photo-cured by exposure using a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, or a far ultraviolet lamp, with an exposure apparatus and exposure irradiation conditions appropriately selected.

The alkali development after the exposure is performed for the purpose of removing the resist of the unexposed portion, and a desired pattern is formed by the development. Examples of the developer suitable for the alkali development include an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal, an aqueous solution of a hydroxide of an alkali metal, and the like, and particularly, a weakly alkaline aqueous solution containing 0.05 to 3 mass% of a carbonate such as sodium carbonate, potassium carbonate, or lithium carbonate is preferably used to perform development at a temperature of 23 to 28 ℃.

After the development, it is preferable to perform a heat treatment (post-baking) at a temperature of 180 to 250 ℃ for 20 to 60 minutes. The post baking is performed for the purpose of improving adhesion between the patterned light-shielding film and the substrate. This is performed by heating with an oven, a hot plate, or the like, as in the case of the prebaking. The patterned light-shielding film of the present invention is formed through the above-described steps by photolithography.

As described above, the photosensitive resin composition for a light-shielding film of the present invention is suitable for forming a fine pattern by an operation such as exposure and alkali development. The photosensitive resin composition for a light-shielding film of the present invention is suitably used as a coating material, particularly as an ink for a color filter used in a liquid crystal display device or an image pickup device, and the light-shielding film thus formed is useful as a color filter, a black matrix for liquid crystal projection, a light-shielding film for a touch panel, and the like.

The light-shielding film with high light-shielding and high resistance obtained in the invention can ensure 1 × 10 under the application voltage of 10V when OD is more than 3.9/μm ⁸ Volume resistivity of not less than Ω · cm. 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 to 8 μm are formedAnd (3) distinguishing.

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

[ solid content concentration ]

A glass filter was impregnated with 1g of the resin solution obtained in synthesis example (mass: w ₀ (g) Neutralization and weighing [ W ] ₁ (g) According to mass [ W ] after heating at 160 ℃ for 2hr ₂ (g) And is obtained by the following equation.

Solid content concentration (mass%) =100 × (W) ₂ -W ₀ )/(W ₁ -W ₀ )

[ acid value ]

The resin solution was dissolved in dioxane and titrated with a 1/10N-KOH aqueous solution using a potentiometric titrator (product name COM-1600 manufactured by Hi-Marsh Ltd.).

[ molecular weight ]

The Gel Permeation Chromatography (GPC) method (manufactured by Tosoh, tosoh) under the trade name of HLC-8220GPC, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2 roots) + TSKgelSuperH-3000 (1 root) + TSKgelSuperH-4000 (1 root) + TSKgelSuperH-5000 (1 root) [ manufactured by Tosoh (Strand) ], temperature: 40 ℃, speed: 0.6ml/min, and the weight average molecular weight (Mw) was determined as a value converted to a standard polystyrene (PS-oligomer kit manufactured by Tosoh corporation).

[ epoxy equivalent ]

The measurement target epoxy compound was dissolved in dioxane, and then an acetic acid solution of tetraethylammonium bromide was added thereto, followed by titration with a 1/10N-perchloric acid solution using a potentiometric titrator "COM-1600" (manufactured by heimagawa industries, ltd.).

The abbreviations used in the synthesis examples are as follows.

AA: acrylic acid (acrylic acid)

BPFE:9,9-bis (4-hydroxyphenyl) fluorene with chloromethyl oxacyclopropane. In the compound of the general formula (I), A is fluorene-9,9-diyl, R ₁ ～R ₄ A compound which is a hydrogen atom.

BPDA:3,3',4,4' -Biphenyl Tetracarboxylic dianhydride (3,3 ',4,4' -biphenyl tetracarboxylic dianhydride)

THPA:1,2,3,6-Tetrahydrophthalic anhydride (1,2,3,6-tetra hydro phthalic anhydride)

TPP: triphenylphosphine (triphenylphosphinane)

PGMEA: propylene glycol monomethyl ether acetate

TEAB: tetraethylammonium bromide (tetraethylammonium bromide)

[ Synthesis example 1]

A500 ml four-necked flask equipped with a reflux condenser was charged with 114.4g (0.23 mol) of BPFE, 33.2g (0.46 mol) of AA, 157g of PGMEA, and 0.48g of TEAB, and the mixture was stirred at 100 to 105 ℃ for 20 hours to effect a reaction. Subsequently, 35.3g (0.12 mol) of BPDA and 18.3g (0.12 mol) of THPA were put into the flask, and the mixture was heated at 120 to 125 ℃ and stirred for 6 hours to obtain an alkali-soluble resin solution containing a polymerizable unsaturated group. The resin solution thus obtained had a solid content of 56.1% by mass, an acid value (in terms of solid content) of 103mgKOH/g, and Mw of 3600 as determined by GPC analysis.

[ preparation of photosensitive resin composition for light-shielding film ]

Photosensitive resin compositions of examples 1 to 34, comparative examples 1 to 9, and reference comparative examples 1 to 5 were prepared by blending the components shown in tables 1 to 4. The ingredients used in the formulation were as described below, and the numerical values in the table are in parts by mass.

(A) Epoxy compound (c):

(A) -1: bisphenol fluorene-based epoxy compound [ ESF-300C manufactured by ferrimagnetic chemistry & materials (strand), epoxy equivalent 240, number of aromatic rings relative to number of glycidyl groups: 2.09)

(A) -2:1,6-naphthalenediol aralkyl type epoxy compound [ the compound represented by said formula (2), epoxy equivalent 167, number of aromatic rings relative to number of glycidyl groups: 1.30)

(A) -3: 1-naphthol aralkyl type epoxy compound [ the compound represented by said formula (3), epoxy equivalent 317, number of aromatic rings relative to the number of glycidyl groups: 3.13)

(A) -4: phenol novolac-type epoxy compound [ YDPN-6300 manufactured by hitachi chemical & materials (stock), epoxy equivalent 175, number of aromatic rings relative to the number of glycidyl groups: 1]

(A) -5 the method comprises the following steps: alicyclic epoxy compound [ ZX-1658GS manufactured by nicol & materials (stock), epoxy equivalent 132, number of aromatic rings relative to number of glycidyl groups: 0 ]

(B) Polymerizable unsaturated group-containing alkali-soluble resin:

the alkali-soluble resin solution containing a polymerizable unsaturated group obtained in Synthesis example 1

(C) Photopolymerizable monomer:

mixture of dipentaerythritol pentaacrylate and hexaacrylate [ DPHA, acrylic equivalent 96-115, manufactured by Nippon Kagaku K.K. ]

(D) Pigment dispersion containing light-screening ingredient:

(D) -1: 25.0% by mass of carbon black, 5.0% by mass of a dispersion resin, and 3.5% by mass of a polymer dispersant

(D) -2: pigment dispersion of propylene glycol monomethyl ether acetate solvent containing 25.0% by mass of carbon black and 6.3% by mass of polymeric dispersant

(D) -3: a pigment dispersion of propylene glycol monomethyl ether acetate solvent containing 16.0% by mass of an organic black pigment and 4.8% by mass of a polymeric dispersant

(D) -4: pigment dispersion of propylene glycol monomethyl ether acetate solvent containing 15.0% by mass of titanium black and 4.0% by mass of polymeric dispersant

(D) -5: 25.0% by mass of dye-coated carbon black, 8.1% by mass of a dispersion resin (alkali-soluble resin (component (B) used)) and 2.0% by mass of a polymer dispersant

(E) Photopolymerization initiator:

oxime ester photopolymerization initiator [ Ai Dike (ADEKA) (NCI-831 by Kunststoff.)

(F) Solvent:

(F) -1: propylene glycol monomethyl ether acetate

(F) -2: diethylene glycol dimethyl ether

(F) -3 the method comprises the following steps: diethylene glycol ethyl methyl ether

(F) -4: diethylene glycol dibutyl ether

(G) Silane coupling agent: KBM-803 manufactured by shin-Etsu chemistry

(H) Surfactant (b): BYK-330 manufactured by BYK-Chemie Japan, bi Kehua, inc

[ Table 1]

[ Table 3]

[ Table 4]

[ evaluation ]

The photosensitive resin compositions of examples 1 to 34, comparative examples 1 to 9, and comparative examples 1 to 5 were used to perform the following evaluations. The evaluation results are shown in tables 5 to 8.

< evaluation of OD/. Mu.m >

Using rotationEach of the photosensitive resin compositions obtained above was applied onto a 125mm × 125mm glass substrate (Corning 1737) by a coater so that the film thickness after the post-baking became 1.0 μm, and was prebaked at 90 ℃ for 1 minute. Thereafter, the film was irradiated with i-ray at an illuminance of 30mW/cm without coating a negative photomask ² Is irradiated by an extra-high pressure mercury lamp at 40mJ/cm ² The ultraviolet ray of (2) to perform a photo-curing reaction.

Next, the plate after the completion of the exposure was coated with a 0.04% aqueous solution of potassium hydroxide at 1kgf/cm at 23 ℃ ² The development was carried out for 80 seconds under the shower pressure of (3), and then 5kgf/cm was carried out ² Spray water washing under pressure, and thereafter, post-heat baking at 230 ℃ for 30 minutes using a hot air dryer. The OD value of the coated plate was evaluated using a transmission densitometer. The film thickness of the light-shielding film formed on the coating plate was measured, and the value obtained by dividing the OD value by the film thickness was defined as OD/μm.

< evaluation of residual film ratio after Heat curing >

Each of the photosensitive resin compositions obtained above was coated on a 125mm × 125mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post baking became 3.0 μm, and was prebaked at 90 ℃ for 1 minute, and then the film thickness of a light-shielding film formed on the coated plate was measured. After that, post-baking was performed at 230 ℃ for 180 minutes using a hot air dryer, and then the film thickness of the light-shielding film formed on the coated sheet was measured again, and the film thickness was calculated from the film thickness before and after post-baking based on the following calculation formula.

Residual film ratio (%) = 100X film thickness after post-baking (μm)/film thickness before post-baking (μm)

< evaluation of volume resistivity increase >

Each of the photosensitive resin compositions thus obtained was coated on a 100mm × 100mm chromium deposition glass substrate (Corning 1737) using a spin coater so that the film thickness after post baking became 3.0 μm, and was prebaked at 90 ℃ for 1 minute. Thereafter, after post-baking was performed at 230 ℃ for 180 minutes using a hot air dryer, the volume resistivity at 1V to 10V was measured using an electrometer (manufactured by Keithley, inc., "6517A") under a condition of stepping at 1V and maintaining the voltage at each applied voltage for 60 seconds. The increase in volume resistivity at 10V was calculated based on the following equations for examples 1 to 11 and comparative examples 1 to 3 based on reference comparative example 1 in which component (a) was not used, for examples 12 to 24 based on reference comparative example 2 in which component (a) was not used, for examples 4 to 6 based on reference comparative example 3 in which component (a) was not used, for examples 7 to 9 based on reference comparative example 4 in which component (a) was not used, and for examples 25 to 33 based on reference comparative example 5 in which component (a) was not used. In the following table, the reference person is expressed as "ref.

Degree of rise = volume resistivity (Ω · cm) of each example or comparative example/volume resistivity (Ω · cm) of reference comparative example

The calculated increase degree of volume resistivity is determined based on the following determination criterion.

O: 100 or less volume resistivity rising degree

And (delta): 10 is less than or equal to the volume resistivity rising degree of less than 100

X: volume resistivity rise <10

< evaluation of development characteristics (minimum resolution linewidth) >

Each of the photosensitive resin compositions obtained above was coated on a 125mm × 125mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post baking became 1.2 μm, and was prebaked at 90 ℃ for 1 minute. Then, a negative photomask having a line pattern with an opening width of 1 to 20 μm was closely adhered to the dried coating film, and the illuminance of the negative photomask was 30mW/cm by using i-ray ² Is irradiated by an extra-high pressure mercury lamp at 40mJ/cm ² The ultraviolet ray of (2) to perform a photo-curing reaction of the photosensitive portion.

Next, the plate after the completion of the exposure was immersed in a 0.04% aqueous solution of potassium hydroxide at 23 ℃ at 1kgf/cm ² The development was carried out for +60 seconds from the development time (break time) = BT) at which the pattern appeared after the shower development pressure of (1) and (5) kgf/cm ² Spray washing under pressure to remove unexposed portions of the coating film to form a line pattern on the glass substrate, thereafter, post-heat baking at 230 ℃ for 30 minutes using a hot air dryer, and then obtaining a line pattern, the minimum opening line where pattern peeling was not generated in the obtained line pattern was taken as the minimum resolution line width.

Very good: 2 μm or more and less than 5 μm

O: 5 μm or more and less than 9 μm

And (delta): 9 μm or more and less than 11 μm

X: 11 μm or more

< evaluation of volume resistivity reduction rate (Heat resistance) >

Each of the photosensitive resin compositions obtained in examples 15 to 17 and 34 and comparative reference example 2 was coated on a 100mm × 100mm chromium deposition glass substrate (Corning 1737) so that the film thickness after baking became 3.0 μm by using a spin coater, and was prebaked at 90 ℃ for 1 minute. Thereafter, after post-baking was performed at 230 ℃ for 180 minutes using a hot air dryer, the volume resistivity at applied voltages of 1V to 10V was measured using an electrometer (manufactured by Keithley, inc., "6517A") under the condition of stepping at 1V and holding the voltage at each applied voltage for 60 seconds. In addition, in contrast to these, the thermal post-baking temperature was changed to 270 ℃, and the same procedure was performed in the same manner for each of the photosensitive resin compositions of examples 15 to 17 and example 34 and reference comparative example 2 to measure the volume resistivity.

The decrease rate (absolute value) of the volume resistivity at the time when the temperature of the post-heat baking was changed from 230 ℃ to 270 ℃ was calculated for the volume resistivity at the time of applying 10V based on the following calculation formula. When the reduction rate in reference comparative example 2 is regarded as 1, the relative values [ relative value (x) of the reduction rate ] of each of examples 15 to 17 and 34 with respect to reference comparative example 2 are calculated based on the following calculation formula. In addition, reference comparative example 2 is expressed as "ref" in the following table.

Reduction rate (absolute value) =100 × (logA-logB)/logB

(Here, A is a measurement value of volume resistivity (Ω. Cm) at 270 ℃ in the hot post-baking, and B is a measurement value of volume resistivity (Ω. Cm) at 230 ℃ in the hot post-baking.)

Relative value of reduction rate (x) = reduction rate of each reduction rate of example 15, example 16, example 17, or example 34/reduction rate of reference comparative example 2

The calculated relative value of the reduction rate is determined as heat resistance based on the following determination criteria.

◎：0≤x＜0.5

○：0.5≤x＜0.8

△：0.8≤x＜1.0

×：1.0≤x

[ Table 5]

The results of examples 1 to 34, comparative examples 1 to 9, and comparative examples 1 to 5 are clearly shown below: the volume resistivity is improved by adding an epoxy compound as the component (a) to a photosensitive resin composition containing a light-shielding component containing carbon black as a light-shielding material. Among them, particularly in examples 15 to 17, 21 to 24, and 28 to 30, the increase in volume resistivity is very high and the minimum resolution line width is fine, so that the photosensitive resin composition for a light-shielding film is excellent in development adhesion and combines high light shielding, high resistance, and high definition. It is also understood that the heat resistance is excellent in the case of examples 15 to 17 using the epoxy compounds (A) -1 to (A) -3 in the component (A), and that the heat resistance is more excellent particularly in the case of (A) -1 and (A) -2.

Claims

1. A photosensitive resin composition for a light-shielding film, comprising the following components (A) up to c

(F) The components are used as the necessary components, and the components are mixed,

(A) An epoxy compound,

(B) An alkali-soluble resin containing a polymerizable unsaturated group,

(D) Containing carbon black as a light-shielding component,

(E) Photopolymerization initiator, and

(F) A solvent, a water-soluble organic solvent,

2. The photosensitive resin composition for a light-shielding film according to claim 1, wherein: (B) The mass ratio (B)/(C) of the component (C) to the component (B) is 50/50 to 90/10, the component (A) is contained in an amount of 0.5 to 15 parts by mass per 100 parts by mass of the component (D), and the component (D) is contained in an amount of 40 to 70% by mass in the solid content of the photosensitive resin composition for a light-shielding film.

3. A light-shielding film, characterized in that: the photosensitive resin composition for a light-shielding film according to claim 1 or 2 is cured.

4. A color filter, comprising: comprising the light-shielding film of claim 3.

5. A display device having the color filter according to claim 4.