KR20220080728A - Photosensitive resin composition, cured product, partition wall, organic electroluminescent element, color filter, and image display device - Google Patents

Abstract

(식 (c1) 중, R^c11 은 수소 원자 또는 메틸기를 나타내고, R^c12 는 치환기를 가지고 있어도 되는 2 가의 탄화수소기를 나타내고, n 은 2 또는 3 의 정수를 나타내고, 식 (c1) 중의 벤젠 고리는, 추가로 임의의 치환기에 의해 치환되어 있어도 되고, * 는 각각 결합손을 나타낸다.)The photosensitive resin composition which can ensure sufficient ink repellency even if it is a low exposure amount is provided. The photosensitive resin composition of this invention contains (A) an ethylenically unsaturated compound, (B) a photoinitiator, (C) alkali-soluble resin, and (D) liquid repellent, Said (C) alkali-soluble resin is the following It contains alkali-soluble resin (C-1) which has a partial structure represented by general formula (c1), Said (D) liquid repellent contains the fluorine atom containing resin which has a crosslinking group, It is characterized by the above-mentioned.
[Formula 1]

(in formula (c1), R ^c11 represents a hydrogen atom or a methyl group, R ^c12 represents a divalent hydrocarbon group which may have a substituent, n represents an integer of 2 or 3, and the benzene ring in formula (c1) is, Furthermore, it may be substituted by arbitrary substituents, and * represents a bond, respectively.)

Description

Photosensitive resin composition, cured product, partition wall, organic electroluminescent element, color filter, and image display device {PHOTOSENSITIVE RESIN COMPOSITION, CURED PRODUCT, PARTITION WALL, ORGANIC ELECTROLUMINESCENT ELEMENT, COLOR FILTER, AND IMAGE DISPLAY DEVICE}

This invention relates to the photosensitive resin composition, Further, the hardened|cured material which hardened the photosensitive resin composition; bulkhead composed of hardened material; Organic electroluminescent element provided with a partition, a color filter, and an image display apparatus; is about

This application claims priority based on Japanese Patent Application No. 2019-201108 for which it applied to Japan on November 6, 2019, and uses the content here.

In recent years, color filters in which pixels are formed using luminescent nanocrystal particles such as quantum dots have been studied due to reduction in power consumption and wide color gamut of displays. As a manufacturing method of a color filter, there exist a photolithography method and an inkjet method, and it is known that the latter can reduce the loss of an ink material (for example, refer patent document 1).

In the case of manufacturing a color filter containing luminescent nanocrystal particles by the inkjet method, pixels are formed by discharging ink containing luminescent nanocrystal particles into a region (pixel portion) surrounded by a barrier rib prepared in advance.

Moreover, organic electroluminescent elements used for organic electroluminescent display etc. are manufactured by forming barrier ribs (banks) on a board|substrate, and laminating|stacking various functional layers in the area|region surrounded by the barrier ribs. The inkjet method is known as a method of laminating|stacking a functional layer in a partition.

Neither the partition walls for color filters containing luminescent nanocrystal particles nor the partition walls for organic electroluminescent elements are necessary to prevent mixing of inks between adjacent pixel portions when ink is ejected by inkjet. There is, and high ink repellency is calculated|required.

As a material for forming a barrier rib having ink repellency by photolithography, Patent Document 2 describes that a colored photosensitive resin composition having high ink repellency and good linearity is obtained by using two specific alkali-soluble resins in combination. have.

Moreover, in patent documents 3 and 4, the photosensitive resin composition containing specific resin is described.

Japanese Laid-Open Patent Publication No. 2019-086745 International Publication No. 2019/146685 Japanese Patent Laid-Open No. 2016-047919 Japanese Patent Laid-Open No. 2017-190403

As a result of the present inventors examining, with the photosensitive resin composition of patent document 2, when exposure amount was low, it discovered that it was difficult to ensure sufficient ink repellency.

On the other hand, patent documents 3 and 4 do not have description about a liquid repellent, and it is unknown about the ink repellency at the time of using a liquid repellent.

Then, an object of this invention is to provide the photosensitive resin composition which can ensure sufficient ink repellency even with a low exposure amount.

Moreover, an object of this invention is to provide the hardened|cured material which hardened the said photosensitive resin composition, the partition comprised from this hardened|cured material, and the image display apparatus provided with this partition.

As a result of the present inventors earnestly examining, the photosensitive resin composition containing a liquid repellent WHEREIN: By using specific alkali-soluble resin, it discovered that the said subject was solvable, and came to complete this invention.

That is, the summary of this invention is as follows.

[1] A photosensitive resin composition comprising (A) an ethylenically unsaturated compound, (B) a photoinitiator, (C) an alkali-soluble resin, and (D) a liquid repellent,

Said (C) alkali-soluble resin contains alkali-soluble resin (C-1) which has a partial structure represented by the following general formula (c1),

Said (D) liquid repellent contains the fluorine atom containing resin which has a crosslinking group, The photosensitive resin composition characterized by the above-mentioned.

[Formula 1]

(In formula (c1), R ^c11 represents a hydrogen atom or a methyl group.

R ^c12 represents a divalent hydrocarbon group which may have a substituent.

n represents the integer of 2 or 3.

The benzene ring in Formula (c1) may be further substituted by arbitrary substituents.

* denotes each bond.)

[2] The photosensitive resin composition according to [1], wherein in the general formula (c1), R ^c12 is a group represented by the following general formula (c1-1).

[Formula 2]

[3] The photosensitive resin composition according to [1] or [2], wherein the content ratio of the alkali-soluble resin (C-1) in the (C) alkali-soluble resin is 60 mass% or more.

[4] The photosensitive resin composition according to any one of [1] to [3], further comprising (E) a coloring agent.

[5] The photosensitive resin composition as described in [4] whose content rate of the said (E) coloring agent is 50 mass % or less in total solid of the photosensitive resin composition.

[6] [4] or [5] wherein the (E) colorant contains at least one selected from the group consisting of a red pigment and an orange pigment, and at least one selected from the group consisting of a blue pigment and a purple pigment. ] The photosensitive resin composition as described in.

[7] The photosensitive resin composition according to any one of [4] to [6], wherein the (E) colorant contains a purple pigment.

[8] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [7].

[9] A partition composed of the cured product according to [8].

[10] An organic electroluminescent device comprising the barrier rib according to [9].

[11] A color filter comprising the luminescent nanocrystal particles provided with the partition according to [9].

[12] An image display device comprising the partition wall according to [9].

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which can ensure sufficient ink repellency even if it is a low exposure amount can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section of an example of a color filter provided with the partition of this invention.

Hereinafter, the present invention will be described in detail. In addition, the following description is an example of embodiment of this invention, and this invention is not specific to these unless it departs from the summary.

In addition, in this invention, "(meth)acryl" shall mean "any one or both of acryl and methacryl", and "total solid content" means all components other than the solvent in the photosensitive resin composition. make it mean In addition, in this invention, the numerical range shown using "-" means a range including the numerical value described before and after "-" as a lower limit and an upper limit.

In the present invention, "(co)polymer" means including both a homopolymer (homopolymer) and a copolymer (copolymer), and "(acid) anhydride", "(anhydride)... Acid" means containing both an acid and its anhydride.

In the present invention, a partition material refers to a bank material, a wall material, and a wall material, and similarly, a partition material refers to a bank, a wall, and a wall.

In this invention, a weight average molecular weight means the weight average molecular weight (Mw) of polystyrene conversion by GPC (gel permeation chromatography).

In the present invention, unless otherwise specified, acid value means an acid value in terms of effective solid content, and is calculated by neutralization titration.

In the present invention, the barrier rib can be used as, for example, partitioning a functional layer (organic layer, light emitting portion) in an active driving type organic electroluminescent device, and a functional layer is formed in the partitioned region (pixel region) It can be used in order to form the pixel etc. which contain a functional layer and a partition by discharging and drying the ink which is a material for the following. Moreover, it can be used as a thing for partitioning the pixel part in the color filter containing a luminescent nanocrystal particle, and can be used for forming a pixel by discharging and drying ink in the partitioned area|region.

[1] Photosensitive resin composition

The photosensitive resin composition of this invention contains (A) an ethylenically unsaturated compound, (B) a photoinitiator, (C) alkali-soluble resin, and (D) liquid repellent as essential components, Furthermore, as needed, other The component may be included and the (E) coloring agent, (F) dispersing agent, etc. may be included, for example.

[1-1] Components and composition of photosensitive resin composition

The component which comprises the photosensitive resin composition of this invention, and its composition are demonstrated in order.

[1-1-1] (A) component; ethylenically unsaturated compounds

The photosensitive resin composition of this invention contains (A) an ethylenically unsaturated compound. (A) By including an ethylenically unsaturated compound, sclerosis|hardenability of a coating film becomes high and it is thought that ink repellency improves.

As an ethylenically unsaturated compound as used herein, it means a compound having one or more ethylenically unsaturated bonds in a molecule, which can widen the difference in polymerizability, crosslinkability, and the accompanying solubility in the developer solution of the exposed and unexposed parts. It is preferable that it is a compound having two or more ethylenically unsaturated bonds in the molecule, and the unsaturated bond is derived from a (meth)acryloyloxy group, that is, a (meth)acrylate compound It is more preferable that

In this invention, it is especially preferable to use the polyfunctional ethylenic monomer which has 2 or more of ethylenically unsaturated bonds in 1 molecule. Although the number of ethylenically unsaturated groups which a polyfunctional ethylenic monomer has is not specifically limited, Preferably it is 2 or more, More preferably, it is 3 or more, More preferably, it is 5 or more, More preferably, it is 15 pieces. Below, more preferably, it is 10 or less, More preferably, it is 8 or less, Especially preferably, it is 7 or less. For example, 2-15 pieces are preferable, 2-10 pieces are more preferable, 3-8 pieces are still more preferable, and 5-7 pieces are especially preferable. There exists a tendency for polymerizability to improve and ink repellency to become high by setting it as more than the said lower limit. By using below the said upper limit, there exists a tendency for developability to become more favorable.

As a specific example of an ethylenically unsaturated compound, For example, Ester of an aliphatic polyhydroxy compound and unsaturated carboxylic acid; Ester of aromatic polyhydroxy compound and unsaturated carboxylic acid; Ester obtained by esterification of polyhydric hydroxy compounds, such as an aliphatic polyhydroxy compound and an aromatic polyhydroxy compound, and unsaturated carboxylic acid and polybasic carboxylic acid is mentioned.

As ester of the said aliphatic polyhydroxy compound and unsaturated carboxylic acid, For example, ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propane triacrylate, trimethylolethane triacrylate, pentaerythritol Aliphatic polyhydrides such as diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate Acrylic acid esters of hydroxy compounds, methacrylic acid esters in which acrylates of these exemplary compounds are replaced with methacrylates, itaconic acid esters similarly replaced with itaconate, crotonic acid esters replaced with crotonate or maleate replaced with methacrylate Maleic acid ester is mentioned.

As ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, pyrogallol triacrylate, for example Acrylic acid ester and methacrylic acid ester of aromatic polyhydroxy compounds, such as these are mentioned.

The ester obtained by the esterification reaction of a polyhydric hydroxy compound such as an aliphatic polyhydroxy compound and an aromatic polyhydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid is not necessarily a single substance, but representative specific examples include: For example, condensates of acrylic acid, phthalic acid, and ethylene glycol, condensates of acrylic acid, maleic acid, and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol and glycerin condensates of

In addition, examples of the polyfunctional ethylenic monomer used in the present invention include urethane ( meth)acrylates; Epoxy acrylates like the addition reaction product of a polyhydric epoxy compound and hydroxy (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; Vinyl group-containing compounds, such as divinyl phthalate, are useful.

The urethane (meth) acrylates include, for example, DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA , U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B , UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Mitsubishi Chemical Corporation).

Among these, it is preferable to use an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid or urethane (meth)acrylates as the (A) ethylenically unsaturated compound from the viewpoint of adhesion of the barrier rib to the substrate and ink repellency. , dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2-tris (meth) acryloyloxymethylethyl phthalic acid, pentaerythritol tetra (meth) acrylate, pentaerythritol It is more preferable to use tri(meth)acrylate, the dibasic acid anhydride adduct of dipentaerythritol penta(meth)acrylate, and the dibasic acid anhydride adduct of pentaerythritol tri(meth)acrylate.

These may be used individually by 1 type, and may use 2 or more types together.

In the present invention, (A) the molecular weight of the ethylenically unsaturated compound is not particularly limited, but from the viewpoint of forming a high-definition barrier rib having thin ink repellency and line width, it is preferably 100 or more, more preferably 150 or more. and more preferably 200 or more, still more preferably 300 or more, particularly preferably 400 or more, and most preferably 500 or more, preferably 1000 or less, more preferably 700 or less. For example, 100-1000 are preferable, 150-1000 are more preferable, 200-1000 are still more preferable, 300-700 are still more preferable, 400-700 are still more preferable, 500-700 are especially preferable. do.

(A) Although carbon number of an ethylenically unsaturated compound is not specifically limited, From a viewpoint of ink repellency and residue suppression, Preferably it is 7 or more, More preferably, it is 10 or more, More preferably, it is 15 or more, Even more preferably is 20 or more, particularly preferably 25 or more, preferably 50 or less, more preferably 40 or less, still more preferably 35 or less, particularly preferably 30 or less. For example, 7-50 are preferable, 10-50 are more preferable, 15-40 are still more preferable, 20-35 are still more preferable, 25-30 are especially preferable.

From the viewpoint of forming high-definition partition walls with thin ink repellency and line width, ester (meth) acrylates, epoxy (meth) acrylates, and urethane (meth) acrylates are preferable, and among them, penta Erythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate or more trifunctional ester (meth) acrylates , 2,2,2-tris(meth)acryloyloxymethylethylphthalic acid, dibasic acid anhydride adduct of dipentaerythritol penta(meth)acrylate, acid to trifunctional or higher ester (meth)acrylates The addition of anhydride is more preferable from the viewpoint of forming a high-definition partition wall having a thin ink repellency and a thin line width.

Although the content rate of (A) ethylenically unsaturated compound in the photosensitive resin composition of this invention is not specifically limited, Preferably it is 1 mass % or more in total solid of the photosensitive resin composition, More preferably, it is 5 mass % or more, More preferably Preferably it is 10 mass % or more, More preferably, it is 15 mass % or more, Especially preferably, it is 20 mass % or more, More preferably, it is 80 mass % or less, More preferably, it is 60 mass % or less, More preferably, It is 40 mass % or less, More preferably, it is 30 mass % or less. For example, 1-80 mass % is preferable, 5-80 mass % is more preferable, 10-60 mass % is still more preferable, 15-40 mass % is still more preferable, 20-30 mass % is more preferable Especially preferred. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency which can form the high definition partition with a thin line|wire width by setting it as below the said upper limit.

(C) Although the content rate of (A) ethylenically unsaturated compound with respect to 100 mass parts of alkali-soluble resin is not specifically limited, Preferably it is 1 mass part or more, More preferably, it is 5 mass parts or more, More preferably, it is 10 mass parts. parts by mass or more, still more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, more particularly preferably 25 parts by mass or more, most preferably 30 parts by mass or more, and preferably 150 parts by mass or more. Hereinafter, more preferably, it is 100 mass parts or less, More preferably, it is 70 mass parts or less, More preferably, it is 50 mass parts or less, Especially preferably, it is 40 mass parts or less. For example, 1-150 mass parts is preferable, 5-150 mass parts is more preferable, 10-100 mass parts is still more preferable, 15-100 mass parts is still more preferable, 20-70 mass parts is still more preferable, 25 -50 mass parts is especially preferable, and 30-40 mass parts is the most preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency which can form the high definition partition with a thin line|wire width by setting it as below the said upper limit.

[1-1-2] (B) component; photopolymerization initiator

The photosensitive resin composition of this invention contains (B) a photoinitiator. (B) A photoinitiator will not be specifically limited if it is a compound which polymerizes (A) ethylenically unsaturated compound by actinic light, for example, (A) the ethylenically unsaturated bond which the ethylenically unsaturated compound has.

The photosensitive resin composition of this invention can use the photoinitiator normally used in this field|area as (B) photoinitiator. As such a photoinitiator, For example, the metallocene compound containing the titanocene compound of Unexamined-Japanese-Patent No. 59-152396 and Unexamined-Japanese-Patent No. 61-151197; The hexaarylbiimidazole derivatives described in Unexamined-Japanese-Patent No. 2000-56118; Halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, and N-aryl-α- radical activators such as amino acid salts and N-aryl-α-amino acid esters, and α-aminoalkylphenone derivatives; The oxime ester type compound described in Unexamined-Japanese-Patent No. 2000-80068, Unexamined-Japanese-Patent No. 2006-36750, etc. is mentioned.

Specifically, for example, as the metallocene compound, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6) -Pentafluorophenyl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis (2,4,6-trifluorophenyl), dicyclo Clopentadienyl titanium di (2,6-difluorophenyl), dicyclopentadienyl titanium di (2,4-difluorophenyl), di (methylcyclopentadienyl) titanium bis (2,3, 4,5,6-pentafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,6-difluorophenyl), dicyclopentadienyl titanium [2,6-di-fluoro-3 -(pyrro-1-yl)-phenyl].

Examples of the biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis( 3'-methoxyphenyl) imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5- Diphenylimidazole dimer and (4'-methoxyphenyl) -4,5-diphenylimidazole dimer are mentioned.

Examples of the halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β]. -(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6"-benzofuryl)vinyl)]-1,3 and ,4-oxadiazole and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

Examples of the halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaph). tyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4 -ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

As α-aminoalkylphenone derivatives, for example, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2- Ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-( diethylamino) chalcone.

Especially as a photoinitiator, an oxime ester type compound is effective from a point of a sensitivity and plate-making property, For example, when using alkali-soluble resin containing a phenolic hydroxyl group, it becomes disadvantageous from a point of sensitivity. For this reason, especially the oxime ester type compound excellent in such a sensitivity is useful. Since the oxime ester compound has both a structure for absorbing ultraviolet light, a structure for transmitting light energy, and a structure for generating radicals in its structure, it is highly sensitive to a small amount, and is stable against thermal reaction, and is stable to a small amount. It is possible to obtain a highly sensitive photosensitive resin composition.

As an oxime ester type compound, the compound represented by the following general formula (IV) is mentioned, for example.

[Formula 3]

In formula (IV), R ^21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.

R ^21b represents an optional substituent including an aromatic ring.

R ^22a represents an optionally substituted alkanoyl group or an optionally substituted aryloyl group.

n represents an integer of 0 or 1.

Although the number of carbon atoms of the alkyl group in R ^21a is not particularly limited, from the viewpoint of solubility and sensitivity to a solvent, preferably 1 or more, more preferably 2 or more, further preferably 20 or less, more preferably 15 Below, More preferably, it is 10 or less. Specific examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, and a propyl group.

Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, a 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl group, N -Acetyl-N-acetoxyamino group is mentioned. As an alkyl group, it is preferable from a viewpoint of synthetic|combination easiness that it is unsubstituted.

Examples of the aromatic cyclic group for R ^21a include an aromatic hydrocarbon cyclic group and an aromatic heterocyclic group. Although carbon number of an aromatic ring group is not specifically limited, From a soluble viewpoint with respect to the photosensitive resin composition, it is preferable that it is 5 or more. Moreover, from a developable viewpoint, it is preferable that it is 30 or less, It is more preferable that it is 20 or less, It is more preferable that it is 12 or less. For example, 5-30 are preferable, 5-20 are more preferable, 5-12 are still more preferable.

Specific examples of the aromatic ring group include, for example, a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among them, from the viewpoint of developability, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.

Examples of the substituent which the aromatic ring group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group to which these substituents are linked, and from the viewpoint of developability, an alkyl group, an alkoxy group, these The group which connected is preferable, and the connected alkoxy group is more preferable.

Among these, from a viewpoint of a sensitivity, it is preferable that R ^21a is an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.

As R ^21b , an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, or an optionally substituted diphenyl sulfide group is mentioned. Among these, the carbazolyl group which may be substituted from a viewpoint of a sensitivity is preferable.

Although carbon number of the alkanoyl group in R ^22a is not specifically limited, From a viewpoint of solubility to a solvent and a sensitivity, Preferably it is 2 or more, More preferably, 3 or more, More preferably, it is 20 or less, More preferably is 15 or less, more preferably 10 or less, even more preferably 5 or less. Specific examples of the alkanoyl group include, for example, an acetyl group, an ethyloyl group, a propanoyl group, and a butanoyl group.

As a substituent which the alkanoyl group may have, an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, and an amide group are mentioned, for example. As an alkanoyl group, from a viewpoint of synthetic|combination easiness, it is preferable that it is unsubstituted.

Although carbon number of the aryl group in R ^22a is not specifically limited, From a viewpoint of solubility to a solvent and a sensitivity, Preferably it is 7 or more, More preferably, 8 or more, More preferably, it is 20 or less, More preferably is 15 or less, more preferably 10 or less. Specific examples of the aryl group include, for example, a benzoyl group and a naphthoyl group.

As a substituent which the aryl group may have, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and an alkyl group are mentioned, for example. As an aryloyl group, it is preferable from a viewpoint of synthetic|combination ease that it is unsubstituted.

Among these, from a viewpoint of a sensitivity, it is preferable that R ^22a is an alkanoyl group which may have a substituent, It is more preferable that it is an unsubstituted alkanoyl group, It is still more preferable that it is an acetyl group.

A photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type. A sensitizing dye according to the wavelength of an image exposure light source and a polymerization accelerator can be mix|blended with a photoinitiator as needed in order to raise a sensitivity. As a sensitizing dye, For example, the xanthene dye described in Unexamined-Japanese-Patent No. 4-221958 and Unexamined-Japanese-Patent No. 4-219756, Unexamined-Japanese-Patent No. 3-239703, Unexamined-Japanese-Patent No. Hei 5, for example. Heterocyclic coumarin pigment described in -289335, 3-ketocoumarin compound described in Japanese Patent Application Laid-Open No. 3-239703 and Japanese Unexamined Patent Publication No. 5-289335, Japanese Unexamined Patent Publication No. 6-19240 Pyromethene dye described in Japanese Patent Application Laid-Open No. 47-2528, Japanese Unexamined Patent Publication No. 54-155292, Japanese Patent Publication No. 45-37377, Japanese Unexamined Patent Publication No. 48-84183, Japanese Unexamined Patent Publication No. 52 -112681, Japanese Unexamined Patent Publication No. 58-15503, Japanese Unexamined Patent Publication No. 60-88005, Japanese Unexamined Patent Publication No. 59-56403, Japanese Unexamined Patent Publication No. 2-69, Japanese Unexamined Patent Publication No. 57 -The pigment|dye which has dialkylamino benzene skeleton of Unexamined-Japanese-Patent No. 168088, Unexamined-Japanese-Patent No. 5-107761, Unexamined-Japanese-Patent No. 5-210240, and Unexamined-Japanese-Patent No. 4-288818 is mentioned.

Among these sensitizing dyes, an amino group-containing sensitizing dye is preferable, and the compound which has an amino group and a phenyl group in the same molecule|numerator is more preferable. For example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3 Benzophenone-type compounds, such as '- diaminobenzophenone and 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p -Dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-oxazole, 2-(p-dimethylaminophenyl)benzothiazole , 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p- Diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylamino A compound containing a p-dialkylaminophenyl group, such as phenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, and (p-diethylaminophenyl)pyrimidine, is more preferable. Among these, 4,4'- dialkylamino benzophenone is especially preferable.

A sensitizing dye may be used individually by 1 type, and may use 2 or more types together.

As the polymerization accelerator, for example, aromatic amines such as p-dimethylaminobenzoate ethyl and 2-dimethylaminoethyl benzoate, and aliphatic amines such as n-butylamine and N-methyldiethanolamine can be used. A polymerization accelerator may be used individually by 1 type, and may use 2 or more types together.

Although the content rate of (B) photoinitiator in the photosensitive resin composition of this invention is not specifically limited, In total solid of the photosensitive resin composition, Preferably it is 0.01 mass % or more, More preferably, it is 0.1 mass % or more, More Preferably it is 1 mass % or more, More preferably, it is 2 mass % or more, Especially preferably, it is 3 mass % or more, More preferably, it is 25 mass % or less, More preferably, it is 20 mass % or less, More preferably is 15 mass% or less, even more preferably 10 mass% or less, particularly preferably 7 mass% or less, and most preferably 5 mass% or less. For example, 0.01-25 mass % is preferable, 0.01-20 mass % is more preferable, 0.1-15 mass % is still more preferable, 1-10 mass % is still more preferable, 2-7 mass % is More preferably, 3-5 mass % is especially preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for a residue to reduce by using below the said upper limit.

As a compounding ratio of (B) photoinitiator with respect to (A) ethylenically unsaturated compound in the photosensitive resin composition, 1 mass part or more is preferable with respect to 100 mass parts of (A) ethylenically unsaturated compounds, and 5 mass parts or more more preferably, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, more preferably 200 parts by mass or less, more preferably 100 parts by mass or less, , 50 parts by mass or less is more preferable, and 30 parts by mass or less is particularly preferable. For example, 1-200 mass parts is preferable, 5-200 mass parts is more preferable, 10-100 mass parts is still more preferable, 15-50 mass parts is still more preferable, 20-30 mass parts is especially preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for a residue to reduce by using below the said upper limit.

It may use together with a photoinitiator, and you may use a chain transfer agent. As a chain transfer agent, a mercapto group containing compound and carbon tetrachloride are mentioned, for example. Among these, it is more preferable to use a mercapto group-containing compound since it exists in the tendency for a chain transfer effect to be high. It is thought that this is because bond cleavage tends to occur when the S-H bond energy is small, and hydrogen extraction reaction and chain transfer reaction are likely to occur. Use of a chain transfer agent is effective for a sensitivity improvement and surface hardening property.

As a mercapto group containing compound, you may have two or more mercapto groups in a molecule|numerator, For example, 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 3-mer mercapto group-containing compounds having an aromatic ring, such as capto-1,2,4-triazole, 2-mercapto-4(3H)-quinazoline, β-mercaptonaphthalene, and 1,4-dimethyl mercaptobenzene;

Hexanedithiol, decanedithiol, butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxyethyl tristhiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3- Mercaptopropionate), butanediol bis (3-mercaptobutyrate), ethylene glycol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercapto) butyrate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H) and aliphatic mercapto group-containing compounds such as ,5H)-trione.

Among the mercapto group-containing compounds having an aromatic ring, 2-mercaptobenzothiazole and 2-mercaptobenzoimidazole are preferable, and among the aliphatic mercapto group-containing compounds, trimethylolpropanetris (3-mercapto propionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetra Kiss (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4 ,6(1H,3H,5H)-trione is preferred.

In terms of sensitivity, an aliphatic mercapto group-containing compound is preferable, and specifically, trimethylol propane tris (3-mercapto propionate), pentaerythritol tetrakis (3-mercapto propionate), Pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate) , 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferable, and pentaerythritoltetra Kiss (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) are more preferable.

These may be used individually by 1 type, and may use 2 or more types together.

Among these, from the viewpoint of increasing the taper angle, one or two or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, and 2-mercaptobenzooxazole, and a photopolymerization initiator are combined, , it is preferable to use it as a photoinitiator system. For example, 2-mercaptobenzothiazole may be used, 2-mercaptobenzoimidazole may be used, and 2-mercaptobenzothiazole and 2-mercaptobenzoimidazole may be used together and may be used.

From the viewpoint of sensitivity, it is preferable to use one or two or more selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate). In addition, from the viewpoint of sensitivity, one or two or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, and 2-mercaptobenzooxazole, and pentaerythritol tetrakis (3-mer It is preferable to use one or two or more selected from the group consisting of captopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) and a photopolymerization initiator in combination.

Although the content rate of the chain transfer agent in the photosensitive resin composition of this invention is not specifically limited, In total solid of the photosensitive resin composition, Preferably it is 0.01 mass % or more, More preferably, it is 0.1 mass % or more, More preferably, 0.5 It is mass % or more, More preferably, it is 0.8 mass % or more, More preferably, it is 5 mass % or less, More preferably, it is 4 mass % or less, More preferably, it is 3 mass % or less, More preferably, it is 2 mass % or less. % or less. For example, 0.01-5 mass % is preferable, 0.1-4 mass % is more preferable, 0.5-3 mass % is still more preferable, 0.8-2 mass % is especially preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency which can form the high definition partition with a thin line|wire width by setting it as below the said upper limit.

As a content rate of the chain transfer agent with respect to (B) photoinitiator in the photosensitive resin composition, 5 mass parts or more are preferable with respect to 100 mass parts of (B) photoinitiators, 10 mass parts or more are more preferable, 15 More preferably, 20 parts by mass or more is particularly preferable, and 500 parts by mass or less is preferable, 300 parts by mass or less is more preferable, 100 parts by mass or less is still more preferable, and 50 parts by mass or less is Especially preferred. For example, 5-500 mass parts is preferable, 10-300 mass parts is more preferable, 15-100 mass parts is still more preferable, 20-50 mass parts is especially preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency which can form the high definition partition with a thin line|wire width by setting it as below the said upper limit.

[1-1-3] (C) component; Alkali-soluble resin

The photosensitive resin composition of this invention contains (C) alkali-soluble resin. In this invention, as (C) alkali-soluble resin, if it can develop with an alkali developing solution, it will not specifically limit.

(C) Alkali-soluble resin in the photosensitive resin composition of this invention contains alkali-soluble resin (C-1) which has a partial structure represented by the following general formula (c1).

[Formula 4]

(In formula (c1), R ^c11 represents a hydrogen atom or a methyl group.

R ^c12 represents a divalent hydrocarbon group which may have a substituent.

n represents the integer of 2 or 3.

The benzene ring in Formula (c1) may be further substituted by arbitrary substituents.

* denotes each bond.)

Alkali-soluble resin (C-1) has a partial structure represented by formula (c1), and by having a benzene ring in the main chain, the hydrophobicity of the film tends to increase, and particularly by having two or more crosslinking groups in the side chain, crosslinking density even at low exposure dose is high, and the liquid repellent is likely to remain on the surface of the film even after development, and it is considered that the ink repellency is improved.

(R ^c12 )

In the formula (c1), R ^c12 represents a divalent hydrocarbon group which may have a substituent.

Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups are linked with one or more divalent aromatic ring groups.

Examples of the divalent aliphatic group include linear, branched and cyclic ones. Among these, a linear thing is preferable from a viewpoint of image development solubility, on the other hand, a cyclic thing is preferable from a viewpoint of heat resistance. The carbon number is preferably 1 or more, more preferably 3 or more, still more preferably 6 or more, more preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. For example, 1-20 are preferable, 3-15 are more preferable, and 6-10 are still more preferable. There exists a tendency for developability to improve by using more than the said lower limit. There exists a tendency for ink repellency to improve by using below the said upper limit.

Specific examples of the divalent linear aliphatic group include methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, and n-heptylene group. Among these, a methylene group is preferable from a heat resistant viewpoint.

Specific examples of the divalent branched aliphatic group include the aforementioned divalent linear aliphatic group, as a side chain, for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, A structure having an iso-butyl group, a sec-butyl group, and a tert-butyl group is exemplified.

Although the number of rings which a bivalent cyclic aliphatic group has is not specifically limited, Preferably it is 1 or more, 2 or more are more preferable, More preferably, it is 10 or less, and 5 or less are more preferable. For example, 1-10 are preferable, 1-5 are more preferable, and 2-5 are still more preferable. There exists a tendency for ink repellency to become favorable by setting it as more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Specific examples of the divalent cyclic aliphatic group include, for example, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclo and groups in which two hydrogen atoms have been removed from rings, such as a dodecane ring and a dicyclopentane ring. Among these, groups in which two hydrogen atoms have been removed from the dicyclopentane ring and the adamantane ring from the viewpoint of heat resistance are preferable.

As a substituent which the divalent aliphatic group may have, For example, C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; hydroxyl group; nitro group; cyano group; and a carboxyl group. The divalent aliphatic group is preferably unsubstituted from the viewpoint of synthesis easiness.

Examples of the divalent aromatic cyclic group include a divalent aromatic hydrocarbon cyclic group and a divalent aromatic heterocyclic group. The carbon number is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, more preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. For example, 4-20 are preferable, 5-15 are more preferable, and 6-10 are still more preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

As the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group, a monocyclic ring may be sufficient or a condensed ring may be sufficient as it. The divalent aromatic hydrocarbon ring group includes, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, having two free valences. , a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring are mentioned.

A monocyclic ring may be sufficient as an aromatic heterocyclic ring in an aromatic heterocyclic group, and a condensed ring may be sufficient as it. The divalent aromatic heterocyclic group includes, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, having two free valences. , indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoox Xazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinoline ring, quinoxaline ring, phenanthridine a ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring are mentioned. Among these, from a viewpoint of manufacturing cost, the benzene ring or naphthalene ring which has two free valences is preferable, and the benzene ring which has two free valences is more preferable.

Examples of the substituent which the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. As a divalent aromatic cyclic group, unsubstituted is preferable from a sclerosis|hardenable viewpoint.

Examples of the group in which one or more divalent aliphatic groups are connected to one or more divalent aromatic ring groups include groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups described above are connected.

Although the number of divalent aliphatic groups is not specifically limited, Preferably it is 1 or more, 2 or more are more preferable, More preferably, it is 10 or less, 5 or less are more preferable, 3 or less are still more preferable. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. There exists a tendency for developability to improve by using more than the said lower limit. There exists a tendency for ink repellency to improve by using below the said upper limit.

Although the number of divalent aromatic ring groups is not specifically limited, Preferably it is 1 or more, 2 or more are more preferable, More preferably, it is 10 or less, 5 or less are more preferable, 3 or less are still more preferable. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. There exists a tendency for developability to improve by using more than the said lower limit. There exists a tendency for ink repellency to improve by using below the said upper limit.

Specific examples of the group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups include groups represented by the following formulas (c1-1) to (c1-6). Among these, the group represented by Formula (c1-1) from a viewpoint of developability and ink repellency is preferable. In the formula, * represents a bond, respectively.

[Formula 5]

As above-mentioned, the benzene ring in Formula (c1) may be further substituted by arbitrary substituents. As a substituent, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group are mentioned, for example. The number of substituents is not specifically limited, The number may be one, and two or more may be sufficient as them.

It is preferable that the benzene ring in Formula (c1) is unsubstituted from a sclerosis|hardenable viewpoint.

(n)

In formula (c1), n represents the integer of 2 or 3. It is preferable that n is 2 from a viewpoint of adhesiveness with a board|substrate.

Moreover, it is preferable that the partial structure represented by Formula (c1) is a partial structure represented by a following formula (c2) from a viewpoint of developing solubility.

[Formula 6]

(In formula (c2), R ^c11 , R ^c12 and n have the same meaning as in the formula (c1).

R ^c13 represents a hydrogen atom or a polybasic acid residue.

The benzene ring in Formula (c2) may be further substituted by arbitrary substituents.

* denotes each bond.)

The polybasic acid residue means a monovalent group obtained by removing one OH group from the polybasic acid or anhydride thereof. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydro Phthalic acid, chlorendic acid, methyl tetrahydrophthalic acid, and biphenyl tetracarboxylic acid are mentioned.

Among these, from a viewpoint of a patterning characteristic, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable, tetrahydrophthalic acid, biphenyltetra Carboxylic acid is more preferable.

Alkali-soluble resin (C-1) may have a partial structure represented by the following general formula (c3) other than the partial structure represented by Formula (c1). When alkali-soluble resin (C-1) further has the partial structure represented by Formula (c3), it is easy to adjust the number of crosslinking sites, and there exists a tendency for developability to improve.

[Formula 7]

(In formula (c3), R ^c14 represents a hydrogen atom or a methyl group.

R ^c15 represents a divalent hydrocarbon group which may have a substituent.

The benzene ring in Formula (c3) may be further substituted by arbitrary substituents.

* denotes each bond.)

As R ^c15 in the formula (c3), those exemplified as R ^c12 in the formula (c1) can be preferably employed. In addition, as a substituent which the benzene ring in Formula (c3) may have, what was illustrated as a substituent which the benzene ring in Formula (c1) may have is employable preferably.

The partial structure represented by the formula (c3) is preferably a partial structure represented by the following formula (c4) from the viewpoint of developing solubility.

[Formula 8]

(In formula (c4), R ^c14 and R ^c15 have the same meaning as in the formula (c3).

R ^c16 represents a hydrogen atom or a polybasic acid residue.

The benzene ring in Formula (c4) may be further substituted by arbitrary substituents.

* indicates a bond.)

As R ^c16 in formula (c4), those exemplified as R ^c13 in formula (c2) can be preferably employed.

Moreover, it is preferable that alkali-soluble resin (C-1) contains both the partial structure represented by Formula (c1), and the partial structure represented by Formula (c3) from a viewpoint of developability and ink repellency.

Although the ratio of the formula (c1) to the total number of moles of the partial structure represented by the formula (c1) and the partial structure represented by the formula (c3) is not particularly limited, it is preferably 20 mol% or more, and 40 mol% or more. Preferably, 50 mol% or more is more preferable, and is usually 100 mol% or less, 90 mol% or less is preferable, and 80 mol% or less is still more preferable. For example, 20-100 mol% is preferable, 40-90 mol% is more preferable, 50-80 mol% is still more preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

It is preferable that alkali-soluble resin (C-1) contains both the partial structure represented by Formula (c2), and the partial structure represented by Formula (c4) from a viewpoint of developability and ink repellency.

Although the ratio of the formula (c2) to the total number of moles of the partial structure represented by the formula (c2) and the partial structure represented by the formula (c4) is not particularly limited, it is preferably 20 mol% or more, and 40 mol% or more. Preferably, 50 mol% or more is more preferable, and is usually 100 mol% or less, 90 mol% or less is preferable, and 80 mol% or less is still more preferable. For example, 20-100 mol% is preferable, 40-90 mol% is more preferable, 50-80 mol% is still more preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Each of the partial structures represented by the formulas (c1), (c2), (c3), and (c4) contained in one molecule of the alkali-soluble resin (C-1) may be one or two or more.

Although the number of the partial structures represented by Formula (c1) contained in 1 molecule of alkali-soluble resin (C-1) is not specifically limited, 1 or more is preferable, 2 or more are more preferable, 3 or more are still more preferable, Moreover, 10 or less are preferable and 8 or less are more preferable. For example, 1-10 are preferable, 2-10 are more preferable, and 3-8 are still more preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Although the number of the partial structures represented by Formula (c2) contained in 1 molecule of alkali-soluble resin (C-1) is not specifically limited, 1 or more is preferable, 2 or more are more preferable, 3 or more are still more preferable, Moreover, 15 or less are preferable, 10 or less are more preferable, and 5 or less are still more preferable. For example, 1-15 are preferable, 2-10 are more preferable, and 3-5 are still more preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Specific examples of alkali-soluble resin (C-1) are given below.

[Formula 9]

[Formula 10]

[Formula 11]

Among these, the alkali-soluble resin of the said Formula (C-1-1) from a viewpoint of ink repellency is more preferable.

Although the manufacturing method of alkali-soluble resin (C-1) is not specifically limited, For example, an ethylenically unsaturated monocarboxylic acid or an ester compound is added to the epoxy resin which has a partial structure represented by following formula (c5), and, optionally, After reacting the isocyanate group-containing compound, it can be prepared by further reacting a polybasic acid or anhydride thereof. For example, by ring-opening addition of the carboxyl group of an unsaturated monocarboxylic acid to the epoxy group of an epoxy resin, while adding an ethylenically unsaturated bond to an epoxy compound through an ester bond (-COO-), the hydroxyl group generated at that time , one carboxyl group of the polybasic acid anhydride can be added. When adding polybasic acid anhydride, the method of adding and adding polyhydric alcohol simultaneously is also mentioned.

[Formula 12]

(In formula (c5), R ^c12 and n have the same meaning as in the formula (c1).

The benzene ring in Formula (c5) may be further substituted by arbitrary substituents.

* denotes each bond.)

Alkali-soluble resin (C-1) can also be manufactured by the method of Unexamined-Japanese-Patent No. 2016-47919, and Unexamined-Japanese-Patent No. 2017-190403.

Although the acid value of alkali-soluble resin (C-1) is not specifically limited, 20 mgKOH/g or more is preferable, 30 mgKOH/g or more is more preferable, 40 mgKOH/g or more is still more preferable, 50 mg KOH/g or more is still more preferable, 150 mgKOH/g or less is preferable, 140 mgKOH/g or less is more preferable, 130 mgKOH/g or less is still more preferable, 120 mgKOH/g or less is more preferable than For example, 20-150 mgKOH/g is preferable, 30-140 mgKOH/g is more preferable, 40-130 mgKOH/g is still more preferable, 50-120 mgKOH/g is especially preferable. . There exists a tendency for developability to improve by using more than the said lower limit. There exists a tendency for ink repellency to improve by using below the said upper limit.

Although the weight average molecular weight (Mw) of alkali-soluble resin (C-1) is not specifically limited, Preferably it is 1000 or more, More preferably, it is 2000 or more, More preferably, it is 3000 or more, More preferably, it is 20000 or less, More preferably, it is 15000 or less, More preferably, it is 10000 or less, Especially preferably, it is 8000 or less. For example, 1000-20000 are preferable, 1000-15000 are more preferable, 2000-10000 are still more preferable, 3000-8000 are especially preferable. There exists a tendency for image development adhesiveness to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Although the double bond equivalent of alkali-soluble resin (C-1) is not specifically limited, 600 or less are preferable, 500 or less are more preferable, 450 or less are still more preferable, 400 or less are especially preferable, and 100 or more It is preferable, 150 or more are more preferable, 200 or more are still more preferable, 300 or more are especially preferable. There exists a tendency for ink repellency to improve by using below the said upper limit. For example, 100-600 are preferable, 150-500 are more preferable, 200-450 are still more preferable, 300-400 are especially preferable. There exists a tendency for developability to improve by using more than the said lower limit.

The double bond equivalent of alkali-soluble resin (C-1) is computable from a following formula.

(Double bond equivalent of alkali-soluble resin (C-1))

= (molecular weight of alkali-soluble resin (C-1))/(number of ethylenically unsaturated double bonds per molecule of alkali-soluble resin (C-1))

(C) alkali-soluble resin in the photosensitive resin composition of this invention contains alkali-soluble resin (Hereinafter, it may call "other alkali-soluble resin") other than alkali-soluble resin (C-1) further You can do it. By containing other alkali-soluble resin, there exists a tendency for developability to improve, and it is preferable.

As other alkali-soluble resin, from a viewpoint of developing solubility, epoxy (meth)acrylate resin (C-2) other than (C-1) (henceforth "epoxy (meth)acrylate resin (C-2)" It is preferable to include). On the other hand, it is preferable to include the acrylic copolymer resin (C-3) (henceforth "acrylic copolymer resin (C-3)") which has an ethylenically unsaturated group in a side chain from a viewpoint of ink repellency.

First, the epoxy (meth)acrylate resin (C-2) will be described in detail.

[Epoxy (meth) acrylate resin (C-2)]

The epoxy (meth)acrylate resin (C-2) is obtained by adding an ethylenically unsaturated monocarboxylic acid or an ester compound to an epoxy resin having no partial structure represented by the formula (c5), and optionally reacting an isocyanate group-containing compound. Then, it is resin with which polybasic acid or its anhydride was further reacted. For example, by ring-opening addition of a carboxyl group of an unsaturated monocarboxylic acid to the epoxy group of the epoxy resin, an ethylenically unsaturated group is added to the epoxy resin via an ester bond (-COO-), and a polybasic acid is added to the hydroxyl group generated at that time. The thing to which one carboxy group of an anhydride was added is mentioned. When adding polybasic acid anhydride, the thing added by adding polyhydric alcohol simultaneously is mentioned.

Resin obtained by making the carboxy group of resin obtained by the said reaction react with the compound which has a functional group which can further react is also contained in the said epoxy (meth)acrylate resin (C-2).

Here, the epoxy resin is specifically, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolak epoxy resin, trisphenol Epoxy resin, polymerization epoxy resin of phenol and dicyclopentadiene, dihydrooxylfluorene type epoxy resin, dihydrooxylalkyleneoxylfluorene type epoxy resin, 9,9-bis(4'-hydroxyphenyl)fluorene and diglycidyl ether of 1,1-bis(4'-hydroxyphenyl)adamantane. As the epoxy resin, an epoxy resin having an aromatic ring in the main chain as described above can be preferably used.

Among them, from the viewpoint of heat resistance, bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolak epoxy resin, polymerization epoxy resin of phenol and dicyclopentadiene, 9,9-bis (4'-hydroxyphenyl) flu A diglycidyl ether product of orene is preferable, and a bisphenol A epoxy resin is more preferable.

As the epoxy resin, for example, a bisphenol A epoxy resin (for example, "jER (registered trademark, hereinafter the same) 828" manufactured by Mitsubishi Chemical Corporation), "jER1001", "jER1002", "jER1004", "NER-1302" (epoxy equivalent 323, softening point 76°C) manufactured by Pharma Co., etc.), bisphenol F-type resin (eg, "jER807", "jER4004P", "jER4005P", "jER4007P", manufactured by Mitsubishi Chemical Corporation), "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66°C), etc.), bisphenol S-type epoxy resin, biphenyl glycidyl ether (eg, "jERYX-4000" manufactured by Mitsubishi Chemical) , phenol novolac type epoxy resin (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "jER152", "jER154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Company), (o ,m,p-) cresol novolac-type epoxy resin (for example, "EOCN (registered trademark, hereinafter the same)-102S" manufactured by Nippon Kayaku Co., Ltd., "EOCN-1020", "EOCN-104S"), triglycy Diisocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Corporation), trisphenolmethane type epoxy resin (for example, "EPPN (registered trademark, hereinafter the same)" -501 manufactured by Nippon Kayaku Co., Ltd. ” “EPPN-502”, “EPPN-503”), alicyclic epoxy resin (“Celoxide (registered trademark, hereinafter the same) 2021P” manufactured by Daicel Co., Ltd., “Celoxide EHPE”), dicyclopentadiene and phenol Epoxy resin obtained by glycidylation of phenol resin by reaction (for example, "EXA-7200" manufactured by DIC, "NC-7300" manufactured by Nippon Kayaku Co., Ltd., "XD-1000"), biphenyl type epoxy resin (For example, "NC-7000" by Nippon Kayaku Co., Ltd.) and "E-201" by Osaka Organic Chemical Industry can be used preferably. Among these, "XD-1000" manufactured by Nippon Kayaku Co., Ltd., "NC-3000" manufactured by Nippon Kayaku Co., Ltd., "ESF-300" manufactured by Nippon Kayaku Co., Ltd., and "E-201" manufactured by Osaka Organic Chemical Industries, Ltd. are preferable. do.

Examples of the ethylenically unsaturated monocarboxylic acid include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and pentaerythritol tri(meth)acrylate succinic anhydride adduct; Pentaerythritol tri (meth) acrylate tetrahydro phthalic anhydride adduct, dipentaerythritol penta (meth) acrylate succinic anhydride adduct, dipentaerythritol penta (meth) acrylate phthalic anhydride adduct, dipentaerythritol penta(meth)acrylate tetrahydrophthalic anhydride adduct, and a reaction product of (meth)acrylic acid and ε-caprolactone. Among these, the viewpoint of a sensitivity to (meth)acrylic acid is preferable.

As the polybasic acid (anhydride), for example, succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetra Hydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and anhydrides thereof. Among these, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride and hexahydrophthalic anhydride are preferable, and succinic anhydride and tetrahydrophthalic anhydride are more preferable from the viewpoint of suppressing outgassing from the cured product and ensuring long-term reliability. desirable.

By using a polyhydric alcohol, the molecular weight of the epoxy (meth)acrylate resin (C-2) can be increased, branching can be introduced into the molecule, and there is a tendency that a balance between molecular weight and viscosity can be achieved. Moreover, the introduction rate of an acidic radical into a molecule|numerator can be increased, and there exists a tendency which is easy to take the balance of a sensitivity and adhesiveness.

The polyhydric alcohol is preferably one or two or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. do.

Examples of the epoxy (meth)acrylate resin (C-2) include those described in Korean Patent Application Laid-Open No. 10-2013-0022955 other than those described above.

Among the epoxy (meth)acrylate resins (C-2), from the viewpoint of developing solubility, an epoxy (meth)acrylate having a partial structure represented by the following general formula (i) and not having a partial structure represented by the formula (c1) It has a resin (hereinafter, sometimes referred to as "epoxy (meth) acrylate resin (C-2-1)"), and a partial structure represented by the following general formula (ii), and a partial structure represented by the formula (c1) It is preferable to include at least 1 sort(s) selected from the group which consists of an epoxy (meth)acrylate resin (Hereinafter, it may call "epoxy (meth)acrylate resin (C-2-2)") which does not have it.

[Formula 13]

(In formula (i), R ^a represents a hydrogen atom or a methyl group.

R ^b represents a divalent hydrocarbon group which may have a substituent.

The benzene ring in Formula (i) may be further substituted by arbitrary substituents.

* denotes each bond.)

[Formula 14]

(In formula (ii), R ^c each independently represents a hydrogen atom or a methyl group.

R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.

R ^e and R ^f each independently represent a divalent aliphatic group which may have a substituent.

l and m each independently represent the integer of 0-2.

* denotes each bond.)

The epoxy (meth)acrylate resin (C-2-1) will be described in detail.

[Formula 15]

(In formula (i), R ^a represents a hydrogen atom or a methyl group.

R ^b represents a divalent hydrocarbon group which may have a substituent.

The benzene ring in Formula (i) may be further substituted by arbitrary substituents.

* denotes each bond.)

As R ^b in formula (i), those exemplified as R ^c12 in formula (c1) can be preferably employed.

The benzene ring in formula (i) may be further substituted by arbitrary substituents, and as a substituent, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group are mentioned, for example. can The number of substituents is not specifically limited, The number may be one, and two or more may be sufficient as them.

It is preferable that the partial structure represented by Formula (i) is a partial structure represented by a following formula (i-1) from a viewpoint of image development solubility.

[Formula 16]

(In formula (i-1), R ^a and R ^b have the same meanings as R ^a and R ^b in formula (i).

R ^Y represents a hydrogen atom or a polybasic acid residue.

The benzene ring in Formula (i-1) may be further substituted by arbitrary substituents.

* denotes each bond.)

As R ^Y in formula (i-1), those exemplified as R ^c13 in formula (c2) can be preferably employed.

The benzene ring in Formula (i-1) may be further substituted by arbitrary substituents. As a substituent, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group are mentioned, for example. The number of substituents is not specifically limited, The number may be one, and two or more may be sufficient as them.

The number of repeating unit structures represented by Formula (i-1) contained in 1 molecule of epoxy (meth)acrylate resin (C-2-1) may be one, or 2 or more types may be sufficient as it.

Although the number of partial structures represented by Formula (i) contained in 1 molecule of epoxy (meth)acrylate resin (C-2-1) is not specifically limited, 1 or more is preferable, 2 or more are more preferable, 3 The above is more preferable, and 10 or less are preferable, and 8 or less are still more preferable. For example, 1-10 are preferable, 2-10 are more preferable, and 3-8 are still more preferable. There exists a tendency for developability to improve by using more than the said lower limit. There exists a tendency for ink repellency to improve by using below the said upper limit.

Although the number of partial structures represented by Formula (i-1) contained in 1 molecule of epoxy (meth)acrylate resin (C-2-1) is not specifically limited, 1 or more is preferable, and 2 or more are more preferable, , 3 or more are more preferable, 10 or less are preferable, and 8 or less are still more preferable. For example, 1-10 are preferable, 2-10 are more preferable, and 3-8 are still more preferable. There exists a tendency for developability to improve by using more than the said lower limit. There exists a tendency for ink repellency to improve by using below the said upper limit.

Specific examples of the epoxy (meth)acrylate resin (C-2-1) are given below.

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

Next, the epoxy (meth)acrylate resin (C-2-2) will be described in detail.

[Formula 24]

(In formula (ii), R ^c each independently represents a hydrogen atom or a methyl group.

R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.

R ^e and R ^f each independently represent a divalent aliphatic group which may have a substituent.

l and m each independently represent the integer of 0-2.

* denotes each bond.)

(R ^d )

In formula (ii), R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.

Examples of the cyclic hydrocarbon group include an aliphatic cyclic group or an aromatic cyclic group.

Although the number of rings which an aliphatic cyclic group has is not specifically limited, Usually, 1 or more, 2 or more are preferable, More preferably, it is 10 or less, 5 or less are more preferable, and 3 or less are still more preferable. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Further, the number of carbon atoms in the alicyclic group is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, further preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, , 15 or less are particularly preferred. For example, 4-40 are preferable, 4-30 are more preferable, 6-20 are still more preferable, 8-15 are especially preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Specific examples of the aliphatic ring in the aliphatic ring group include, for example, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclo and a dodecane ring. Among these, an adamantane ring is preferable from a heat resistant viewpoint.

Although the number of rings which an aromatic cyclic group has is not specifically limited, Usually, 1 or more, 2 or more are preferable, 3 or more are more preferable, Furthermore, Preferably it is 10 or less, 5 or less are more preferable, 4 or less is more preferable. For example, 1-10 are preferable, 2-5 are more preferable, and 3-4 are still more preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Examples of the aromatic cyclic group include an aromatic hydrocarbon cyclic group and an aromatic heterocyclic group. Moreover, carbon number of an aromatic ring group becomes like this. Preferably it is 4 or more, 6 or more are more preferable, 8 or more are still more preferable, 10 or more are still more preferable, 12 or more are especially preferable, and 40 or less are preferable. and 30 or less are more preferable, 20 or less are still more preferable, and 15 or less are especially preferable. For example, 4-40 are preferable, 6-40 are more preferable, 8-30 are still more preferable, 10-20 are still more preferable, 12-15 are especially preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Specific examples of the aromatic ring in the aromatic ring group include, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a tri A phenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring are mentioned. Among these, a fluorene ring is preferable from a heat resistant viewpoint.

The divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and for example, a divalent aliphatic group, a divalent aromatic ring group, one or more divalent aliphatic groups and one or more divalent aromatic groups. and a group linking a cyclic group.

Examples of the divalent aliphatic group include linear, branched and cyclic ones. Among these, a linear thing is preferable from a viewpoint of developability improvement. On the other hand, from the viewpoint of heat resistance, a cyclic one is preferable. The carbon number is usually 1 or more, 3 or more are preferable, 6 or more are more preferable, and 25 or less are preferable, 20 or less are more preferable, and 15 or less are still more preferable. For example, 1-25 are preferable, 3-20 are more preferable, and 6-15 are still more preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Specific examples of the divalent linear aliphatic group include methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, and n-heptylene group. Among these, a methylene group is preferable from a heat resistant viewpoint.

Specific examples of the divalent branched aliphatic group include, as a side chain, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso to the aforementioned divalent linear aliphatic group. The structure which has a -butyl group, a sec-butyl group, and a tert-butyl group is mentioned.

Although the number of rings which a bivalent cyclic aliphatic group has is not specifically limited, Usually, 1 or more, 2 or more are preferable, More preferably, it is 10 or less, 5 or less are more preferable, 3 or less are still more preferable. do. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Specific examples of the divalent cyclic aliphatic group include, for example, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclo and a group in which two hydrogen atoms have been removed from the dodecane ring. Among these, groups in which two hydrogen atoms have been removed from the adamantane ring from the viewpoint of heat resistance are preferable.

As a substituent which the divalent aliphatic group may have, For example, C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; hydroxyl group; nitro group; cyano group; and a carboxyl group. The divalent aliphatic group is preferably unsubstituted from the viewpoint of synthesis easiness.

Examples of the divalent aromatic cyclic group include a divalent aromatic hydrocarbon cyclic group and a divalent aromatic heterocyclic group. The carbon number is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, more preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. For example, 4-30 are preferable, 5-20 are more preferable, and 6-15 are still more preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

As the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group, a monocyclic ring may be sufficient or a condensed ring may be sufficient as it. The divalent aromatic hydrocarbon ring group includes, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, having two free valences. , a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring are mentioned.

A monocyclic ring may be sufficient as an aromatic heterocyclic ring in an aromatic heterocyclic group, and a condensed ring may be sufficient as it. The divalent aromatic heterocyclic group includes, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, having two free valences. , indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoox Xazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinoline ring, quinoxaline ring, phenanthridine a ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring are mentioned. Among these, from a viewpoint of manufacturing cost, the benzene ring or naphthalene ring which has two free valences is preferable, and the benzene ring which has two free valences is more preferable.

As a substituent which the divalent aromatic ring group may have, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group, etc. are mentioned. As a divalent aromatic cyclic group, unsubstituted is preferable from a sclerosis|hardenable viewpoint.

Examples of the group in which one or more divalent aliphatic groups are connected to one or more divalent aromatic ring groups include groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups described above are connected.

Although the number of divalent aliphatic groups is not specifically limited, Usually, 1 or more, 2 or more are preferable, More preferably, it is 10 or less, 5 or less are more preferable, and 3 or less are still more preferable. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. There exists a tendency for developability to improve by using more than the said lower limit. There exists a tendency for heat resistance to improve by using below the said upper limit.

Although the number of divalent aromatic ring groups is not specifically limited, Usually, 1 or more, 2 or more are preferable, More preferably, it is 10 or less, 5 or less are more preferable, and 3 or less are still more preferable. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Specific examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the above formulas (c1-1) to (c1-6). Among these, the group represented by the said formula (c1-3) from a viewpoint of film|membrane strength is preferable.

With respect to these divalent hydrocarbon groups, the bonding mode of the cyclic hydrocarbon group as a side chain is not particularly limited, For example, an aspect in which one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with a cyclic hydrocarbon group as a side chain, The aspect which comprised the cyclic hydrocarbon group which is a side chain including one carbon atom of an aliphatic group is mentioned.

(R ^e , R ^g )

In formula (ii), R ^e and R ^g each independently represent a divalent aliphatic group which may have a substituent.

Examples of the divalent aliphatic group include linear, branched and cyclic ones. Among these, a linear thing is preferable from a viewpoint of image development solubility. On the other hand, from the viewpoint of heat resistance, a cyclic one is preferable.

The carbon number is normally 1 or more, 3 or more are preferable, 6 or more are more preferable, 20 or less are preferable, 15 or less are more preferable, and 10 or less are still more preferable. For example, 1-20 are preferable, 3-15 are more preferable, and 6-10 are still more preferable. There exists a tendency for adhesiveness with a board|substrate and ink repellency to improve by using more than the said lower limit. By setting it below the said upper limit, it is easy to suppress the deterioration of a sensitivity and the film|membrane decrease at the time of image development, and there exists a tendency for resolution to improve.

Specific examples of the divalent linear aliphatic group include, for example, a methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, and n-heptylene group. can be heard Among these, a methylene group is preferable from a viewpoint of the rigidity of frame|skeleton.

As a divalent branched aliphatic group, as a side chain in the above-mentioned divalent linear aliphatic group, for example, a methyl group, an ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso- The structure which has a butyl group, a sec-butyl group, and a tert- butyl group is mentioned.

Although the number of rings which a bivalent cyclic aliphatic group has is not specifically limited, Usually, 1 or more, 2 or more are preferable, More preferably, it is 12 or less, and 10 or less are more preferable. For example, 1-12 are preferable, 1-10 are more preferable, and 2-10 are still more preferable. There exists a tendency for adhesiveness with a board|substrate and ink repellency to improve by using more than the said lower limit. By setting it below the said upper limit, it is easy to suppress the deterioration of a sensitivity and the film|membrane decrease at the time of image development, and there exists a tendency for resolution to improve.

Specific examples of the divalent cyclic aliphatic group include, for example, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclo and groups in which two hydrogen atoms have been removed from a dodecane ring and a dicyclopentadiene ring. Among these, groups in which two hydrogen atoms have been removed from the dicyclopentadiene ring and the adamantane ring from the viewpoint of heat resistance are preferable.

As a substituent which the divalent aliphatic group may have, For example, C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; hydroxyl group; nitro group; cyano group; A carboxy group etc. are mentioned. The divalent aliphatic group is preferably unsubstituted from the viewpoint of synthesis easiness.

(l, m)

In formula (ii), l and m respectively independently represent the integer of 0-2. There exists a tendency for adhesiveness with a board|substrate to improve by using more than the said lower limit. There exists a tendency for developability to become favorable by using below the said upper limit. From a viewpoint of developability, it is preferable that l and m are 0. On the other hand, it is preferable that l and m are 1 or more from a viewpoint of adhesiveness with a board|substrate.

It is preferable that the partial structure represented by Formula (ii) is a partial structure represented by following formula (ii-1) from a viewpoint of film strength and ink repellency.

[Formula 25]

(In formula (ii-1), R ^c , ^{Re , R f ,} l and m have the same meanings as in the formula (ii).

R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent.

n is an integer greater than or equal to 1;

The benzene ring in Formula (ii-1) may be further substituted by arbitrary substituents.

* denotes each bond.)

(R ^α )

In the formula (ii-1), R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent.

Examples of the cyclic hydrocarbon group include an aliphatic cyclic group or an aromatic cyclic group.

Although the number of rings which an aliphatic cyclic group has is not specifically limited, Usually, 1 or more, 2 or more are preferable, More preferably, it is 6 or less, 4 or less are more preferable, and 3 or less are still more preferable. For example, 1-6 are preferable, 1-4 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

The number of carbon atoms in the alicyclic group is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, further preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and 15 The following are particularly preferred. For example, 4-40 are preferable, 4-30 are more preferable, 6-20 are still more preferable, 8-15 are especially preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Specific examples of the aliphatic ring in the aliphatic ring group include, for example, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclo and a dodecane ring. Among these, an adamantane ring is preferable from a viewpoint of coexistence of ink repellency and developability.

On the other hand, although the number of rings which an aromatic cyclic group has is not specifically limited, Usually, 1 or more, 2 or more are preferable, 3 or more are more preferable, Furthermore, Preferably it is 10 or less, and 5 or less are more preferable. . For example, 1-10 are preferable, 2-10 are more preferable, and 3-5 are still more preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Examples of the aromatic cyclic group include an aromatic hydrocarbon cyclic group and an aromatic heterocyclic group. Moreover, carbon number of an aromatic ring group becomes like this. Preferably it is 4 or more, 5 or more are more preferable, 6 or more are still more preferable, 30 or less are preferable, 20 or less are more preferable, and 15 or less are still more preferable. . For example, 4-30 are preferable, 5-20 are more preferable, and 6-15 are still more preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, the viewpoint of coexistence of ink repellency and developability to a fluorene ring is preferable.

Examples of the substituent that the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an amyl group, an iso-a group A C1-C5 alkyl group, such as a push group; C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; nitro group; cyano group; and a carboxyl group. As the cyclic hydrocarbon group, unsubstituted is preferable from the viewpoint of easiness of synthesis.

Although n represents an integer of 1 or more, 2 or more are preferable and 3 or less are preferable. For example, 1-3 are preferable and 2-3 are more preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Among these, from a viewpoint of coexistence of ink repellency and developability, it is preferable that R ^<alpha> is a monovalent|monohydric aliphatic cyclic group, and it is more preferable that it is an adamantyl group.

As mentioned above, the benzene ring in Formula (ii-1) may be further substituted by arbitrary substituents. As a substituent, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group are mentioned, for example. The number of substituents is not specifically limited, The number may be one, and two or more may be sufficient as them. As a benzene ring in Formula (ii-1), from a sclerosis|hardenable viewpoint, it is preferable that it is unsubstituted.

The specific example of the partial structure represented by Formula (ii-1) below is given.

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

Moreover, it is preferable that the partial structure represented by Formula (ii) is a partial structure represented by a following formula (ii-2) from a viewpoint of image development adhesiveness.

[Formula 31]

(In formula (ii-2), R ^c , ^{Re , R f ,} l and m have the same meanings as in the formula (ii).

R ^β represents a divalent cyclic hydrocarbon group which may have a substituent.

The benzene ring in Formula (ii-2) may be further substituted by arbitrary substituents.

* denotes each bond.)

(R ^β )

In the formula (ii-2), R ^β represents a divalent cyclic hydrocarbon group which may have a substituent.

Examples of the cyclic hydrocarbon group include an aliphatic cyclic group or an aromatic cyclic group.

* Although the number of rings which an aliphatic cyclic group has is not specifically limited, Usually, 1 or more, 2 or more are preferable, More preferably, it is 10 or less, and 5 or less are more preferable. For example, 1-10 are preferable and 2-5 are more preferable. There exists a tendency for developability to improve by using more than the said lower limit. There exists a tendency for ink repellency to improve by using below the said upper limit.

The number of carbon atoms of the alicyclic group is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, more preferably 40 or less, more preferably 35 or less, still more preferably 30 or less. For example, 4-40 are preferable, 6-35 are more preferable, 8-30 are still more preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Specific examples of the aliphatic ring in the aliphatic ring group include, for example, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclo and a dodecane ring. Among these, an adamantane ring is preferable from a viewpoint of coexistence of ink repellency and developability.

Although the number of rings which an aromatic cyclic group has is not specifically limited, Usually, 1 or more, 2 or more are preferable, 3 or more are more preferable, More preferably, it is 10 or less, and 5 or less are more preferable. For example, 1-10 are preferable, 2-10 are more preferable, and 3-5 are still more preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Examples of the aromatic cyclic group include an aromatic hydrocarbon cyclic group and an aromatic heterocyclic group. Moreover, carbon number of an aromatic ring group becomes like this. Preferably it is 4 or more, 6 or more are more preferable, 8 or more are still more preferable, 10 or more are especially preferable, and 40 or less are preferable, and 30 or less are more preferable. , 20 or less are more preferable, and 15 or less are particularly preferable. For example, 4-40 are preferable, 6-30 are more preferable, 8-20 are still more preferable, 10-15 are especially preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, a fluorene ring is preferable from a viewpoint of ink repellency and developability.

Examples of the substituent that the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, and amyl group. , an alkyl group having 1 to 5 carbon atoms, such as an iso-amyl group; C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; nitro group; cyano group; and a carboxyl group. As a cyclic hydrocarbon group, unsubstituted is preferable from a viewpoint of synthetic|combination simplicity.

Among these, it is preferable that it is a bivalent aliphatic cyclic group, and it is more preferable that it is a bivalent ^adamantane cyclic group from a viewpoint of ink repellency, developability, and heat resistance. On the other hand, it is preferable that it is a ^bivalent aromatic cyclic group, and, from a viewpoint of coexistence of ink repellency, developability, and heat resistance, it is more preferable that it is a bivalent fluorene ring group.

The benzene ring in Formula (ii-2) may be further substituted by arbitrary substituents. As a substituent, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group are mentioned, for example. The number of substituents is not specifically limited, The number may be one, and two or more may be sufficient as them. As a benzene ring in Formula (ii-2), it is preferable from a sclerosis|hardenable viewpoint that it is unsubstituted.

The specific example of the partial structure represented by Formula (ii-2) below is given.

[Formula 32]

[Formula 33]

[Formula 34]

[Formula 35]

On the other hand, it is preferable that the partial structure represented by Formula (ii) is a partial structure represented by a following formula (ii-3) from a developable viewpoint.

[Formula 36]

(In formula (ii-3), R ^c , R ^d , ^Re , R ^f , l and m have the same meanings as in formula (ii).

R ^Z represents a hydrogen atom or a polybasic acid residue.)

The polybasic acid residue means a monovalent group obtained by removing one OH group from the polybasic acid or anhydride thereof. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydro Phthalic acid, chlorendic acid, methyl tetrahydrophthalic acid, and biphenyl tetracarboxylic acid are mentioned.

Among these, from a viewpoint of a patterning characteristic, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable, tetrahydrophthalic acid, biphenyltetra Carboxylic acid is more preferable.

One type or two or more types may be sufficient as the partial structure represented by Formula (ii-3) contained in 1 molecule of epoxy (meth)acrylate resin (C-2-2).

Although the number of the partial structures represented by Formula (ii) contained in 1 molecule of epoxy (meth)acrylate resin (C-2-2) is not specifically limited, 1 or more is preferable, 3 or more are more preferable, and , 20 or less are preferable, 15 or less are more preferable, and 10 or less are still more preferable. For example, 1-20 are preferable, 1-15 are more preferable, and 3-10 are still more preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Although the number of partial structures represented by Formula (ii-1) contained in 1 molecule of epoxy (meth)acrylate resin (C-2-2) is not specifically limited, 1 or more is preferable, 3 or more are more preferable, Moreover, 20 or less are preferable, 15 or less are more preferable, and 10 or less are still more preferable. For example, 1-20 are preferable, 1-15 are more preferable, and 3-10 are still more preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Although the number of partial structures represented by Formula (ii-2) contained in 1 molecule of epoxy (meth)acrylate resin (C-2-2) is not specifically limited, 1 or more is preferable, 3 or more are more preferable, Moreover, 20 or less are preferable, 15 or less are more preferable, and 10 or less are still more preferable. For example, 1-20 are preferable, 1-15 are more preferable, 1-10 are still more preferable, 3-10 are especially preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for developability to improve by using below the said upper limit.

Although the number of partial structures represented by Formula (ii-3) contained in 1 molecule of epoxy (meth)acrylate resin (C-2-2) is not specifically limited, 1 or more is preferable, 3 or more are more preferable, Moreover, 20 or less are preferable, 15 or less are more preferable, and 10 or less are still more preferable. For example, 1-20 are preferable, 1-15 are more preferable, 1-10 are still more preferable, 3-10 are especially preferable. There exists a tendency for developability to improve by using more than the said lower limit. There exists a tendency for ink repellency to improve by using below the said upper limit.

Although the acid value of epoxy (meth)acrylate resin (C-2) is not specifically limited, 10 mgKOH/g or more is preferable, 30 mgKOH/g or more is more preferable, 50 mgKOH/g or more is still more preferable. and more preferably 70 mgKOH/g or more, particularly preferably 80 mgKOH/g or more, more preferably 200 mgKOH/g or less, more preferably 180 mgKOH/g or less, and more preferably 150 mg KOH/g or less is still more preferable, 120 mgKOH/g or less is still more preferable, and 110 mgKOH/g or less is especially preferable. For example, 10-200 mgKOH/g is preferable, 30-180 mgKOH/g is more preferable, 50-150 mgKOH/g is still more preferable, 70-120 mgKOH/g is still more preferable. and 80 to 110 mgKOH/g is particularly preferable. There exists a tendency for developability to improve by using more than the said lower limit. There exists a tendency for ink repellency and film|membrane intensity|strength to improve by using below the said upper limit.

Although the weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (C-2) is not specifically limited, Preferably it is 1000 or more, More preferably, it is 2000 or more, More preferably, it is 3000 or more, Especially preferably, 3500 or more. More preferably, it is 30000 or less, More preferably, it is 15000 or less, More preferably, it is 10000 or less, More preferably, it is 8000 or less, Especially preferably, it is 5000 or less. For example, 1000-30000 are preferable, 1000-15000 are more preferable, 2000-10000 are still more preferable, 3000-8000 are still more preferable, 3500-5000 are especially preferable. There exists a tendency for ink repellency and film|membrane intensity|strength to improve by setting it as more than the said lower limit. There exists a tendency for a residue to reduce by using below the said upper limit.

Next, the acrylic copolymer resin (C-3) will be described in detail.

[Acrylic copolymer resin (C-3)]

Acrylic copolymer resin (C-3) has an ethylenically unsaturated group in a side chain. By setting it as having an ethylenically unsaturated group, the film|membrane reduction|decrease by an alkali developing solution does not occur easily at the time of image development by photocuring by exposure, and surface smoothness becomes favorable. Moreover, there exists a tendency for adhesiveness with a board|substrate to improve by having a flexible main skeleton.

(partial structural unit represented by general formula (1))

Although the partial structure containing the side chain which has an ethylenically unsaturated group which the acrylic copolymer resin (C-3) has is not specifically limited, From a viewpoint of the easiness of emission of radical accompanying the flexibility of a film|membrane, adhesiveness with a board|substrate, For example, , it is preferable to have a partial structural unit represented by the following general formula (1).

[Formula 37]

(In formula (1), R ^a1 and R ^a2 each independently represent a hydrogen atom or a methyl group.

* indicates a bond.)

Moreover, the repeating unit represented by the following general formula (1') from a viewpoint of a sensitivity or alkali developability among the partial structural units represented by Formula (1) is preferable.

[Formula 38]

(In formula (1'), R ^a1 and R ^a2 each independently represent a hydrogen atom or a methyl group.

R ^x represents a hydrogen atom or a polybasic acid residue.)

The polybasic acid residue means a monovalent group obtained by removing one OH group from the polybasic acid or anhydride thereof. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydro Phthalic acid, chlorendic acid, methyl tetrahydrophthalic acid, and biphenyl tetracarboxylic acid are mentioned.

Among these, from a viewpoint of a patterning characteristic, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable, tetrahydrophthalic acid, biphenyltetra Carboxylic acid is more preferable.

When the acrylic copolymer resin (C-3) contains the partial structural unit represented by the general formula (1), the content is not particularly limited, but is preferably 10 mol% or more, and 20 mol% or more with respect to all repeating units. More preferably, 30 mol% or more is more preferable, 40 mol% or more is still more preferable, 50 mol% or more is particularly preferable, 90 mol% or less is preferable, and 85 mol% or less is more preferable , 80 mol% or less is more preferable, 75 mol% or less is still more preferable, and 70 mol% or less is particularly preferable. For example, 10-90 mol% is preferable, 20-85 mol% is more preferable, 30-80 mol% is still more preferable, 40-75 mol% is still more preferable, 50-70 mol% is more preferable Especially preferred. There exists a tendency for ink repellency to improve by using more than the said lower limit. There exists a tendency for a residue to reduce by using below the said upper limit.

When the acrylic copolymer resin (C-3) contains the repeating unit represented by the general formula (1'), the content rate is not particularly limited, but in all repeating units, 10 mol% or more is preferable, and 20 mol% or more More preferably, 25 mol% or more is more preferable, 30 mol% or more is still more preferable, 35 mol% or more is particularly preferable, 80 mol% or less is preferable, and 75 mol% or less is more preferable , 70 mol% or less is more preferable, and 65 mol% or less is particularly preferable. For example, 10-80 mol% is preferable, 20-80 mol% is more preferable, 25-75 mol% is still more preferable, 30-70 mol% is still more preferable, 35-65 mol% is more preferable Especially preferred. There exists a tendency for ink repellency to improve by using more than the said lower limit. By using below the said upper limit, there exists a tendency for image development adhesiveness to be easy to ensure.

(repeating unit represented by general formula (2))

When the acrylic copolymer resin (C-3) contains the partial structural unit represented by the general formula (1), the repeating unit included is not particularly limited, but from the viewpoint of developing adhesiveness, for example, the following general formula ( It is also preferable to have a repeating unit represented by 2).

[Formula 39]

(In formula (2), R ^a3 represents a hydrogen atom or a methyl group.

R ^a4 represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent.)

(R ^a4 )

In Formula (2), R ^a4 represents the alkyl group which may have a substituent, the aromatic ring group which may have a substituent, or the alkenyl group which may have a substituent.

Examples of the alkyl group for R ^a4 include a linear, branched or cyclic alkyl group. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, particularly preferably 8 or more, more preferably 20 or less, more preferably 18 or less, more preferably 16 or less. It is preferable, 14 or less are still more preferable, and 12 or less are especially preferable. For example, 1-20 are preferable, 1-18 are more preferable, 3-16 are still more preferable, 5-14 are still more preferable, 8-12 are especially preferable. By using more than the said lower limit, film|membrane intensity|strength becomes high and there exists a tendency for image development adhesiveness to improve. There exists a tendency for a residue to reduce by using below the said upper limit.

Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group. Among these, a dicyclopentanyl group or a dodecanyl group is preferable from a developable viewpoint, and a dicyclopentanyl group is more preferable.

In addition, as a substituent which the alkyl group may have, for example, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxy group, an acrylo group A diyl group and a methacryloyl group are mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

Examples of the aromatic ring group for R ^a4 include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. 6 or more are preferable, and, as for the carbon number, 24 or less are preferable, 22 or less are more preferable, 20 or less are still more preferable, 18 or less are especially preferable. For example, 6-24 are preferable, 6-22 are more preferable, 6-20 are still more preferable, 6-18 are especially preferable. There exists a tendency for image development adhesiveness to improve by using more than the said lower limit. There exists a tendency for a residue to reduce by using below the said upper limit.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring a ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring are mentioned.

The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, Dazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, Thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinoline ring, and a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. Among these, a benzene ring or a naphthalene ring is preferable from a developable viewpoint, and a benzene ring is more preferable.

In addition, as a substituent which the aromatic ring group may have, for example, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, oligoethylene glycol group, a phenyl group, and a carboxy group are mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

Examples of the alkenyl group for R ^a4 include a linear, branched or cyclic alkenyl group. 2 or more are preferable, and, as for the carbon number, 22 or less are preferable, 20 or less are more preferable, 18 or less are still more preferable, 16 or less are still more preferable, and 14 or less are especially preferable. For example, 2-22 are preferable, 2-20 are more preferable, 2-18 are still more preferable, 2-16 are still more preferable, 2-14 are especially preferable. There exists a tendency for image development adhesiveness to improve by using more than the said lower limit. There exists a tendency for a residue to reduce by using below the said upper limit.

Further, examples of the substituent that the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxy group. and a hydroxyl group and an oligoethylene glycol group are preferable from the viewpoint of developability.

As R ^a4 , among these, an alkyl group and an alkenyl group are preferable from a viewpoint of developability and film strength, and an alkyl group is more preferable.

When the acrylic copolymer resin (C-3) contains the repeating unit represented by the general formula (2), the content is not particularly limited, but in all the repeating units, 1 mol% or more is preferable, and 5 mol% or more is more Preferably, 10 mol% or more is more preferable, 20 mol% or more is particularly preferable, and 70 mol% or less is preferable, 60 mol% or less is more preferable, 50 mol% or less is still more preferable, 40 mol% or less is particularly preferred. For example, 1-70 mol% is preferable, 5-60 mol% is more preferable, 10-50 mol% is still more preferable, 20-40 mol% is especially preferable. There exists a tendency for image development adhesiveness to improve by using more than the said lower limit. There exists a tendency for a residue to reduce by using below the said upper limit.

(repeating unit represented by general formula (3))

When the acrylic copolymer resin (C-3) contains the partial structural unit represented by the general formula (1), as another repeating unit included, the repeating unit represented by the following general formula (3) from the viewpoint of heat resistance and film strength is preferably included.

[Formula 40]

(In the formula (3), R ^a5 represents a hydrogen atom or a methyl group.

R ^a6 is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxy group, a carboxy group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or a substituent The alkyl sulfide group which may exist is shown.

t represents an integer of 0 to 5.)

(R ^a6 )

In Formula (3), R ^a6 is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxy group, a carboxy group, a halogen atom, an alkoxy group which may have a substituent, a thiol group or an optionally substituted alkyl sulfide group.

Examples of the alkyl group for R ^a6 include a linear, branched or cyclic alkyl group. The carbon number is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, more preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, more preferably 14 or less. More preferably, 12 or less are particularly preferable. For example, 1-20 are preferable, 1-18 are more preferable, 3-16 are still more preferable, 3-14 are still more preferable, 5-12 are especially preferable. There exists a tendency for image development adhesiveness to improve by using more than the said lower limit. There exists a tendency for a residue to reduce by using below the said upper limit.

Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group. Among these, a dicyclopentanyl group and a dodecanyl group are preferable from a viewpoint of developability and film strength, and a dicyclopentanyl group is more preferable.

Examples of the substituent that the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxy group, an acryloyl group, A methacryloyl group is mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

Examples of the alkenyl group for R ^a6 include a linear, branched or cyclic alkenyl group. 2 or more are preferable, and, as for the carbon number, 22 or less are preferable, 20 or less are more preferable, 18 or less are still more preferable, 16 or less are still more preferable, and 14 or less are especially preferable. For example, 2-22 are preferable, 2-20 are more preferable, 2-18 are still more preferable, 2-16 are still more preferable, 2-14 are especially preferable. There exists a tendency for image development adhesiveness to improve by using more than the said lower limit. There exists a tendency for a residue to reduce by using below the said upper limit.

Examples of the substituent that the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxy group, From a viewpoint of , developability, a hydroxyl group and an oligoethylene glycol group are preferable.

Examples of the alkynyl group for R ^a6 include a linear, branched or cyclic alkynyl group. 2 or more are preferable, and, as for the carbon number, 22 or less are preferable, 20 or less are more preferable, 18 or less are still more preferable, 16 or less are still more preferable, and 14 or less are especially preferable. For example, 2-22 are preferable, 2-20 are more preferable, 2-18 are still more preferable, 2-16 are still more preferable, 2-14 are especially preferable. There exists a tendency for image development adhesiveness to improve by using more than the said lower limit. There exists a tendency for a residue to reduce by using below the said upper limit.

Examples of the substituent that the alkynyl group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, A phenyl group and a carboxy group are mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

A fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned as a halogen atom in R ^<a> , Among these, a fluorine atom is preferable from a developable viewpoint.

Examples of the alkoxy group for R ^a6 include a linear, branched or cyclic alkoxy group. 1 or more are preferable, and, as for the carbon number, 20 or less are preferable, 18 or less are more preferable, 16 or less are still more preferable, 14 or less are still more preferable, 12 or less are especially preferable. For example, 1-20 are preferable, 1-18 are more preferable, 1-16 are still more preferable, 1-14 are still more preferable, 1-12 are especially preferable. There exists a tendency for image development adhesiveness to improve by using more than the said lower limit. There exists a tendency for a residue to reduce by using below the said upper limit.

Examples of the substituent that the alkoxy group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxy group, an acryloyl group, A methacryloyl group is mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

Examples of the alkyl sulfide group for R ^a6 include a linear, branched or cyclic alkyl sulfide group. 1 or more are preferable, and, as for the carbon number, 20 or less are preferable, 18 or less are more preferable, 16 or less are still more preferable, 14 or less are still more preferable, 12 or less are especially preferable. For example, 1-20 are preferable, 1-18 are more preferable, 1-16 are still more preferable, 1-14 are still more preferable, 1-12 are especially preferable. There exists a tendency for image development adhesiveness to improve by using more than the said lower limit. There exists a tendency for a residue to reduce by using below the said upper limit.

As a substituent which the alkyl group in the alkyl sulfide group may have, for example, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, A carboxy group, an acryloyl group, and a methacryloyl group are mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

As R ^a6 , among these, a hydroxyl group or a carboxy group is preferable from a developable viewpoint, and a carboxy group is more preferable.

In Formula (3), although t represents the integer of 0-5, it is preferable that t is 0 from a viewpoint of manufacturing easiness.

When the acrylic copolymer resin (C-3) contains the repeating unit represented by the general formula (3), the content is not particularly limited, but in all the repeating units, 0.5 mol% or more is preferable, and 1 mol% or more is more Preferably, 2 mol% or more is more preferable, and 5 mol% or more is especially preferable. Moreover, 50 mol% or less is preferable, 40 mol% or less is more preferable, 30 mol% or less is still more preferable, 20 mol% or less is still more preferable, 15 mol% or less is especially preferable. For example, 0.5-50 mol% is preferable, 0.5-40 mol% is more preferable, 1-30 mol% is still more preferable, 2-20 mol% is still more preferable, 5-15 mol% is Especially preferred. There exists a tendency for image development adhesiveness to improve by using more than the said lower limit. There exists a tendency for a residue to reduce by using below the said upper limit.

(repeating unit represented by general formula (4))

When the acrylic copolymer resin (C-3) has a partial structural unit represented by the general formula (1), it is also preferable to have a repeating unit represented by the following general formula (4) from the viewpoint of developability as another repeating unit included. .

*[Formula 41]

(In the formula (4), R ^a7 represents a hydrogen atom or a methyl group.)

When the acrylic copolymer resin (C-3) contains the repeating unit represented by the general formula (4), the content is not particularly limited, but in all the repeating units, 5 mol% or more is preferable, and 10 mol% or more is more Preferably, 20 mol% or more is more preferable, 80 mol% or less is preferable, 70 mol% or less is more preferable, and 60 mol% or less is still more preferable. For example, 5-80 mol% is preferable, 10-70 mol% is more preferable, 20-60 mol% is still more preferable. There exists a tendency for developability to improve by using more than the said lower limit. There exists a tendency for image development adhesiveness to improve by using below the said upper limit.

Although the acid value of acrylic copolymer resin (C-3) is not specifically limited, 30 mgKOH/g or more is preferable, 40 mgKOH/g or more is more preferable, 50 mgKOH/g or more is still more preferable, 60 mg KOH/g or more is still more preferable, 150 mgKOH/g or less is preferable, 140 mgKOH/g or less is more preferable, 130 mgKOH/g or less is still more preferable, 120 mgKOH/g or less is more preferable than For example, 30-150 mgKOH/g is preferable, 40-140 mgKOH/g is more preferable, 50-130 mgKOH/g is still more preferable, 60-120 mgKOH/g is especially preferable. . There exists a tendency for developability to improve by using more than the said lower limit. There exists a tendency for image development adhesiveness to improve by using below the said upper limit.

Although the weight average molecular weight (Mw) of acrylic copolymer resin (C-3) is not specifically limited, Preferably it is 1000 or more, More preferably, it is 2000 or more, More preferably, it is 4000 or more, More preferably, it is 6000 or more, Especially Preferably it is 7000 or more, Most preferably, it is 8000 or more, More preferably, it is 30000 or less, More preferably, it is 20000 or less, More preferably, it is 15000 or less, Especially preferably, it is 10000 or less. For example, 1000-30000 are preferable, 2000-30000 are more preferable, 4000-20000 are still more preferable, 6000-20000 are still more preferable, 7000-15000 are still more preferable, 8000-10000 are especially preferable. do. There exists a tendency for image development adhesiveness to improve by using more than the said lower limit. There exists a tendency for developability to become favorable by using below the said upper limit.

Moreover, as a specific example of acrylic copolymer resin (C-3), resin of Unexamined-Japanese-Patent No. 8-297366 and Unexamined-Japanese-Patent No. 2001-89533 is mentioned, for example.

(C) alkali-soluble resin in this invention contains alkali-soluble resin other than epoxy (meth)acrylate resin (C-2) and acrylic copolymer resin (C-3) as another alkali-soluble resin may be doing

(C) Although the acid value of alkali-soluble resin is not specifically limited, 30 mgKOH/g or more is preferable, 50 mgKOH/g or more is more preferable, 60 mgKOH/g or more is preferable, and 300 mgKOH or more /g or less is preferable, 200 mgKOH/g or less is more preferable, 100 mgKOH/g or less is still more preferable, 80 mgKOH/g or less is especially preferable. For example, 30-300 mgKOH/g is preferable, 30-200 mgKOH/g is more preferable, 50-100 mgKOH/g is still more preferable, 60-80 mgKOH/g is especially preferable. . There exists a tendency for developability to improve by using more than the said lower limit. There exists a tendency for image development adhesiveness to improve by using below the said upper limit.

In addition, when (C) alkali-soluble resin is a mixture of 2 or more types, an acid value means the weighted average value according to the content rate.

Although the content rate of (C) alkali-soluble resin in the photosensitive resin composition of this invention is not specifically limited, In the total solid of the photosensitive resin composition, Preferably it is 5 mass % or more, More preferably, it is 10 mass % or more, More Preferably it is 20 mass % or more, More preferably, it is 30 mass % or more, Especially preferably, it is 40 mass % or more, More preferably, it is 50 mass % or more, Most preferably, it is 60 mass % or more. Preferably it is 90 mass % or less, More preferably, it is 80 mass % or less, More preferably, it is 70 mass % or less. For example, 5-90 mass % is preferable, 10-90 mass % is more preferable, 20-90 mass % is still more preferable, 30-80 mass % is still more preferable, 40-80 mass % is more preferable More preferably, 50-70 mass % is especially preferable, and 60-70 mass % is the most preferable. There exists a tendency for a residue to reduce by setting it as more than the said lower limit. There exists a tendency for ink repellency to improve by using below the said upper limit.

Although the content rate of alkali-soluble resin (C-1) in the photosensitive resin composition of this invention is not specifically limited, 20 mass % or more is preferable in the total solid of the photosensitive resin composition, and 30 mass % or more is more preferable, , more preferably 40 mass % or more, still more preferably 50 mass % or more, particularly preferably 60 mass % or more, more preferably 90 mass % or less, more preferably 80 mass % or less, more preferably 70 mass % or more. % or less is more preferable, and 65 mass % or less is especially preferable. For example, 20-90 mass % is preferable, 30-90 mass % is more preferable, 40-80 mass % is still more preferable, 50-70 mass % is still more preferable, 60-65 mass % is more preferable Especially preferred. There exists a tendency for ink repellency and image development adhesiveness to improve by using more than the said lower limit. There exists a tendency for a residue to reduce by using below the said upper limit.

(C) Although the content rate of alkali-soluble resin (C-1) in alkali-soluble resin is not specifically limited, 20 mass % or more is preferable, 40 mass % or more is more preferable, and 60 mass % or more is still more preferable. and more preferably 70 mass % or more, particularly preferably 80 mass % or more, most preferably 90 mass % or more, and usually 100 mass % or less. There exists a tendency for ink repellency and image development adhesiveness to improve by using more than the said lower limit.

In addition, the total of the content rate of the (A) ethylenically unsaturated compound and the content rate of (C) alkali-soluble resin in the total solid of the photosensitive resin composition of this invention is although it does not specifically limit, 10 mass % or more is preferable , 30 mass % or more is more preferable, 60 mass % or more is still more preferable, 80 mass % or more is especially preferable, 95 mass % or less is preferable, 92 mass % or less is more preferable, 90 mass % or more The following are more preferable. For example, 10-95 mass % is preferable, 30-95 mass % is more preferable, 60-92 mass % is still more preferable, 80-90 mass % is especially preferable. There exists a tendency for the adhesiveness to the board|substrate of a partition to improve by using more than the said lower limit. There exists a tendency for light-shielding property and ink repellency to improve by using below the said upper limit.

[1-1-4] (D) Liquid repellent

The photosensitive resin composition of this invention contains the fluorine atom containing resin which has a crosslinking group as (D) liquid repellent. Since ink repellency can be provided to the surface of the barrier rib obtained by containing the fluorine atom containing resin which has a crosslinking group, it is thought that the color mixing of each pixel can be prevented in the barrier rib obtained.

As a crosslinking group, an epoxy group or an ethylenically unsaturated group is mentioned, for example, An ethylenically unsaturated group is preferable from a viewpoint of the outflow suppression to the developing solution of a liquid repellent.

By using a liquid repellent having a crosslinking group, when the formed coating film is exposed to light, the crosslinking reaction on the surface can be accelerated, and the liquid repellent is less likely to flow out by the developing treatment, and as a result, the obtained partition wall has high ink repellency. It is thought that it can be done by representing

Moreover, the liquid repellent (D) which is a fluorine atom containing resin orientates on the surface of a partition, and tends to act to prevent the spreading of ink or color mixing. More specifically, the group having a fluorine atom tends to crater the ink and function to prevent the ink from spreading or mixing colors due to the ink entering the adjacent region across the barrier rib.

The fluorine atom-containing resin having a crosslinking group preferably has either or both of a perfluoroalkyl group and a perfluoroalkylene ether chain. By having either or both of the perfluoroalkyl group and the perfluoroalkylene ether chain, the fluorine atom-containing resin is more easily oriented on the surface of the partition wall, exhibits higher ink repellency, and prevents ink bleeding and color mixing. more prone to prevention.

Examples of the perfluoroalkyl group include a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group. Perfluoroalkyleneether chains include, for example, -CF ₂ -O-, -(CF ₂ ) ₂ -O-, -(CF ₂ ) ₃ -O-, -CF ₂ -C(CF ₃ ) O-, -C(CF ₃ )-CF ₂ -O- and a divalent group having a repeating unit thereof are mentioned.

Specific examples of the fluorine atom-containing resin having a crosslinking group include, for example, an acrylic copolymer resin having an epoxy group and a perfluoroalkyl group, an acrylic copolymer resin having an epoxy group and a perfluoroalkylene ether chain, an ethylenically unsaturated group, and purple An acrylic copolymer resin having a luoroalkyl group, an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain, an epoxy (meth)acrylate resin having an epoxy group and a perfluoroalkyl group, an epoxy group and a perfluoroalkylene Epoxy (meth) acrylate resin having an ether chain, an epoxy (meth) acrylate resin having an ethylenically unsaturated group and a perfluoroalkyl group, an epoxy (meth) acrylic having an ethylenically unsaturated group and a perfluoroalkylene ether chain a rate resin is mentioned. Among these, from the viewpoint of ink repellency, an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkyl group, an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain are preferable, and an ethylenically unsaturated group and An acrylic copolymer resin having a perfluoroalkylene ether chain is more preferable.

Examples of commercially available resins containing fluorine atoms having these crosslinking groups include "Megapac (registered trademark, hereinafter the same) F116" manufactured by DIC, "Megapac F120", "Megapac F142D", "Megapac F144D", and "Megapac F144D" F150”, “Mega-Park F160”, “Mega-Park F171”, “Mega-Park F172”, “Mega-Park F173”, “Mega-Park F177”, “Mega-Park F178A”, “Mega-Park F178K”, “Mega-Park F179” , 「Mega Park F183」, 「Mega Park F184」, 「Mega Park F191」, 「Mega Park F812」, 「Mega Park F815」, 「Mega Park F824」, 「Mega Park F833」, 「Mega Park RS101」, 「 Mega Park RS102" "Mega Park RS105", "Mega Park RS201", "Mega Park RS202", "Mega Park RS301", "Mega Park RS303" "Mega Park RS304", "Mega Park RS401", "Mega Park RS402" , 「Mega Park RS501」, 「Mega Park RS502」, 「Mega Park RS-72-K」, 「Mega Park RS-78」, 「Mega Park RS-90」, 「DEFENSA (registered trademark, hereinafter the same) MCF300」 , "DEFENSA MCF310", "DEFENSA MCF312", "DEFENSA MCF323", 3M Japan "Fluorad FC430", "Fluorad FC431", "FC-4430", "FC4432", AGC's "Asahi Guard (Registered) Trademark) AG710”, “Sufflon (registered trademark, hereinafter the same) S-382”, “Sufflon SC-101”, “Sufflon SC-102”, “Sufflon SC-103”, “Sufflon SC-104” ', "Suflon SC-105", "Suflon SC-106", etc., commercially available fluorine-containing organic compounds can be used.

Among these, as the acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene group, "Megapac RS-72-K", "Megapac RS-78", and "Megapac RS-90" can be preferably used. have.

The content of fluorine atoms in the fluorine atom-containing resin having a crosslinking group is not particularly limited, but in the fluorine atom-containing resin having a crosslinking group, preferably 5 mass% or more, more preferably 10 mass% or more, and still more preferably 20 mass% or more and 25 mass % or more is still more preferable. Moreover, 50 mass % or less is preferable, and 35 mass % or less is more preferable. For example, 5-50 mass % is preferable, 10-50 mass % is more preferable, 20-35 mass % is still more preferable, 25-35 mass % is especially preferable. There exists a tendency that the outflow to a pixel part can be suppressed by setting it as the said lower limit or more. There exists a tendency to show a high contact angle by using below the said upper limit.

The molecular weight in particular of the fluorine atom containing resin which has a crosslinking group is not restrict|limited, A low molecular weight compound may be sufficient, and a high molecular weight body may be sufficient. It is preferable that it is a high molecular weight body, since the fluidity|liquidity by a post-baking can be suppressed and the outflow from a partition can be suppressed. In the case of a high molecular weight fluorine atom-containing resin having a crosslinking group, the number average molecular weight of the fluorine atom-containing resin having a crosslinking group is preferably 100 or more, more preferably 500 or more, preferably 100000 or less, and more preferably 10000 or less. . For example, 100-100000 are preferable and 500-10000 are more preferable.

Although the content rate of (D) liquid repellent in the photosensitive resin composition of this invention is not specifically limited, Preferably it is 0.01 mass % or more in total solid of the photosensitive resin composition, More preferably, it is 0.1 mass % or more, More preferably is 0.5 mass% or more, preferably 5 mass% or less, more preferably 3 mass% or less, still more preferably 2 mass% or less. For example, 0.01-5 mass % is preferable, 0.1-3 mass % is more preferable, 0.5-2 mass % is still more preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. By using below the said upper limit, when apply|coating ink to a pixel part after partition formation, there exists a tendency for a uniform coating film to become easy to be obtained.

Although the content rate of the fluorine atom containing resin which has a crosslinking group in the photosensitive resin composition of this invention is not specifically limited, Preferably it is 0.01 mass % or more in total solid of the photosensitive resin composition, More preferably, 0.1 mass % or more, further Preferably it is 0.5 mass % or more, More preferably, it is 5 mass % or less, More preferably, it is 3 mass % or less, More preferably, it is 2 mass % or less. For example, 0.01-5 mass % is preferable, 0.1-3 mass % is more preferable, 0.5-2 mass % is still more preferable. There exists a tendency for ink repellency to improve by using more than the said lower limit. By using below the said upper limit, when apply|coating ink to a pixel part after partition formation, there exists a tendency for a uniform coating film to become easy to be obtained.

In the photosensitive resin composition of this invention, you may use surfactant with (D) liquid repellent. Surfactants can be used, for example, for the purpose of improving applicability as a coating liquid of the photosensitive resin composition and developability of a coating film, and among them, silicone-based surfactants and fluorine-based surfactants having no crosslinking group are preferable. .

In particular, silicone-based surfactants are preferable, and polyether-modified silicone-based surfactants are more preferable because they have a function of removing residues of the photosensitive resin composition from unexposed areas during development and also have a function of expressing wettability. .

As a fluorochemical surfactant which does not have a crosslinking group, the compound which has a fluoroalkyl or a fluoroalkylene group in at least any site|part of a terminal, a main chain, and a side chain is preferable.

As these commercially available products, "BM-1000", "BM-1100" manufactured by BM Chemie, "Megapac F142D" manufactured by DIC, "Megapac F172", "Megapac F173", "Megapac" F183", "Megapac F470", "Megapac F475", "Megapac F554", "Megapac F559", "FC430" by 3M Japan, "DFX-18" by Neos, etc. are mentioned.

In addition, as a silicone type surfactant, "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032 Additive", "SH8400" made by Toray Dow Corning Co., Ltd., for example, are, for example, Commercial items, such as "BYK (trademark, the same hereafter) 323" by Big Chemi company, and "BYK330", are mentioned.

As surfactant, things other than a fluorochemical surfactant and silicone type surfactant may be included, and nonionic, anionic, cationic, and amphoteric surfactant are mentioned as surfactant in addition.

As a nonionic surfactant, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters are, for example, , Glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythrit fatty acid esters, polyoxyethylene pentaerythrit fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitan fatty acid esters and polyoxyethylene sorbit fatty acid esters.

As these commercial items, polyoxyethylene-type surfactant, such as "Emulgen (trademark, the same hereafter) 104P" by Kao Corporation, and "Emulgen A60", is mentioned, for example.

Examples of the anionic surfactant include alkyl sulfonates, alkylbenzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, higher alcohol sulfate esters, aliphatic alcohols. Sulfate ester salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate, and special high molecular weight surfactants can Among them, a special polymer-based surfactant is preferable, and a special polycarboxylic acid-type polymer-based surfactant is more preferable.

As these commercially available products, in the case of alkyl sulfate ester salts, for example, “Emal (registered trademark, hereinafter the same) 10” manufactured by Kao Corporation, and in the case of alkylnaphthalene sulfonates, “Perex (registered trademark)” manufactured by Kao Corporation, for example. ) NB-L", as a special polymer type surfactant, "Homogenol (trademark, the same hereafter) L-18" manufactured by Kao Corporation, "Homogenol L-100" is mentioned, for example.

As cationic surfactant, quaternary ammonium salts, imidazoline derivatives, and alkylamine salts are mentioned, for example. Moreover, as amphoteric surfactant, betaine type compounds, imidazolium salts, imidazolines, and amino acids are mentioned, for example.

Among these, quaternary ammonium salts are preferable and stearyl trimethylammonium salts are more preferable.

As these commercially available products, in the case of alkylamine salts, for example, “Acetamine (registered trademark) 24” manufactured by Kao Corporation, and quaternary ammonium salts are, for example, “Cotamine (registered trademark) 24” manufactured by Kao Corporation, “Cotamine (registered trademark, below)” same) 24P" and "Cotamine 86W" are mentioned.

Surfactant may be used individually by 1 type, and may be used in combination of 2 or more type. For example, a combination of a silicone-based surfactant and a fluorine-based surfactant, a combination of a silicone-based surfactant and a special polymer-based surfactant, and a combination of a fluorine-based surfactant and a special polymer-based surfactant are mentioned. Especially, the combination of a silicone type surfactant and a fluorine type surfactant is preferable.

In the combination of silicone surfactant and fluorine surfactant, for example, "DFX-18" manufactured by Neos, "BYK-300" or "BYK-330" manufactured by Big Chemical, and "S-393" manufactured by AGC Semi-Chemical Company combination of ; Combination of "KP340" by Shin-Etsu Silicone Co., Ltd. and "F-554" or "F-559" by DIC; Combination of "SH7PA" by Toray Dow Corning and "DS-401" by Daikin; The combination of "L-77" by NUC Corporation and "FC4430" by 3M Japan is mentioned.

[1-1-5] (E) Colorant

The photosensitive resin composition of this invention may contain the (E) coloring agent further. (E) By containing a coloring agent, moderate light absorptivity can be acquired and, when using for the use which forms the light-shielding member containing especially a colored partition, moderate light-shielding property can be acquired.

The kind of (E) coloring agent used by this invention is not specifically limited, A pigment may be used and dye may be used. Among these, it is preferable to use a pigment from a durable viewpoint.

(E) The number of pigments contained in a coloring agent may be one, or 2 or more types may be sufficient as them. In particular, from a viewpoint of uniformly shielding light in a visible region, it is preferable that it is 2 or more types.

(E) Although the kind of pigment which can be used as a coloring agent is not specifically limited, For example, an organic pigment and an inorganic pigment are mentioned. Among these, it is preferable to use an organic pigment from a viewpoint of controlling the transmission wavelength of the photosensitive resin composition and making it harden|cure efficiently.

As an organic pigment, an organic coloring pigment and an organic black pigment are mentioned. Here, an organic coloring pigment means the organic pigment which shows colors other than black, and a red pigment, an orange pigment, a blue pigment, a purple pigment, a green pigment, a yellow pigment, etc. are mentioned.

It is preferable to use an organic coloring pigment from a viewpoint of ultraviolet absorption among organic pigments.

An organic coloring pigment may be used individually by 1 type, and may use 2 or more types together. In particular, when using for a light-shielding use, it is more preferable to use combining the organic coloring pigments from which a color differs, and it is further more preferable to use the combination of the organic coloring pigment which shows the color close to black.

Although the chemical structure of these organic pigments is not specifically limited, For example, an azo type, a phthalocyanine type, a quinacridone type, a benzimidazolone type, an isoindolinone type, a dioxazine type, an indanthrene type, and a perylene type are mentioned. . Hereinafter, the specific example of the pigment which can be used is shown by a pigment number. “C. Terms such as "I. Pigment Red 2" mean a color index (C.I.).

As a red pigment, C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38 , 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1 , 53 : 2, 53 : 3, 57, 57 : 1, 57 : 2, 58 : 4, 60, 63, 63 : 1, 63 : 2, 64, 64 : 1, 68, 69, 81, 81 : 1 , 81 : 2, 81 : 3, 81 : 4, 83, 88, 90 : 1, 101, 101 : 1, 104, 108, 108 : 1, 109, 112, 113, 114, 122, 123, 144, 146 , 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202 , 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250 , 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 can

Among these, from the viewpoint of light-shielding properties and dispersibility, preferably C. I. Pigment Red 48: 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, more preferably and C. I. Pigment Red 177, 209, 224, 254.

In addition, from the viewpoint of dispersibility and light blocking properties, it is preferable to use C.I. Pigment Red 177, 254, and 272, and when curing the photosensitive resin composition with ultraviolet rays, it is preferable to use a red pigment having a low ultraviolet absorption rate. Preferably, from this point of view, it is more preferable to use C. I. Pigment Red 254, 272.

Orange (orange) pigments include C. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79.

Among these, from the viewpoint of dispersibility and light-shielding property, it is preferable to use C.I. Pigment Orange 13, 43, 64, and 72, more preferably to use C. I. Pigment Orange 43, 64, 72, and the photosensitive resin composition In the case of curing with ultraviolet rays, it is preferable to use those having a low ultraviolet absorption rate as the orange pigment, and from this point of view, it is more preferable to use C.I. pigment oranges 64 and 72.

As a blue pigment, C. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27 , 28, 29, 33, 35, 36, 56, 56 : 1, 60, 61, 61 : 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be heard

Among them, from the viewpoint of light-shielding properties, preferably C. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 60, more preferably C. I. Pigment Blue 15: 6 can be mentioned.

Further, from the viewpoint of dispersibility and light-shielding properties, it is preferable to use C. I. Pigment Blue 15: 6, 16, 60, more preferably to use C. I. Pigment Blue 15: 6, 60, and the photosensitive resin composition In the case of curing with ultraviolet rays, it is preferable to use a blue pigment having a low ultraviolet absorption, and from this point of view, it is more preferable to use C.I. Pigment Blue 60.

As a purple pigment, C. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27 , 29, 31, 32, 37, 39, 42, 44, 47, 49, 50.

Among these, from a light-shielding viewpoint, Preferably C.I. Pigment Violet 19 and 23, More preferably, C.I. Pigment Violet 23 is mentioned.

In addition, from the viewpoint of dispersibility and light-shielding properties, it is preferable to use C.I. Pigment Violet 23, 29, and when curing the photosensitive resin composition with ultraviolet rays, it is preferable to use a purple pigment having a low ultraviolet absorption rate, , it is more preferable to use C. I. Pigment Violet 29 from this point of view.

As an organic color pigment which can be used other than a red pigment, an orange pigment, a blue pigment, and a purple pigment, a green pigment, a yellow pigment, etc. are mentioned, for example.

Examples of the green pigment include C. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 can

Among these, Preferably, C.I. Pigment Green 7 and 36 are mentioned.

As a yellow pigment, C. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35 : 1, 36, 36 : 1, 37, 37 : 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62 : 1, 63, 65, 73, 74, 75, 81, 83 , 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134 , 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170 , 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191 : 1, 192, 193, 194, 195, 196, 197, 198, 199 , 200, 202, 203, 204, 205, 206, 207, 208.

Among these, preferably C. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, More preferably, C. I. Pigment Yellow 83, 138, 139, 150, 180 can be mentioned. have.

Among these, it is preferable to use at least 1 sort(s) chosen from the group which consists of a red pigment, an orange pigment, a blue pigment, and a purple pigment from a viewpoint of light-shielding property and ink repellency.

Among these, it is preferable to set it as what contains at least 1 type or more of the following pigments from a viewpoint of light-shielding property and ink repellency.

Red Pigment: C. I. Pigment Red 177, 254, 272

Orange Pigment: C. I. Pigment Orange 64, 72

Blue Pigment: C. I. Pigment Blue 15: 6, 16, 60

Purple Pigment: C. I. Pigment Violet 23, 29

In the case of using two or more organic color pigments in combination, the combination of the organic color pigments is not particularly limited, but from the viewpoint of light-shielding properties, (E) as a colorant, at least one selected from the group consisting of red pigments and orange pigments; , It is preferable to contain at least 1 sort(s) chosen from the group which consists of a blue pigment and a purple pigment.

In addition, the combination of colors is not particularly limited, but from the viewpoint of light-shielding properties, for example, a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, and a combination of a blue pigment, an orange pigment and a purple pigment are mentioned. can

Moreover, it is preferable to contain a purple pigment as a (E) coloring agent from a light-shielding viewpoint of blue light.

It is preferable to use an organic black pigment as a (E) coloring agent from a light-shielding viewpoint. In particular, from the viewpoint of suppressing absorption of ultraviolet rays and improving ink repellency, a compound represented by the following general formula (A) (hereinafter also referred to as “compound (A)”), a geometric isomer of the compound (A), a compound ( An organic black pigment comprising at least one selected from the group consisting of a salt of A) and a salt of a geometric isomer of compound (A) (hereinafter referred to as “organic black pigment represented by the general formula (A)” in some cases) ) is preferably used.

[Formula 42]

(In formula (A), R ¹¹ and R ¹⁶ each independently represent a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom, or a chlorine atom;

R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a halogen atom, R ²¹ , COOH, COOR ²¹ , COO ^- , CONH ₂ , CONHR ²¹ , CONR ²¹ R ²² , CN, OH, OR ²¹ , COCR ²¹ , OOCNH ₂ , OOCNHR ²¹ , OOCNR ²¹ R ²² , NO ₂ , NH ₂ , NHR ²¹ , NR ²¹ R ²² , NHCOR ²² , NR ²¹ COR ²² , N =CH ₂ , N=CHR ²¹ , N=CR ²¹ R ²² , SH, SR ²¹ , SOR ²¹ , SO ₂ R ²¹ , SO ₃ R ²¹ , SO ₃ H, SO ₃ ^- , SO ₂ NH ₂ , SO ₂ NHR ²¹ or SO ₂ NR ²¹ R ²² ;

At least one combination selected from the group consisting of R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ may be directly may be bonded, or may be bonded to each other via an oxygen atom, a sulfur atom, NH or NR ²¹ bridge;

R ²¹ and R ²² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. .

Compound (A) and geometric isomers of compound (A) have the following core structures (provided that the substituents in the structural formulas are omitted), and the trans-trans isomer is probably the most stable.

[Formula 43]

When compound (A) is anionic, its charge is transferred to any known suitable cation, for example a metal, organic, inorganic or metal organic cation, in particular an alkali metal, alkaline earth metal, transition metal, primary ammonium , secondary ammonium, tertiary ammonium, such as trialkylammonium, quaternary ammonium, such as tetraalkylammonium, or a salt compensated with an organometallic complex is preferable. Moreover, when the geometrical isomer of compound (A) is anionic, it is preferable that it is the same salt.

In the substituents of the general formula (A) and their definitions, the following are preferable because the shielding rate tends to increase. This is because the following substituents do not absorb and it is thought that the hue of a pigment is not affected.

R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom.

R ¹³ and R ¹⁸ are each independently, preferably a hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , a bromine atom, a chlorine atom, CH ₃ , C ₂ H ₅ , N(CH ₃ ) ₂ , N( CH ₃ )(C ₂ H ₅ ), N(C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO ₃ -, more preferably a hydrogen atom or SO ₃ H; A hydrogen atom is particularly preferred.

R ¹¹ and R ¹⁶ are each independently, preferably a hydrogen atom, CH ₃ or CF ₃ , and more preferably a hydrogen atom.

Preferably, at least one combination selected from the group consisting of R ¹¹ and R ¹⁶ , R ¹² and R ¹⁷ , R ¹³ and R ¹⁸ , R ¹⁴ and R ¹⁹ , and R ¹⁵ and R ²⁰ is the same, more preferably Preferably, R ¹¹ is identical to R ¹⁶ , R ¹² is identical to R ¹⁷ , R ¹³ is identical to R ¹⁸ , R ¹⁴ is identical to R ¹⁹ , and R ¹⁵ is identical to R ²⁰ .

The C1-C12 alkyl group is, for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n-pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group , 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group.

The cycloalkyl group having 3 to 12 carbon atoms is, for example, a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a trimethylcyclohexyl group, a tuyl group, a norbornyl group, a bor group. nyl group, norcaryl group, caryl group, menthyl group, norphinyl group, pinyl group, adamantan-1-yl group, and adamantan-2-yl group.

The alkenyl group having 2 to 12 carbon atoms is, for example, a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-buten-1-yl group, a 3-buten-1-yl group, and 1,3-butadiene- 2-yl group, 2-penten-1-yl group, 3-penten-2-yl group, 2-menthyl-1-buten-3-yl group, 2-methyl-3-buten-2-yl group, 3-methyl-2- They are a buten-1-yl group, a 1,4-pentadien-3-yl group, a hexenyl group, an octenyl group, a nonenyl group, a decenyl group, and a dodecenyl group.

The cycloalkenyl group having 3 to 12 carbon atoms is, for example, a 2-cyclobuten-1-yl group, a 2-cyclopenten-1-yl group, a 2-cyclohexen-1-yl group, a 3-cyclohexen-1-yl group, 2,4-cyclohexadien-1-yl group, 1-p-menten-8-yl group, 4(10)-tuzen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadi en-1-yl group, 7,7-dimethyl-2,4-norkaradien-3-yl group, and campenyl group.

A C2-C12 alkynyl group is, for example, 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, 2-methyl-3-butyn-2-yl group, 1,4-pentadiyn-3-yl group, 1,3-pentadiyn-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-yn-1-yl group, Trans-3-methyl-2-penten-4-yn-1-yl group, 1,3-hexadiyn-5-yl group, 1-octyne-8-yl group, 1-nonin-9-yl group, 1-decyne- 10-day, 1-dodecin-12-yl.

A halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The organic black pigment represented by the general formula (A) is preferably selected from the group consisting of a compound represented by the following general formula (B) (hereinafter also referred to as “compound (B)”) and a geometric isomer of the compound (B) It is an organic black pigment containing at least 1 sort(s) used.

[Formula 44]

As a specific example of such an organic black pigment, Irgaphor (trademark) Black S 0100 CF (made by BASF) is mentioned as a brand name.

This organic black pigment is preferably used by dispersing it with a dispersing agent, a solvent, and a method described later. When the sulfonic acid derivative of the compound (A), particularly the sulfonic acid derivative of the compound (B), is present during dispersion, dispersibility and storage properties may be improved, so that the organic black pigment preferably contains these sulfonic acid derivatives.

As organic black pigments other than the organic black pigment represented by general formula (A), aniline black, perylene black, etc. are mentioned, for example.

Moreover, as a coloring agent other than these organic pigments, an inorganic black pigment is mentioned. Moreover, in addition to an organic pigment, you may use an inorganic black pigment further.

Examples of the inorganic black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, and titanium black. Among these, carbon black can be preferably used from a light-shielding viewpoint. Examples of carbon black include the following carbon blacks.

Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40 , #144, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, #960, #970, #980, #990, #1000 2200, #12300, #2350, #2400, #2600, #2650, #3030, #3050, #3150, #3250, #3400, #3600, #3750, OIL7B4000, #9B4000, #40 , OIL11B, OIL30B, OIL31B

Manufactured by Degusa: Printex (registered trademark, hereinafter the same) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

Manufactured by Cabot Corporation: Monarch (registered trademark, hereinafter the same) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, hereinafter the same) 99, REGAL99R, REGAL415, REGAL415R , REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark, hereinafter the same) XC72R, ELFTEX (registered trademark) -8

Manufactured by Birla: RAVEN (registered trademark, hereinafter the same) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN78010, RAVEN850, RAVEN890H, RAVEN1060, RAVEN1020, RAVEN , RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

As carbon black, you may use what was coat|covered with resin. When carbon black coated with resin is used, there is an effect that the adhesiveness to the glass substrate and the volume resistance value are improved. As carbon black coated with resin, for example, the carbon black described in Unexamined-Japanese-Patent No. 09-71733, etc. can be used preferably. From the viewpoints of volume resistance and dielectric constant, resin-coated carbon black is preferably used.

As carbon black used for the coating process with resin, it is preferable that the total content of Na and Ca is 100 ppm or less. Carbon black is usually mixed with raw material oil or combustion oil (or gas) during production, reaction stop water or granulated water, furthermore, from the furnace material of the reactor, etc. Na, Ca, K, Mg, Al, It contains ash having a composition such as Fe. Among these, Na and Ca are generally contained in each of several hundred ppm or more, but by reducing these, penetration into the transparent electrode (ITO) or other electrodes is suppressed, and an electrical short circuit tends to be prevented. .

As a method of reducing the content of ash containing these Na and Ca, as raw material oil or fuel oil (or gas) and reaction stop water when manufacturing carbon black, carefully selecting those with the lowest possible content and structure This is possible by making the addition amount of the alkali substance to be adjusted as low as possible. As another method, there may be mentioned a method in which the carbon black produced in the furnace is washed with water or hydrochloric acid to dissolve Na and Ca to remove it.

Specifically, when carbon black is mixed and dispersed in water, hydrochloric acid, or hydrogen peroxide solution and then a solvent that is hardly soluble in water is added, the carbon black migrates to the solvent side, is completely separated from water, and most of the Na present in the carbon black and Ca are dissolved in water or acid and removed. In order to reduce the total amount of Na and Ca to 100 ppm or less, it may be possible to use only the carbon black production process in which raw materials are carefully selected or the water or acid dissolution method alone. The total amount can be 100 ppm or less.

Moreover, it is preferable that resin-coated carbon black is what is called acidic carbon black with a pH of 6 or less. Since the dispersion diameter (agglomerate diameter) in water becomes small, it becomes possible to coat|cover to a fine unit, and it is preferable. Moreover, it is preferable that the average particle diameter is 40 nm or less and the dibutyl phthalate (DBP) absorption amount is 140 ml/100 g or less. By setting it as the said range, there exists a tendency for the coating film with favorable light-shielding property to be obtained. The average particle diameter means a number average particle diameter, and it is obtained by particle image analysis in which several fields are taken of pictures taken at tens of thousands of times by electron microscope observation, and about 2000 to 3000 particles of these pictures are measured by an image processing device. Means the equivalent diameter of a circle.

The method for preparing the carbon black coated with the resin is not particularly limited, but for example, after appropriately adjusting the blending amount of the carbon black and the resin, 1. Mix the resin with a solvent such as cyclohexanone, toluene, and xylene and heat it The dissolved resin solution and the suspension in which carbon black and water are mixed are mixed and stirred to separate carbon black and water, water is removed, and a composition obtained by heating and kneading is formed into a sheet, pulverized, and dried. Way ; 2. A method of mixing and stirring the resin solution and suspension prepared in the same manner as above to granulate carbon black and resin, then separating and heating the obtained granular material to remove residual solvent and water; 3. Dissolve carboxylic acids such as maleic acid and fumaric acid in the solvents exemplified above, add carbon black, mix and dry, remove the solvent to obtain carboxylic acid-impregnated carbon black, and add a resin thereto How to dry blend; 4. The reactive group-containing monomer component constituting the resin to be coated and water are stirred at high speed to prepare a suspension, and after polymerization and cooling to obtain a reactive group-containing resin from the polymer suspension, carbon black is added thereto and kneaded; A method of reacting black with a reactive group (by grafting carbon black), cooling and pulverization, and the like can be employed.

The type of resin to be coated is also not particularly limited, but synthetic resins are common, and a resin having a benzene ring in its structure is preferable from the viewpoint of dispersibility and dispersion stability because the amphoteric surfactant-like action is stronger. do.

Specific synthetic resins include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyphtal resin, epoxy resin, and alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, and polybutylene. Terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfopolyphenylenesulfone, polyarylate, polyetheretherketone, etc. of thermoplastic resins can be used. As for the quantity of coating resin, 1-30 mass % is preferable with respect to the total amount of carbon black and resin. There exists a tendency which can make covering|covering into a sufficient thing by setting it as more than the said lower limit. On the other hand, by using below the said upper limit, adhesion of resins is prevented and there exists a tendency for dispersibility to be good.

The carbon black formed by coating with resin in this way can be used as a coloring agent for a colored partition in accordance with a conventional method. When such carbon black is used, there is a tendency that a colored partition wall having a high light-shielding rate and a low surface reflectance can be formed at low cost. Moreover, it is estimated that there exists an effect|action which encloses the ash content containing Na and Ca in carbon black by coat|covering the carbon black surface with resin.

These organic pigments and inorganic pigments are preferably dispersed and used so that the average particle diameter is usually 1 µm or less, preferably 0.5 µm or less, and more preferably 0.25 µm or less. Here, the standard of the average particle diameter is the number of pigment particles.

In addition, the average particle diameter of a pigment is the value calculated|required from the pigment particle diameter measured by dynamic light scattering (DLS). Particle size measurement is carried out with respect to a sufficiently diluted photosensitive resin composition (usually diluted and prepared with a pigment concentration of about 0.005 to 0.2 mass%. However, if there is a concentration recommended by the measuring instrument, it follows the concentration.) , measured at 25 °C.

Moreover, you may use dye other than the organic pigment and inorganic black pigment mentioned above. Examples of the dye usable as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

Examples of the azo dye include C. I. Acid Yellow 11, C. I. Acid Orange 7, C. I. Acid Red 37, C. I. Acid Red 180, C. I. Acid Blue 29, C. I. Direct Red 28, C. I. Direct Red 83, C. I. Direct Yellow 12, C. I. Direct Orange 26, C. I. Direct Green 28, C. I. Direct Green 59, C. I. Reactive Yellow 2, C. I. Reactive Red 17, C. I. Reactive Red 120, C. I. Reactive Black 5, C. I. Disperse Orange 5, C. I. Disperse Red 58 , C. I. Disperse Blue 165, C. I. Basic Blue 41, C. I. Basic Red 18, C. I. Mordant Red 7, C. I. Mordant Yellow 5, C. I. Mordant Black 7.

Examples of the anthraquinone dye include C. I. Butt Blue 4, C. I. Acid Blue 40, C. I. Acid Green 25, C. I. Reactive Blue 19, C. I. Reactive Blue 49, C. I. Disperse Red 60, C. I. Disperse Blue 56, C. I. Disperse Blue 60.

As the phthalocyanine-based dye, for example, C. I. Butt Blue 5 is exemplified, and as the quinoneimine-based dye, for example, C. I. Basic Blue 3 and C. I. Basic Blue 9 are exemplified, and as the quinoline-based dye, for example, , C. I. Solvent Yellow 33, C. I. Acid Yellow 3, C. I. Disperse Yellow 64, and as a nitro-based dye, for example, C. I. Acid Yellow 1, C. I. Acid Orange 3, C. I. Disperse Yellow 42.

When the photosensitive resin composition of this invention contains (E) coloring agent, Although the content rate of (E) coloring agent is not specifically limited, Preferably it is 1 mass % or more in total solid of the photosensitive resin composition, and 2 mass % or more This is more preferable, 3 mass % or more is more preferable, 4 mass % or more is especially preferable, More preferably, 50 mass % or less, 30 mass % or less is more preferable, 20 mass % or less is still more preferable, , more preferably 15 mass% or less, particularly preferably 12 mass% or less, and most preferably 10 mass% or less. For example, 1-50 mass % is preferable, 1-30 mass % is more preferable, 2-20 mass % is still more preferable, 2-15 mass % is still more preferable, 3-12 mass % is more preferable It is more preferable, and 4-10 mass % is especially preferable. There exists a tendency for light-shielding property to be securable by setting it as more than the said lower limit. Since alkali-soluble resin and an ethylenically unsaturated compound can be increased relatively by carrying out below the said upper limit, sclerosis|hardenability of a coating film, and ink repellency tend to improve.

[1-1-6] (F) dispersant

When the photosensitive resin composition of this invention contains (E) a coloring agent, in order to disperse|distribute (E) a coloring agent finely and to stabilize the dispersion state, it is preferable to contain (F) a dispersing agent.

(F) As a dispersing agent, the polymeric dispersing agent which has a functional group is preferable, Furthermore, from the point of dispersion stability, a carboxy group; phosphate group; sulfonic acid group; or a base thereof; a primary, secondary or tertiary amino group; quaternary ammonium base; A polymer dispersing agent having a functional group such as a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine or pyrazine is preferable. Among them, a primary, secondary, or tertiary amino group; quaternary ammonium base; A polymer dispersing agent having a basic functional group such as a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine or pyrazine is particularly preferable from the viewpoint of dispersing the pigment with a small amount of the dispersing agent.

In addition, as the polymer dispersant, for example, a urethane dispersant, an acrylic dispersant, a polyethyleneimine dispersant, a polyallylamine dispersant, a dispersant composed of a monomer having an amino group and a macromonomer, a polyoxyethylene alkyl ether dispersant, polyoxyethylene and a diester dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.

As a specific example of such a dispersing agent, it is a brand name, for example, EFKA (trademark. BASF company make.), DISPERBYK (trademark. Bigchemi company make.), Disperon (trademark. Kusumoto chemical company make.), for example. ), SOLSPERSE (trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflo (manufactured by Kyoeisha Chemical), and Azisper (registered trademark, manufactured by Ajinomoto Corporation).

A polymer dispersing agent may be used individually by 1 type, and may use 2 or more types together.

The weight average molecular weight (Mw) of the polymer dispersant is preferably 700 or more, more preferably 1000 or more, and more preferably 100000 or less, more preferably 50000 or less. For example, 700-100000 are preferable and, as for the weight average molecular weight (Mw) of a polymer dispersing agent, 1000-50000 are more preferable.

Among these, from the viewpoint of dispersibility of the pigment, (F) the dispersing agent preferably contains either or both of a urethane-based polymer dispersing agent having a functional group and an acrylic polymer dispersing agent, and particularly preferably containing an acrylic polymer dispersing agent.

Moreover, the polymer dispersing agent which has a basic functional group and has either one or both of a polyester bond and a polyether bond from the point of dispersibility and storage property is preferable.

Examples of the urethane-based and acrylic polymer dispersants include DISPERBYK-160 to 167 and 182 series (all of which are urethane-based), DISPERBYK-2000, 2001, and BYK-LPN21116 (all of which are acrylic-based) (all of which are manufactured by Bikchemi).

If a chemical structure suitable as a urethane-based polymer dispersant is specifically illustrated, for example, a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the molecule, and active hydrogen and tertiary in the same molecule Dispersion resin with a weight average molecular weight of 1000-20000 obtained by making the compound which has an amino group react is mentioned. By treating these with a quaternizing agent such as benzyl chloride, all or a part of the tertiary amino groups can be made into quaternary ammonium base groups.

Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, tolidine di Aliphatic diisocyanate, such as aromatic diisocyanate, such as isocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, 4,4'-methylene Bis(cyclohexyl isocyanate), ω,ω'-diisocyanate, alicyclic diisocyanate such as dimethylcyclohexane, xylylene diisocyanate, α,α,α',α'-tetramethylxylylene diisocyanate, etc. Aliphatic diisocyanate having, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate , tris(isocyanatephenylmethane), tris(isocyanatephenyl)thiophosphate, and the like triisocyanates, and trimers thereof, water adducts, and polyol adducts thereof. As polyisocyanate, the trimer of organic diisocyanate is preferable, and the trimer of tolylene diisocyanate and the trimer of isophorone diisocyanate are especially preferable.

These may be used individually by 1 type, and may use 2 or more types together.

As a method for producing a trimer of isocyanate, polyisocyanate is used as a suitable trimerization catalyst, for example, tertiary amines, phosphines, alkoxides, metal oxides, and carboxylates using partial 3 of isocyanate groups. A method of obtaining the target isocyanurate group-containing polyisocyanate by removing the unreacted polyisocyanate by solvent extraction and thin film distillation after performing quantification and stopping trimerization by addition of a catalyst poison is mentioned have.

Compounds having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and one terminal hydroxyl group of these compounds having 1 to 25 carbon atoms. alkoxylated with an alkyl group of , and mixtures of two or more thereof.

As polyether glycol, polyether diol, polyether ester diol, and these 2 or more types of mixture are mentioned. Examples of the polyetherdiol include those obtained by copolymerizing alkylene oxides alone or with polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and A mixture of 2 or more types thereof is mentioned.

The polyether ester diol is obtained by reacting an ether group-containing diol or a mixture with other glycols with dicarboxylic acid or anhydrides thereof, or reacting polyester glycol with alkylene oxide, for example, poly(polyoxytetramethylene) adipate. The most preferable polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Examples of the polyester glycol include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycols (ethylene glycol, diethylene glycol, triethylene glycol). , Propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol , 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1 ,6-Hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2 Aliphatic glycols such as ,5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, xyl Aromatic glycol such as rylene glycol and bishydroxyethoxybenzene, N-alkyl dialkanolamine such as N-methyldiethanolamine) obtained by polycondensation, for example, polyethylene adipate, polybutylene adipate, poly Hexamethylene adipate, polyethylene/propylene adipate, or polylactonediol or polylactone monool obtained by using the above diols or monohydric alcohols having 1 to 25 carbon atoms as an initiator, such as polycaprolactone glycol, polymethylvale Lolactone and mixtures of two or more thereof are mentioned. As polyester glycol, polycaprolactone glycol and polycaprolactone which used C1-C25 alcohol as an initiator are especially preferable.

As polycarbonate glycol, for example, poly(1,6-hexylene) carbonate, poly(3-methyl-1,5-pentylene) carbonate, etc. As polyolefin glycol, polybutadiene glycol, hydrogenated polybutadiene glycol and hydrogenated polyisoprene glycol.

These may be used individually by 1 type, and may use 2 or more types together.

The number average molecular weight of the compound which has one or two hydroxyl groups in the same molecule becomes like this. Preferably it is 300-10000, More preferably, it is 500-6000, More preferably, it is 1000-4000.

A compound having an active hydrogen and a tertiary amino group in the same molecule is described.

Active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom, or a sulfur atom includes, for example, a hydrogen atom in a functional group of a hydroxyl group, an amino group, and a thiol group. A hydrogen atom of the amino group is preferred.

Although the tertiary amino group is not specifically limited, For example, the amino group which has a C1-C4 alkyl group, or a heterocyclic structure, More specifically, an imidazole ring and a triazole ring are mentioned, for example.

Examples of the compound having active hydrogen and a tertiary amino group in the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N,N- Dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N-dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, and N,N-dibutyl-1,4-butanediamine.

Examples of the nitrogen-containing heterocyclic ring when the tertiary amino group is a nitrogen-containing heterocyclic structure include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, Nitrogen-containing hetero 5-membered rings such as benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring and benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline A nitrogen-containing hetero 6-membered ring, such as a ring, an acridine ring, and an isoquinoline ring, is mentioned. Among these nitrogen-containing heterocycles, an imidazole ring and a triazole ring are preferable.

Examples of the compound having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, and 1-(2-aminoethyl)imidazole.

Examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl-1H-1,2 ,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino- 1,4-diphenyl-1,2,3-triazole and 3-amino-1-benzyl-1H-2,4-triazole are mentioned.

Among them, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, 3-amino-1,2,4 - Triazole is preferred.

These may be used individually by 1 type, and may use 2 or more types together.

A preferable blending ratio of the raw materials for producing the urethane-based polymer dispersant is 10 to 200 parts by mass of a compound having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by mass of the polyisocyanate compound, Preferably it is 20-190 mass parts, More preferably, it is 30-180 mass parts, 0.2-25 mass parts of compounds which have active hydrogen and a tertiary amino group in the same molecule, Preferably it is 0.3-24 mass parts.

The urethane-based polymer dispersant can be prepared according to a known method for producing a polyurethane resin. As a solvent at the time of manufacture, usually, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, Esters, such as ethyl acetate, butyl acetate, and cellosolve acetate , hydrocarbons such as benzene, toluene, xylene, and hexane, some alcohols such as diacetone alcohol, isopropanol, second butanol and tertiary butanol, chlorides such as methylene chloride and chloroform, tetrahydrofuran, diethyl ether, etc. Aprotic polar solvents such as ethers, dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide are used.

These may be used individually by 1 type, and may use 2 or more types together.

In the production of the urethane-based polymer dispersant, a urethanization reaction catalyst is usually used. As a urethanation reaction catalyst, For example, tin-type, such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stannus octoate, iron-type, such as iron acetylacetonate, ferric chloride, and tertiary amines such as triethylamine and triethylenediamine.

These may be used individually by 1 type, and may use 2 or more types together.

The amount of the compound having active hydrogen and a tertiary amino group introduced into the same molecule is preferably controlled in the range of the amine value after the reaction, preferably 1 to 100 mgKOH/g, more preferably 5 to 95 mgKOH/g. The amine value is a value expressed by the number of mg of KOH by titration by neutralizing a basic amino group with an acid and corresponding to the acid value. By using more than the said lower limit, there exists a tendency for a dispersion|distribution ability to improve. By using below the said upper limit, there exists a tendency for developability to improve.

When the isocyanate group remains in the polymer dispersant, it is preferable to inactivate the isocyanate group with an alcohol or an amino compound because the stability of the product over time increases.

The weight average molecular weight (Mw) of the urethane-based polymer dispersant is preferably from 1000 to 200000, more preferably from 2000 to 100000, still more preferably from 3000 to 50000. There exists a tendency for dispersibility and dispersion stability to improve by setting it as more than the said lower limit. There exists a tendency for solubility to improve and dispersibility to become favorable by setting it as below the said upper limit.

Examples of the acrylic polymer dispersant include a random copolymer of an unsaturated group-containing monomer having a functional group (a functional group referred to herein is a functional group described above as a functional group contained in the polymer dispersing agent) and an unsaturated group-containing monomer having no functional group, a graft copolymer, Preference is given to using block copolymers. These copolymers can be prepared by a known method.

As an unsaturated group containing monomer which has a functional group, For example, (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acrylo Unsaturated monomers having a carboxyl group such as yloxyethylhexahydrophthalic acid and acrylic acid dimer, tertiary amino groups such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and quaternary products thereof, and quaternary ammonium salts and unsaturated monomers having a group.

These may be used individually by 1 type, and may use 2 or more types together.

Examples of the unsaturated group-containing monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate , phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N- N-substituted maleimides such as vinylpyrrolidone, styrene and derivatives thereof, α-methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide and N-benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl Macromonomers, such as a (meth)acrylate macromonomer, a polystyrene macromonomer, a poly 2-hydroxyethyl (meth)acrylate macromonomer, a polyethyleneglycol macromonomer, a polypropylene glycol macromonomer, and a polycaprolactone macromonomer, are mentioned. .

These may be used individually by 1 type, and may use 2 or more types together.

The acrylic polymer dispersant is particularly preferably an A-B or B-A-B block copolymer composed of an A block having a functional group and a B block not having a functional group. In addition to the structure, a partial structure derived from an unsaturated group-containing monomer containing no functional group may be contained, and these may be contained in the A block in any aspect of random copolymerization or block copolymerization.

Content in A block of the partial structure which does not contain a functional group becomes like this. Preferably it is 80 mass % or less, More preferably, it is 50 mass % or less, More preferably, it is 30 mass % or less.

The B block consists of a partial structure derived from an unsaturated group-containing monomer that does not contain the functional group, but one B block may contain a partial structure derived from two or more types of monomers, and these are random copolymerized in the B block. Or you may contain in any aspect of block copolymerization.

A-B or B-A-B block copolymer is prepared by the living polymerization method shown below, for example.

The living polymerization method includes an anionic living polymerization method, a cationic living polymerization method, and a radical living polymerization method.

When synthesizing this acrylic polymer dispersant, for example, Japanese Patent Application Laid-Open No. 9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), B. C. Anderson, G. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Ute, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Proceedings of Polymers, 46, 189 (1989) , M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Organic Synthetic Chemistry, 43, 300 (1985), D. Y. Sogoh, W. R. Hertler et al, Macromolecules, 20, 1473 (1987) employing the known method described. can do.

The acrylic polymer dispersant that can be used in the present invention may be an A-B block copolymer or a B-A-B block copolymer, and the A block/B block ratio constituting the copolymer is preferably 1/99 to 80/20 (mass ratio), , particularly preferably 5/95 to 60/40 (mass ratio). By setting it as the said range, there exists a tendency for ensuring the balance of dispersibility and storage stability is possible.

It is preferable that the quantity of the quaternary ammonium base in 1 g of A-B block copolymer and B-A-B block copolymer which can be used by this invention is 0.1-10 mmol. There exists a tendency for favorable dispersibility to be securable by setting it as the said range.

When an amino group generated during the production process is contained in such a block copolymer, the amine value is preferably 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, further preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, still more preferably 75 mgKOH/g is below. For example, 1-100 mgKOH/g is preferable, 10-90 mgKOH/g is more preferable, 30-80 mgKOH/g is still more preferable, 50-75 mgKOH/g is especially preferable. .

The amine titer of a dispersing agent such as a block copolymer is expressed by the amount of the base per 1 g of the solid content excluding the solvent in the dispersant sample and the mass of the equivalent KOH, and is measured by the following method.

In a 100 ml beaker, 0.5 to 1.5 g of the dispersant sample is precisely weighed and dissolved with 50 ml of acetic acid. Using an automatic titrator equipped with a pH electrode, this solution is neutralized and titrated with a 0.1 mol/L HClO ₄ acetic acid solution. Using the inflection point of the titration pH curve as the titration end point, the amine number is calculated by the following formula.

Amine value [mgKOH/g] = (561 × V)/(W × S) [wherein W: precise weight of dispersant sample [g], V: titration at the end point of titration [ml], S: solid content of dispersant sample Concentration [mass %] is shown.]

Although the acid value of a block copolymer also changes with the presence or absence and type of the acidic group used as the origin of the acid value, it is preferable that it is low, Preferably it is 10 mgKOH/g or less.

As for the weight average molecular weight (Mw) of a block copolymer, the range of 1000-100000 is preferable. There exists a tendency for favorable dispersibility to be securable by setting it as the said range.

When having a quaternary ammonium base as a functional group, the specific structure of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, a repeating unit represented by the following formula (r-i) (hereinafter referred to as “repeating unit (r-i)” may be ) is preferred.

[Formula 45]

(In formula (ri), R ³¹ to R ³³ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group;

two or more of R ³¹ to R ³³ may combine with each other to form a cyclic structure;

R ³⁴ is a hydrogen atom or a methyl group;

X is a divalent linking group;

Y ^- is a counter anion.)

Although carbon number of the alkyl group which may have a substituent in ^R31 - ^R33 of Formula (ri) is not specifically limited, It is 1 or more, Moreover, 10 or less are preferable, and 6 or less are more preferable. Specific examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pen A tyl group and a hexyl group are preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable. In addition, any of a linear type and a branched type may be sufficient. Moreover, cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group, may be included.

Although carbon number of the aryl group which may have a substituent in ^R31 - ^R33 of Formula (ri) is not specifically limited, Preferably it is 6 or more, and 16 or less are preferable, and 12 or less are more preferable. . Specific examples of the aryl group include, for example, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group, and among these, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, A diethylphenyl group is preferable, and a phenyl group, a methylphenyl group, and an ethylphenyl group are more preferable.

Although carbon number of the aralkyl group which may have a substituent in ^R31 - ^R33 of Formula (ri) is not specifically limited, Preferably it is 7 or more, and 16 or less are preferable, and 12 or less are more preferable. . Specific examples of the aralkyl group include, for example, a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group. Among these, a phenylmethyl group, a phenylethyl group , a phenylpropyl group and a phenylbutyl group are preferable, and a phenylmethyl group and a phenylethyl group are more preferable.

Among these, from the viewpoint of dispersibility, it is preferable that R ³¹ to R ³³ each independently represent an alkyl group or an aralkyl group, specifically, R ³¹ and R ³³ each independently represent a methyl group or an ethyl group, and R ³² is preferably a phenylmethyl group or a phenylethyl group, more preferably R ³¹ and R ³³ are methyl groups, and R ³² is a phenylmethyl group.

When the polymer dispersing agent has a tertiary amine as a functional group, it is preferable to have a repeating unit represented by the following formula (r-ii) (hereinafter sometimes referred to as “repeating unit (r-ii)”) from the viewpoint of dispersibility. do.

[Formula 46]

(in formula (r-ii), R ³⁵ and R ³⁶ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group;

R ³⁵ and R ³⁶ may combine with each other to form a cyclic structure;

R ³⁷ is a hydrogen atom or a methyl group;

Z is a divalent linking group.)

As the alkyl group which may have a substituent in R ³⁵ and R ³⁶ in the formula (r-ii), those exemplified as R ³¹ to R ³³ in the formula (ri) can be preferably employed.

As the aryl group which may have a substituent in R ³⁵ and R ³⁶ in the formula (r-ii), those exemplified as R ³¹ to R ³³ in the formula (ri) can be preferably employed.

As the aralkyl group which may have a substituent in R ³⁵ and R ³⁶ in the formula (r-ii), those exemplified as R ³¹ to R ³³ in the formula (ri) can be preferably employed.

Among these, it is preferable that R ³⁵ and R ³⁶ are each independently an alkyl group which may have a substituent, and it is more preferable that they are a methyl group or an ethyl group.

Examples of the substituent which the alkyl group, aralkyl group, or aryl group in R ³¹ to R ³³ in the formula (ri) and R ³⁵ and R ³⁶ in the formula (r-ii) may have include a halogen atom, an alkoxy group, A benzoyl group and a hydroxyl group are mentioned.

In the formulas (ri) and (r-ii), the divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R ⁴³ - group, -COOR ⁴⁴ - group (however, R ⁴³ and R ⁴⁴ are a single bond, a C1-C10 alkylene group, or a C2-C10 ether group (alkyloxyalkyl group)) is mentioned, Preferably -COO -R ⁴⁴ - is a group.

In the formula (ri), examples of Y ⁻ serving as a counter anion include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ⁻ .

The content ratio of the repeating unit represented by the formula (r-i) is not particularly limited, but from the viewpoint of dispersibility, the content ratio of the repeating unit represented by the formula (r-i) and the content ratio of the repeating unit represented by the formula (r-ii) is To that, it is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, particularly preferably 35 mol% or less, and preferably 5 mol% or more. and more preferably 10 mol% or more, still more preferably 20 mol% or more, and particularly preferably 30 mol% or more. For example, 5-60 mol% is preferable, 10-50 mol% is more preferable, 20-40 mol% is still more preferable, 30-35 mol% is especially preferable.

Although the content ratio of the repeating unit represented by the said formula (r-i) to all the repeating units of a polymer dispersing agent is not specifically limited, From a dispersibility viewpoint, 1 mol% or more is preferable, 5 mol% or more is more preferable, 10 mol % or more is more preferable, and 50 mol% or less is preferable, 30 mol% or less is more preferable, 20 mol% or less is still more preferable, and 15 mol% or less is especially preferable. For example, 1-50 mol% is preferable, 1-30 mol% is more preferable, 5-20 mol% is still more preferable, 10-15 mol% is especially preferable.

Although the content ratio of the repeating unit represented by the above formula (r-ii) in the total repeating units of the polymer dispersant is not particularly limited, from the viewpoint of dispersibility, it is preferably 5 mol% or more, and more preferably 10 mol% or more, It is more preferably 15 mol% or more, particularly preferably 20 mol% or more, and further preferably 60 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less, and 25 mol% or less It is particularly preferred. For example, 5-60 mol% is preferable, 10-40 mol% is more preferable, 15-30 mol% is still more preferable, 20-25 mol% is especially preferable.

The polymer dispersant is a repeating unit represented by the following formula (r-iii) from the viewpoint of improving compatibility with binder components such as solvents and improving dispersion stability (hereinafter referred to as “repeating unit (r-iii)”) It is preferable to have ).

[Formula 47]

(in formula (r-iii), R ⁴⁰ is an ethylene group or a propylene group;

R ⁴¹ is an optionally substituted alkyl group;

R ⁴² is a hydrogen atom or a methyl group;

n is an integer from 1 to 20.)

Although carbon number of the alkyl group which may have a substituent in R ⁴¹ of Formula (r-iii) is not specifically limited, It is 1 or more, It is preferable that it is 2 or more, It is also preferable that it is 10 or less, It is more preferable that it is 6 or less. do. Specific examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pen A tyl group or a hexyl group is preferable, and a methyl group, an ethyl group, a propyl group, or a butyl group is more preferable. In addition, any of a linear type and a branched type may be sufficient. Moreover, cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group, may be included. For example, 1-10 are preferable and, as for carbon number of an alkyl group, 2-6 are more preferable.

From the viewpoints of compatibility and dispersibility with respect to the solvent or binder component, n in the formula (r-iii) is 1 or more, preferably 2 or more, more preferably 10 or less, and more preferably 5 or less. For example, 1-10 are preferable, 1-5 are more preferable, and 2-5 are still more preferable.

In addition, the content rate of the repeating unit represented by the said formula (r-iii) in all the repeating units of a polymer dispersing agent is although it does not specifically limit, 1 mol% or more is preferable, 2 mol% or more is more preferable, 4 mol% More preferably, 30 mol% or less is preferable, 20 mol% or less is more preferable, and 10 mol% or less is still more preferable. When it falls within the said range, there exists a tendency for compatibility with respect to a solvent or a binder component, and coexistence of dispersion stability to become possible. For example, 1-30 mol% is preferable, as for the content rate of the repeating unit represented by the said Formula (r-iii) to all the repeating units of a polymer dispersing agent, 2-20 mol% is more preferable, 4-10 mol % is more preferable.

In addition, the polymer dispersant is a repeating unit represented by the following formula (r-iv) from the viewpoint of improving the compatibility of the dispersant with a solvent or binder component and improving dispersion stability (hereinafter, “repeating unit (r-iv)” It is preferable to have ).

[Formula 48]

(in formula (r-iv), R ³⁸ is an optionally substituted alkyl group, optionally substituted aryl group, or optionally substituted aralkyl group;

R ³⁹ is a hydrogen atom or a methyl group.)

Although carbon number of the alkyl group which may have a substituent in R ³⁸ of Formula (r-iv) is not specifically limited, It is 1 or more, 2 or more are preferable, 4 or more are more preferable, Moreover, 10 or less are preferable. and 8 or less are more preferable. Specific examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pen A tyl group and a hexyl group are preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable. In addition, any of a linear type and a branched type may be sufficient. Moreover, cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group, may be included. For example, 1-10 are preferable, as for carbon number of an alkyl group, 2-8 are more preferable, 4-8 are still more preferable.

Although carbon number of the aryl group which may have a substituent in R ³⁸ of a formula (r-iv) is not specifically limited, Preferably it is 6 or more, and 16 or less are preferable, and 12 or less are more preferable, 8 or less is more preferable. Specific examples of the aryl group include, for example, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group, and among these, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, A diethylphenyl group is preferable, and a phenyl group, a methylphenyl group, and an ethylphenyl group are more preferable. For example, 6-16 are preferable, as for carbon number of an aryl group, 6-12 are more preferable, 8-12 are still more preferable.

Although carbon number of the aralkyl group which may have a substituent in R ³⁸ of a formula (r-iv) is not specifically limited, Preferably it is 7 or more, and 16 or less are preferable, and 12 or less are more preferable, 10 or less is more preferable. Specific examples of the aralkyl group include, for example, a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group. Among these, a phenylmethyl group, a phenylethyl group , a phenylpropyl group and a phenylbutyl group are preferable, and a phenylmethyl group and a phenylethyl group are more preferable. For example, 7-16 are preferable, as for carbon number of an aralkyl group, 7-12 are more preferable, 7-10 are still more preferable.

Among these, from the viewpoint of solvent compatibility and dispersion stability, R ³⁸ is preferably an alkyl group or an aralkyl group, more preferably a methyl group, an ethyl group or a phenylmethyl group.

As a substituent which the alkyl group in R ³⁸ may have, a halogen atom and an alkoxy group are mentioned, for example. Examples of the substituent for R ³⁸ that the aryl group or the aralkyl group may have include a chain alkyl group, a halogen atom, and an alkoxy group. The linear alkyl group represented by R ³⁸ includes both linear and branched chain types.

From the viewpoint of dispersibility, the content of the repeating unit represented by the formula (r-iv) in the total repeating units of the polymer dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, and 50 mol% or more This is more preferable, and 80 mol% or less is preferable, and 70 mol% or less is more preferable. For example, 30-80 mol% is preferable, 40-80 mol% is more preferable, 50-70 mol% is still more preferable.

The polymer dispersant may have a repeating unit other than the repeating unit (r-i), the repeating unit (r-ii), the repeating unit (r-iii), and the repeating unit (r-iv). As an example of such a repeating unit, For example, Styrene-type monomers, such as styrene and (alpha)-methylstyrene; (meth)acrylate-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide type monomers, such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and repeating units derived from N-methacryloylmorpholine.

From the viewpoint of further enhancing dispersibility, the polymer dispersant includes an A block having a repeating unit (r-i) and a repeating unit (r-ii), and a B block having no repeating unit (r-i) and a repeating unit (r-ii). It is preferable that it is a block copolymer which has. The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. By introducing not only a quaternary ammonium base but also a tertiary amino group into the A block, unexpectedly, the dispersing ability of the dispersing agent tends to be remarkably improved. Moreover, it is preferable that the B block has a repeating unit (r-iii), and it is more preferable that it further has a repeating unit (r-iv).

In the A block, the repeating unit (r-i) and the repeating unit (r-ii) may be contained in either random copolymerization or block copolymerization mode. The repeating unit (r-i) and the repeating unit (r-ii) may each be contained in one type or two or more types in one A block, and in that case, each repeating unit is random copolymerized or block copolymerized in the A block. You may contain it in any aspect of.

A repeating unit other than the repeating unit (r-i) and the repeating unit (r-ii) may be contained in the A block, and examples of such repeating units include, for example, repeating units derived from the (meth)acrylic acid ester monomers described above. units can be included. The content of the repeating unit (r-i) and repeating units other than the repeating unit (r-ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and 0 mol% is particularly desirable.

Repeating units other than the repeating units (r-iii) and (r-iv) may be contained in the B block, and examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide type monomers, such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and repeating units derived from N-methacryloylmorpholine. The content of the repeating units (r-iii) and repeating units other than the repeating unit (r-iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and 0 mol% is particularly preferred.

When the photosensitive resin composition of the present invention contains the (F) dispersing agent, the content ratio is not particularly limited, but in the total solid content of the photosensitive resin composition, 0.1 mass% or more is preferable, and 0.5 mass% or more is more preferable, Moreover, 8 mass % or less is preferable, 5 mass % or less is more preferable, 3 mass % or less is still more preferable, and 2 mass % or less is especially preferable. For example, 0.1-8 mass % is preferable, 0.1-5 mass % is more preferable, 0.5-3 mass % is still more preferable, 0.5-2 mass % is especially preferable. There exists a tendency which can suppress generation|occurrence|production of the residue by an aggregate by setting it as more than the said lower limit. There exists a tendency for ink repellency and developability to improve by using below the said upper limit.

[1-1-7] UV absorber

The photosensitive resin composition of this invention may contain a ultraviolet absorber. The ultraviolet absorber is added for the purpose of controlling the light curing distribution by absorbing the specific wavelength of the light source used for exposure by the ultraviolet absorber. By the addition of the ultraviolet absorber, effects such as forming a high-definition barrier rib with a thin line width or removing a residue remaining in an unexposed portion after development are obtained. As the ultraviolet absorber, from the viewpoint of inhibition of light absorption of the (B) photopolymerization initiator, for example, a compound having an absorption maximum between wavelengths of 250 nm and 400 nm can be used.

It is preferable that any one or both of a benzotriazole type compound and a triazine type compound are included as a ultraviolet absorber. By including either or both of the benzotriazole-based compound and the triazine-based compound, the light absorptivity at the bottom of the initiator is reduced, and the line width under the coating film is reduced, so that a high-definition partition with a thin line width can be formed. I think.

Examples of the benzotriazole-based compound include 2-(5 methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 3 -[3-tert-Butyl-5- (5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl] octyl propionate, 3- [3-tert-butyl-5- (5-chloro) -2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethylhexylpropionate, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotria Sol, 2-(3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole , 2-(2'-hydroxyl-5'-t-octylphenyl)benzotriazole, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl ) Phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, 3-[ ester compounds of 3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionic acid and C7-9 linear and branched alkyl alcohols.

Commercially available benzotriazole compounds include, for example, Smissorb (registered trademark, hereinafter the same) 200, Smisorb 250, Smisorb 300, Smisorb 340, Smisorb 350 (manufactured by Sumitomo Chemical). , JF77, JF78, JF79, JF80, JF83 (manufactured by Johoku Chemical Industry), TINUVIN (registered trademark, hereinafter the same) PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN 326, TINUVIN900, TINUVIN928, TINUVIN1130 (manufactured by BASF) , EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (manufactured by Everlight Chemicals, Taiwan), Tomisorb (registered trademark, hereinafter the same) 100, Tomisorb 600 (the same trademark) API Corporation), SEESORB (trademark, hereinafter the same) 701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB709 (manufactured by Sifro Chemical Co., Ltd.), and RUVA-93 (Otsuka Chemical Co., Ltd.) are mentioned.

Examples of the triazine-based compound include 2-[4,6-di(2,4-xylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol, 2-[ 4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2- (2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-ethylhexylglycidyl ether reaction product, 2,4-bis [2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3-5-triazine is mentioned. Among these, a hydroxyphenyltriazine compound is preferable from a viewpoint of forming the high-definition partition with ink repellency and a thin line|wire width.

As a commercially available triazine type compound, TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, TINUVIN479 (made by BASF) are mentioned, for example.

As another ultraviolet absorber, a benzophenone compound, a benzoate compound, a cinnamic acid derivative, a naphthalene derivative, anthracene and its derivative(s), a dinaphthalene compound, a phenanthroline compound, and dye are mentioned, for example.

More specifically, for example, Sumitomo 130 (manufactured by Sumitomo Chemical), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Everlight Chemical Industry in Taiwan), Tomisorb 800 (manufactured by Ap.i Corporation), SEESORB100, SEESORB101, SEESORB101S, Benzophenone compounds, such as SEESORB102, SEESORB103, SEESORB105, SEESORB106, SEESORB107, and SEESORB151 (made by Cipro Chemicals); Benzoate compounds, such as Sumisorb 400 (made by Sumitomo Chemical) and phenyl salicylate; cinnamic acid derivatives such as 2-ethylhexyl cinnamate, 2-ethylhexyl para-methoxycinnamate, isopropyl methoxycinnamate, and isoamyl methoxycinnamate; α-naphthol, β-naphthol, α-naphthol methyl ether, α-naphthol ethyl ether, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5 -dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene , naphthalene derivatives such as 2,7-dihydroxynaphthalene; anthracene and derivatives thereof, such as anthracene and 9,10-dihydroxyanthracene; dyes such as azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes and p-aminobenzoic acid dyes; can be heard Among these, it is preferable to use a cinnamic acid derivative and a naphthalene derivative from a viewpoint of ink repellency, and it is especially preferable to use a cinnamic acid derivative.

Among these, from a tapered viewpoint, either one or both of a benzotriazole type compound and a hydroxyphenyltriazine type compound are preferable, and a benzotriazole type compound is especially preferable.

As a ultraviolet absorber, 1 type may be used individually, and 2 or more types may be used together.

When the photosensitive resin composition of this invention contains a ultraviolet absorber, the content rate is although it does not specifically limit, Preferably it is 0.01 mass % or more, More preferably, it is 0.05 mass % or more in total solid of the photosensitive resin composition, More preferably Preferably it is 0.1 mass % or more, More preferably, it is 0.5 mass % or more, Especially preferably, it is 1 mass % or more, More preferably, it is 15 mass % or less, More preferably, it is 10 mass % or less, More preferably, It is 5 mass % or less, Especially preferably, it is 3 mass % or less. For example, 0.01-15 mass % is preferable, 0.05-15 mass % is more preferable, 0.1-10 mass % is still more preferable, 0.5-5 mass % is still more preferable, 1-3 mass % is Especially preferred. By setting it as more than the said lower limit, there exists a tendency which can form the high-definition partition with a thin line|wire width. There exists a tendency for ink repellency to become high by setting it as below the said upper limit.

When the photosensitive resin composition of this invention contains a ultraviolet absorber, as a compounding ratio with respect to (B) photoinitiator, As a compounding quantity of the ultraviolet absorber with respect to 100 mass parts of (B) photoinitiator, Preferably it is 1 mass part or more. , More preferably 10 parts by mass or more, still more preferably 30 parts by mass or more, still more preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, further preferably 500 parts by mass or less, more Preferably it is 300 mass parts or less, More preferably, it is 200 mass parts or less, Especially preferably, it is 100 mass parts or less. For example, 1-500 mass parts is preferable, 10-500 mass parts is more preferable, 30-300 mass parts is still more preferable, 50-200 mass parts is still more preferable, 80-100 mass parts is especially preferable. By setting it as more than the said lower limit, there exists a tendency which can form the high-definition partition with a thin line|wire width. There exists a tendency for ink repellency to become high by setting it as below the said upper limit.

[1-1-8] polymerization inhibitor

The photosensitive resin composition of this invention may contain a polymerization inhibitor. Since it inhibits radical polymerization by containing a polymerization inhibitor, there exists a tendency which can enlarge the taper angle of the partition obtained.

Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). Among these, from a viewpoint of a polymerization inhibitory ability, hydroquinone, a methoxyphenol, and methylhydroquinone are preferable, and methylhydroquinone is more preferable.

A polymerization inhibitor may be used individually by 1 type, and may use 2 or more types together.

(C) A polymerization inhibitor may be contained in the manufactured alkali-soluble resin depending on the manufacturing method of alkali-soluble resin. In that case, you may use with the polymerization inhibitor contained in alkali-soluble resin, other than the polymerization inhibitor contained in resin, the same or different polymerization inhibitor may be further added at the time of photosensitive resin composition manufacture.

When the photosensitive resin composition contains a polymerization inhibitor, although the content rate is not specifically limited, In total solid of the photosensitive resin composition, Preferably it is 0.0005 mass % or more, More preferably, it is 0.001 mass % or more, More preferably It is 0.01 mass % or more, Preferably it is 0.1 mass % or less, More preferably, it is 0.08 mass % or less, More preferably, it is 0.05 mass % or less. For example, 0.0005-0.1 mass % is preferable, 0.001-0.08 mass % is more preferable, 0.01-0.05 mass % is still more preferable. There exists a tendency which can make a taper angle high by setting it as more than the said lower limit. There exists a tendency for ink repellency to become high by setting it as below the said upper limit.

[1-1-9] Thermal polymerization initiator

The photosensitive resin composition of this invention may contain a thermal polymerization initiator. By containing a thermal polymerization initiator, there exists a tendency which can make the crosslinking degree of a film|membrane high. As a specific example of such a thermal polymerization initiator, an azo compound, an organic peroxide, and hydrogen peroxide are mentioned, for example.

These may be used individually by 1 type, and may use 2 or more types together.

When a thermal polymerization initiator is used together in anticipation of an improvement in ink repellency and an increase in the crosslinking density of a film to a photoinitiator, it is preferable that the total content of these initiators becomes the content ratio of the photoinitiator in the photosensitive resin composition described above. Moreover, as a combined ratio of a photoinitiator and a thermal polymerization initiator, from a viewpoint of ink repellency, it is preferable to make 5-300 mass parts of thermal polymerization initiators with respect to 100 mass parts of photoinitiators.

[1-1-10] amino compound

The photosensitive resin composition of this invention may contain an amino compound in order to accelerate|stimulate thermosetting. When the amino compound is contained in the photosensitive resin composition of the present invention, the content of the amino compound is preferably 40 mass% or less, more preferably 30 mass% or less, in the total solid content of the photosensitive resin composition, and further, Preferably it is 0.5 mass % or more, More preferably, it is 1 mass % or more. For example, 0.5-40 mass % is preferable, and 1-30 mass % is more preferable. There exists a tendency for storage stability to be maintained by using below the said upper limit. There exists a tendency which sufficient thermosetting property can be ensured by setting it as more than the said lower limit.

As an amino compound, the amino compound which has at least 2 methylol group and the alkoxymethyl group which carried out condensation modification with C1-C8 alcohol as a functional group is mentioned, for example. Melamine resin which polycondensed melamine and formaldehyde specifically, for example; Benzoguanamine resin which polycondensed benzoguanamine and formaldehyde; glycoluril resin obtained by polycondensation of glycoluril and formaldehyde; a urea resin obtained by polycondensation of urea and formaldehyde; Resin which co-condensed 2 or more types, such as a melamine, benzoguanamine, glycoluril, or urea, and formaldehyde; The modified resin which carried out alcohol condensation modification of the methylol group of resin mentioned above is mentioned.

These may be used individually by 1 type, and may use 2 or more types together.

Especially, as an amino compound, a melamine resin and its modified resin are preferable, the modified resin of 70 % or more of modified|denatured ratio of methylol groups is more preferable, and 80 % or more of modified resin is still more preferable.

As a specific example of an amino compound, as a melamine resin and its modified resin, For example, "Cymel" (trademark, hereinafter the same) manufactured by Cytech Co., Ltd. 300, 301, 303, 350, 736, 738, 370, 771, 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and "Nikalac" manufactured by Sanwa Chemical (registered trademark, hereinafter) same) MW-390, MW-100LM, MX-750LM, MW-30M, MX-45, and MX-302 are mentioned.

As a benzoguanamine resin and its modified resin, "Cymel" 1123, 1125, 1128 by the Cytech company is mentioned, for example.

As glycoluril resin and its modified resin, "Cymel" 1170, 1171, 1174, 1172 by the Cytech company, and "Nikalac" MX-270 by the Sanwa Chemical company are mentioned, for example.

As a urea resin and its modified resin, "UFR" (trademark) 65 and 300 by the Cytech company, and "Nikalac" MX-290 by the Sanwa Chemical company are mentioned, for example.

[1-1-11] Silane Coupling Agent

The photosensitive resin composition of this invention may contain a silane coupling agent in order to improve adhesiveness with a board|substrate.

As the silane coupling agent, for example, an epoxy-based, methacrylic-based, amino-based, or imidazole-based silane coupling agent can be used, but from the viewpoint of improving adhesion, an epoxy-based or imidazole-based silane coupling agent is particularly desirable.

When the photosensitive resin composition of this invention contains a silane coupling agent, the content is from an adhesive viewpoint in total solid of the photosensitive resin composition, Preferably it is 20 mass % or less, More preferably, it is 15 mass % or less.

[1-1-12] inorganic filler

The photosensitive resin composition of this invention aims at the improvement of the outstanding verticality of a coating film by moderate interaction (formation of a matrix structure) with an alkali-soluble resin (formation of a matrix structure), a taper angle, etc. with the improvement of the intensity|strength as hardened|cured material, etc., an inorganic filler may contain.

Examples of the inorganic filler include talc, silica, alumina, barium sulfate, magnesium oxide, titanium oxide, or what surface-treated these with various silane coupling agents.

As an average particle diameter of an inorganic filler, Preferably it is 0.005-2 micrometers, More preferably, it is 0.01-1 micrometer. An average particle diameter is the value measured with the laser diffraction scattering particle size distribution analyzer, such as a Beckman Coulter company make. Among the inorganic fillers, silica sol and silica sol-modified products are preferable because they tend to be excellent in the effect of improving the taper angle together with dispersion stability.

When the photosensitive resin composition of the present invention contains an inorganic filler, the content is, from the viewpoint of ink repellency, in the total solid content of the photosensitive resin composition, preferably 5 mass% or more, more preferably 10 mass% or more, , Preferably it is 80 mass % or less, More preferably, it is 70 mass % or less. For example, 5-80 mass % is preferable, and 10-70 mass % is more preferable.

[1-1-13] Adhesion improver

The photosensitive resin composition of this invention may contain an adhesiveness improving agent for the purpose of providing adhesiveness with a board|substrate. As an adhesive improving agent, a phosphoric acid type ethylenic monomer is mentioned, for example.

As a phosphoric acid type ethylenic monomer, (meth)acryloyloxy group containing phosphates are preferable, and what is represented by the following general formula (g1), (g2), (g3) is preferable.

[Formula 49]

(In the formulas (g1), (g2) and (g3), R ⁵¹ represents a hydrogen atom or a methyl group, l and l' are an integer of 1 to 10, and m is 1, 2 or 3.)

These phosphoric acid-type ethylenic monomers may be used individually by 1 type, and may use 2 or more types together.

When the photosensitive resin composition of this invention contains a phosphoric acid type ethylenic monomer as an adhesive improving agent, 0.02 mass % or more is preferable in the total solid of the photosensitive resin composition, 0.05 mass % or more is more preferable, 0.1 Mass % or more is more preferable, 0.2 mass % or more is especially preferable, 4 mass % or less is preferable, 3 mass % or less is more preferable, 2 mass % or less is still more preferable, 1 mass % or less is Especially preferred. For example, 0.02-4 mass % is preferable, 0.05-3 mass % is more preferable, 0.1-2 mass % is still more preferable, 0.2-1 mass % is especially preferable. There exists a tendency for the improvement effect of adhesiveness with a board|substrate to become enough by setting it as more than the said lower limit. There exists a tendency for it to be easy to suppress the deterioration of adhesiveness with a board|substrate by setting it as below the said upper limit.

[1-1-14] solvent

The photosensitive resin composition of this invention contains a solvent normally, and is used in the state which melt|dissolved or disperse|distributed each component contained in the photosensitive resin composition to the solvent. Although there is no restriction|limiting in particular as the solvent, For example, the organic solvent described below is mentioned.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t- Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol Glycol monoalkyl ethers such as 3-methoxy-1-butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether glycol dialkyl ethers such as;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether Acetate, 3-methoxy-1-butyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether glycol alkyl ether acetates such as acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

glycol diacetates such as ethylene glycol diacetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, and 1,6-hexanol diacetate;

alkyl acetates such as cyclohexanol acetate;

ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether;

Acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl amyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketones such as ketone, methyl nonyl ketone, and methoxymethyl pentanone;

Monohydric or monohydric such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol; polyhydric alcohols;

aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene and dodecane;

alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene and bicyclohexyl;

aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

Amyl formate, ethyl formate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl isobutyrate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, Ethyl benzoate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-methoxy propyl propionate, 3-methoxy butyl propionate, γ-butyrolactone chain or cyclic esters such as;

alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

halogenated hydrocarbons such as butyl chloride and amyl chloride;

ether ketones such as methoxymethylpentanone;

nitriles such as acetonitrile and benzonitrile;

tetrahydrofurans such as tetrahydrofuran, dimethyltetrahydrofuran, and dimethoxytetrahydrofuran.

Commercially available solvents include, for example, Mineral Spirit, Barsol #2, Abco #18 Solvent, Abco Thinner, Socal Solvent No.1 and No.2, Solveso #150, Shell TS28 Solvent, Carbitol, Ethyl Carr. Bitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diglyme (all are brand names) are mentioned.

A solvent can melt|dissolve or disperse|distribute each component contained in the photosensitive resin composition, and is selected according to the usage method of the photosensitive resin composition of this invention. From a viewpoint of applicability|paintability, 60-280 degreeC is preferable and, as for the boiling point in atmospheric pressure of a solvent, 70-260 degreeC is more preferable. Among these, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate are preferable.

A solvent may be used individually by 1 type, and may use 2 or more types together.

The solvent has a content ratio of total solids in the photosensitive resin composition solution, preferably 10 mass% or more, more preferably 15 mass% or more, still more preferably 20 mass% or more, particularly preferably 25 mass% or more, Moreover, it is preferable that it is used so that it becomes like this, Preferably it is 90 mass % or less, More preferably, it is 50 mass % or less, More preferably, it is 40 mass % or less, Especially preferably, it is 35 mass % or less. For example, it is preferable to use so that it may become preferably 10-90 mass %, More preferably, it is 15-50 mass %, More preferably, it is 20-40 mass %, Especially preferably, it becomes 25-35 mass %. There exists a tendency which can suppress generation|occurrence|production of application|coating nonuniformity by setting it as more than the said lower limit. There exists a tendency which can suppress generation|occurrence|production of a foreign material, repelling, etc. by setting it as below the said upper limit.

[1-2] Method for preparing photosensitive resin composition

The photosensitive resin composition of this invention is prepared by mixing each component contained in the photosensitive resin composition with a stirrer.

For example, (E) as a colorant, in the case of containing solvent-free components such as pigments, dispersing treatment using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, etc. in advance it is preferable Since the (E) colorant is finely divided by the dispersion treatment, the coating properties of the photosensitive resin composition are improved.

Dispersion treatment is usually preferably performed in a system in which (E) a colorant, a solvent, and (F) a dispersing agent are used in combination, or in a system in which (C) some or all of the alkali-soluble resin is optionally used in combination (hereinafter, dispersion The mixture to be subjected to the treatment and the composition obtained by the dispersion treatment are sometimes referred to as "ink" or "pigment dispersion"). In particular (F), when a polymer dispersing agent is used as the dispersing agent, the obtained ink and the photosensitive resin composition are excellent in dispersion stability and thickening over time is suppressed, so it is preferable.

Thus, the process of manufacturing the photosensitive resin composition WHEREIN: It is preferable to manufacture the pigment dispersion liquid containing at least (E) a coloring agent, a solvent, and (F) a dispersing agent.

As (E) colorant, organic solvent, and (F) dispersing agent which can be used for a pigment dispersion liquid, what was described as what can be used for the photosensitive resin composition, respectively can be employ|adopted preferably. Moreover, what was described as a content rate in the photosensitive resin composition can be preferably employ|adopted also as a content rate of each coloring agent of (E) coloring agent in a pigment dispersion liquid.

When the (E) colorant is dispersed with a sand grinder, glass beads or zirconia beads having a particle diameter of about 0.1 to 8 mm are preferably used. The dispersion treatment condition is that the temperature is usually from 0°C to 100°C, preferably from room temperature to 80°C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid, the size of the dispersion processing apparatus, and the like. Controlling the gloss of the ink is a standard of dispersion so that the 20 degree specular gloss (JIS Z8741) of the photosensitive resin composition is in the range of 50 to 300.

The dispersed particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3 µm, and is measured by a dynamic light scattering method or the like.

Next, the ink obtained by the dispersion process and the other component contained in the photosensitive resin composition are mixed, and it is set as a uniform solution or dispersion liquid. In the manufacturing process of the photosensitive resin composition, since fine dust may be mixed in a liquid, it is preferable to filter the obtained photosensitive resin composition with a filter etc.

[2] Bulkhead and its formation method

By hardening the photosensitive resin composition of this invention, the hardened|cured material of this invention can be obtained. The photosensitive resin composition of the present invention can be used to form a partition wall, for example, a partition wall for partitioning an organic layer of an organic electroluminescent element, or a pixel portion in a color filter containing luminescent nanocrystal particles. In order to form a partition, it can use preferably. The partition of this invention is comprised from the hardened|cured material of this invention.

The method of forming a partition using the photosensitive resin composition of this invention is not specifically limited, A conventionally well-known method is employable. As a formation method of a partition, the method including the application process of apply|coating the photosensitive resin composition on a board|substrate, and forming the photosensitive resin composition layer, and the exposure process of exposing the photosensitive resin composition layer, for example is mentioned, for example. . As a specific example of the formation method of such a partition, the inkjet method and the photolithography method are mentioned.

In the inkjet method, a photosensitive resin composition whose viscosity has been adjusted by dilution with a solvent or the like is used as an ink, and ink droplets are discharged on the substrate by the inkjet method along a pattern of a predetermined partition wall, so that the photosensitive resin composition is applied on the substrate, Forms a pattern of hardening barrier ribs. Then, the uncured barrier rib pattern is exposed to form a hardened barrier rib on the substrate. Exposure of the pattern of the non-hardened partition is performed similarly to the exposure process in the photolithographic method mentioned later except not using a mask.

In the photolithographic method, the photosensitive resin composition is apply|coated to the whole surface of the area|region in which the partition of a board|substrate is formed, and the photosensitive resin composition layer is formed. After exposing the formed photosensitive resin composition layer according to the pattern of a predetermined|prescribed partition, the exposed photosensitive resin composition layer is developed, and a partition is formed on a board|substrate.

In the application process of applying the photosensitive resin composition onto a substrate in the photolithography method, a contact transfer type coating device such as a roll coater, reverse coater, or bar coater, or a spinner (rotary coating device) on a substrate on which a barrier rib is to be formed , The photosensitive resin composition is applied using a non-contact coating device such as a curtain flow coater, and if necessary, the solvent is removed by drying to form a photosensitive resin composition layer.

Next, in the exposure step, using a negative mask, the photosensitive resin composition is irradiated with active energy rays such as ultraviolet rays or excimer laser light to partially expose the photosensitive resin composition layer according to the bank pattern. For exposure, a light source that generates ultraviolet rays such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used. Although the exposure amount changes also with the composition of the photosensitive resin composition, for example, about 10-400 mJ/cm<2> is preferable.

Next, in a developing process, a barrier rib is formed by developing the photosensitive resin composition layer exposed according to the pattern of a barrier rib with a developing solution. The developing method is not specifically limited, An immersion method, a spray method, etc. can be used. Specific examples of the developer include organic substances such as dimethylbenzylamine, monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts. Moreover, an antifoamer and surfactant can also be added to a developing solution.

Then, a post-baking, ie, a heat hardening process, is performed to the partition after image development. As for the conditions of a post-baking, 15 to 180 minutes are preferable at 80-250 degreeC.

The board|substrate used for formation of the barrier rib is not specifically limited, It is suitably selected according to the kind of organic electroluminescent element manufactured using the board|substrate with which the barrier rib was formed. Glass and various resin materials are mentioned as a preferable material of a board|substrate. As a specific example of a resin material, Polyester, such as a polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; polycarbonate; poly(meth)methacrylic resin; polysulfone; Polyimide is mentioned. Among the materials of these substrates, glass and polyimide are preferable because they are excellent in heat resistance. In addition, depending on the kind of organic electroluminescent element to be manufactured, you may form in advance transparent electrode layers, such as ITO and ZnO, on the surface of the board|substrate on which the partition is formed.

The film thickness of the barrier rib of the present invention is preferably 0.1 µm or more, more preferably 1 µm or more, still more preferably 5 µm or more, particularly preferably 10 µm or more, further preferably 1 mm or less, more Preferably it is 100 micrometers or less, More preferably, it is 50 micrometers or less, Even more preferably, it is 30 micrometers or less, Especially preferably, it is 20 micrometers or less. There exists a tendency for light-shielding property to improve by setting it as more than the said lower limit. Moreover, there exists a tendency for adhesiveness to improve by using below the said upper limit. The film thickness of the barrier rib is measured with a level difference, surface roughness, and fine shape measuring apparatus, a scanning white interference microscope, an ellipsometer, a reflection spectroscopic thickness meter, and an electron microscope.

[3] Organic electroluminescent device

The organic electroluminescent element of this invention is equipped with the partition of this invention.

Various organic electroluminescent devices are manufactured using the board|substrate provided with the barrier rib pattern manufactured by the method demonstrated above. The method of forming the organic electroluminescent element is not particularly limited, but preferably, after forming the pattern of barrier ribs on the substrate by the above method, ink is injected into the region surrounded by the barrier ribs on the substrate to form an organic layer such as a pixel. By forming, an organic electroluminescent device is manufactured.

As a type of an organic electroluminescent element, a bottom emission type and a top emission type are mentioned.

In the bottom emission type, for example, a barrier rib is formed on a glass substrate on which a transparent electrode is laminated, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are laminated on an opening surrounded by the barrier rib. On the other hand, in the top emission type, for example, a barrier rib is formed on a glass substrate on which a metal electrode layer is laminated, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are laminated in an opening surrounded by the barrier rib.

In the case where the barrier rib is in the shape of a skirt, the ink for forming the organic layer is repelled from the drooping portion of the barrier rib. Therefore, the area surrounded by the barrier rib may not be sufficiently covered with the ink for forming the organic layer. On the other hand, by setting it as a favorable shape without sagging, the inside of the area|region enclosed by the partition can be fully coat|covered with the ink for organic layer formation. Thereby, the problem of the halation in an organic electroluminescent display element can be eliminated, for example.

As a solvent used when forming the ink for organic layer formation, water, an organic solvent, and these mixed solvent can be used. The organic solvent is not particularly limited as long as it can be removed from the film formed after the ink is injected. Specific examples of the organic solvent include toluene, xylene, anisole, mesitylene, tetralin, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl alcohol, Ethyl acetate, butyl acetate, 3-phenoxytoluene, etc. are mentioned. Moreover, surfactant, antioxidant, a viscosity modifier, a ultraviolet absorber, etc. can be added to ink.

As a method of injecting ink into the region surrounded by the partition wall, the inkjet method is preferable because a small amount of ink can be easily injected at a predetermined point. The ink used for formation of an organic layer is suitably selected according to the kind of organic electroluminescent element manufactured. When the ink is injected by the inkjet method, the viscosity of the ink is not particularly limited as long as the ink can be discharged satisfactorily from the inkjet head, but 4 to 20 mPa·s is preferable, and 5 to 10 mPa·s is more preferable. do. The viscosity of the ink can be adjusted by adjusting the solid content in the ink, changing the solvent, adding a viscosity modifier, and the like.

Moreover, as a light emitting layer, the organic electroluminescent layer described in Unexamined-Japanese-Patent No. 2009-146691 and Unexamined-Japanese-Patent No. 5734681 is mentioned. Moreover, you may use the quantum dot described in Japanese Patent No. 5653387 or Japanese Patent No. 5653101.

[4] Color filter containing luminescent nanocrystal particles

The color filter containing the luminescent nanocrystal particle which concerns on this invention will not be specifically limited if equipped with the partition of this invention, What formed the pixel in the area|region partitioned by the partition is mentioned.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing of an example of the color filter provided with the partition of this invention. As shown in FIG. 1 , the color filter 100 includes a substrate 10 , a barrier rib 20 formed on the substrate, a red pixel 30 , a green pixel 40 , and a blue pixel 50 , have. The red pixel 30 , the green pixel 40 , and the blue pixel 50 are arranged in a grid shape so as to be repeated in this order. The partition wall 20 is formed between these adjacent pixels. In other words, these adjacent pixels are partitioned by the partition wall 20 .

The red pixel 30 contains red luminescent nanocrystal particles 2 , and the green pixel 40 contains green luminescent nanocrystal particles 1 . The blue pixel 50 is a pixel that transmits blue light from the light source.

These nanocrystal particles are nano-sized crystals that absorb excitation light and emit fluorescence or phosphorescence, and have a maximum particle diameter of 100 nm or less as measured by, for example, a transmission electron microscope or a scanning electron microscope.

The luminescent nanocrystal particle can emit light (fluorescence or phosphorescence) of a wavelength different from the absorbed wavelength by absorbing light of a predetermined wavelength. For example, the red luminescent nanocrystal particle 2 is 605 It emits light (red light) having an emission peak wavelength in the range of 665 nm, and the green luminescent nanocrystal particles 1 emit light (green light) having an emission peak wavelength in the range of 500 to 560 nm. will be.

The wavelength (luminescence color) of the light emitted by the luminescent nanocrystal particles depends on the size (eg particle diameter) of the luminescent nanocrystal particles according to the solution of the Schrödinger wave equation of the well-type potential model, but the energy gap of the luminescent nanocrystal particles also depend on Therefore, the luminescent color can be selected by changing the constituent material and size of the luminescent nanocrystal particles to be used. Quantum dots etc. are mentioned as a luminescent nanocrystal particle.

The manufacturing method of the color filter containing the luminescent nanocrystal particles is not particularly limited, but a substrate having barrier ribs composed of the cured product of the present invention is prepared, and a layer containing the luminescent nanocrystal grains is formed in the region partitioned by the barrier ribs. A method of forming is mentioned. Although the method of forming the layer containing the luminescent nanocrystal particles is not particularly limited, for example, an ink composition containing the luminescent nanocrystal particles is selectively attached by an inkjet method, and the ink is irradiated or heated by active energy rays. It can be prepared by a method of curing the composition.

[5] Image display device

The image display apparatus of this invention is equipped with the partition of this invention.

As an image display apparatus of this invention, the image display apparatus containing the organic electroluminescent element of this invention is mentioned, for example. As long as it contains an organic electroluminescent element, there is no restriction|limiting in particular about the form or structure of an image display device, For example, it can assemble according to a conventional method using an active drive type organic electroluminescent element. For example, by the method described in "Organic EL Display" (Oumsa, published on August 20, 2016, by Shizuo Tokito, Chihaya Adachi, Hideyuki Murata), the image display device of the present invention can be formed have. For example, an image may be displayed by combining an organic electroluminescent element emitting white light and a color filter, or an image may be displayed by combining an organic electroluminescent element having different emission colors such as RGB.

Moreover, as an image display apparatus of this invention, the image display apparatus provided with the color filter containing the luminescent nanocrystal particle which concerns on this invention, for example is mentioned.

As a kind of image display apparatus, a liquid crystal display device, the image display apparatus containing an organic electroluminescent element, etc. are mentioned. In the case of a liquid crystal display, a liquid crystal layer including a light source including a blue LED and an electrode for controlling blue light generated from the light source for each pixel unit may be included.

On the other hand, in the image display device containing an organic electroluminescent element, what arrange|positioned the organic electroluminescent element of blue light emission in the position corresponding to each pixel part of the said color filter is mentioned. Specifically, the method described in Unexamined-Japanese-Patent No. 2019-87746 is mentioned.

Example

EMBODIMENT OF THE INVENTION Hereinafter, although the photosensitive resin composition of this invention is given and demonstrated with reference to a specific example, this invention is not limited to a following example, unless the summary is exceeded.

The constituent components of the photosensitive resin composition used in the following Examples and Comparative Examples are as follows.

<Alkali-soluble resin-I (alkali-soluble resin (C-1))>

"ZCR-8024H" manufactured by Nippon Kayaku Co., Ltd. (weight average molecular weight Mw = 3500, acid value = 57 mgKOH/g). It has a partial structure represented by a following formula (C1).

[Formula 50]

<Alkali-soluble resin-II>

"ZCR-1642H" manufactured by Nippon Kayaku Co., Ltd. (weight average molecular weight Mw = 6500, acid value = 98 mgKOH/g). It has a partial structure represented by the following formula (C2), and does not have a partial structure represented by the said formula (C1).

[Formula 51]

<Alkali-soluble resin-III>

Dicyclopentanyl methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.30/0.10/0.60) is subjected to an equivalent addition reaction of acrylic acid to glycidyl methacrylate to a copolymer resin as a constituent monomer, and further Alkali-soluble acrylic copolymer resin obtained by addition reaction of tetrahydrophthalic anhydride so that it might become 0.39 mol with respect to 1 mol of said copolymer resin. The polystyrene conversion weight average molecular weight (Mw) measured by GPC was 9000, and the solid content acid value was 80 mgKOH/g.

<Alkali-soluble resin-IV>

To a copolymer resin containing dicyclopentanyl methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.02/0.05/0.93) as a constituent monomer, acrylic acid and glycidyl methacrylate are subjected to an equivalent addition reaction, and further anhydrous Alkali-soluble acrylic copolymer resin in which tetrahydrophthalic acid was added so as to be 0.10 mol with respect to 1 mol of said copolymer resin. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 7700, and the solid content acid value was 28.5 mgKOH/g.

<Dispersant-I>

BYK-LPN21116 manufactured by Big Chemie (acrylic A-B block copolymer comprising an A block having a quaternary ammonium base and a tertiary amino group, and a B block having no quaternary ammonium base and tertiary amino group. Amine value is 70 mgKOH/g (Acid value is 1 mgKOH/g or less.)

<Solvent-I>

PGMEA: Propylene glycol monomethyl ether acetate

<Solvent-II>

MB: 3-methoxy-1-butanol

<Photopolymerizable monomer>

DPHA: dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.

<Photoinitiator-I>

Compounds having the following chemical structures were used.

[Formula 52]

<Photoinitiator-II>

Compounds having the following chemical structures were used.

[Formula 53]

<Liquid repellent-I>

Megapac RS-90 manufactured by DIC (a fluorine-based, liquid repellent having an ethylenic double bond)

<Surfactant-I>

Megapac F-559 manufactured by DIC (fluorine-based surfactant without a crosslinking group)

<Additive-I>

Showa Denko Co., Ltd. Karenz MT PE1 (pentaerythritol tetrakis (3-mercaptobutyrate)

<Additive-II>

KAYAMER PM-21 manufactured by Nippon Kayaku Co., Ltd. (Phosphate containing methacryloyl group)

<Organic black pigment>

Irgaphor Black S 0100 CF manufactured by BASF

<Preparation of Pigment Dispersion Liquids 1 to 3>

A pigment, a dispersing agent, alkali-soluble resin, and a solvent were mixed so that it might become the mass ratio shown in Table 1. This solution was disperse|distributed by the paint shaker at the temperature range of 25-45 degreeC for 3 hours. For the beads, 0.5 mm phi zirconia beads were used, and 2.5 times the mass of the dispersion was added. After the dispersion was completed, beads and dispersions were separated with a filter to prepare pigment dispersions 1-3.

[Examples 1 to 9 and Comparative Examples 1 to 3]

Using the pigment dispersion liquids 1-3 prepared above, each component is added so that the ratio of the solid content of each component in the total solid content of the photosensitive resin composition becomes the compounding ratio of Table 2, and the content rate of the total solid content is 31 mass %, Moreover, in all the solvents, the solvent was added so that it might become solvent-I/solvent-II=80/20 (mass ratio), it stirred and melt|dissolved, and the photosensitive resin compositions 1-10 were prepared. Using each obtained photosensitive resin composition, the method mentioned later evaluated.

In addition, the compounding ratio of the pigment dispersion liquid, alkali-soluble resin, and liquid repellent in Table 2 is a solid content conversion value.

A method of performance evaluation will be described below.

<Measurement of PGMEA contact angle>

Using a spinner on a glass substrate, the said photosensitive resin composition was apply|coated so that it might become a thickness of 10 micrometers after heat-hardening. This application board|substrate was vacuum-dried for 1 minute, and also heat-dried at 100 degreeC for 120 second on a hotplate. The entire surface was exposed to the obtained coating film at 27 mJ/cm 2 using a high-pressure mercury lamp. The light intensity at the wavelength of 365 nm at this time was 100 mW/cm<2>. Next, this substrate was spray-developed at 24°C for 70 seconds using an aqueous solution in which 0.04 mass% of KOH and 0.07 mass% of emulgen A-60 (manufactured by Kao Corporation, surfactant) were dissolved as a developer, followed by pure water. Washed for 27 seconds. Finally, this board|substrate was heat-hardened for 30 minutes at the temperature shown in Table 2 in oven, and the board|substrate for contact angle measurement was obtained.

Using Drop Master 500 (contact angle measuring device) manufactured by Kyowa Interface Science Co., Ltd., the contact angle of the substrate for contact angle measurement 1 second after PGMEA 0.7 μl was added dropwise under the conditions of 23° C. and 50% RH, and the following standards to evaluate ink repellency. The results are shown in Table 2. A thing with a large contact angle shows that ink repellency is high.

(Evaluation criteria for ink repellency)

A : PGMEA contact angle is 40.0° or more

B : PGMEA contact angle less than 40.0°

<Evaluation of the minimum contact line width>

Using a spinner on a glass substrate, the said photosensitive resin composition was apply|coated so that it might become a thickness of 10 micrometers after heat-hardening. This application board|substrate was vacuum-dried for 1 minute, and also heat-dried at 100 degreeC for 120 second on a hotplate. Next, UV exposure was performed by cutting the wavelength of 330 nm or less with a high-pressure mercury-vapor lamp using a photomask for the obtained coating-film board|substrate. The exposure amount was 50 mJ/cm 2 , and the exposure gap was 5 µm. The light intensity at the wavelength of 365 nm at this time was 45 mW/cm<2>. As the photomask, a photomask having an opening width of 5 to 50 µm (5 to 20 µm: 1 µm interval, 25 to 50 µm: 5 µm interval) and line-shaped openings of various widths with an opening length of 2 mm was used. Next, after developing under the same conditions as in the production of the substrate for measuring the contact angle, washing with pure water for 10 seconds, heating and curing in an oven at the temperature shown in Table 2 for 30 minutes to prepare a line-shaped patterned substrate assuming a barrier rib did.

The entire line (2 mm) on the line-shaped pattern substrate was observed with an optical microscope, and the opening width of the line having the smallest opening width of the corresponding mask among the lines without omission or peeling and in close contact on the substrate was determined as the minimum adhesion line. It was set as the width, and the following references|standards evaluated it. It shows that adhesiveness is so high that the minimum adhesion line width is small.

(Evaluation criteria for minimum contact line width)

A: less than 13 μm

B: 13 μm or more

As is clear from the comparison of Examples 1 to 9 and Comparative Examples 1 and 2 in Table 2, by containing alkali-soluble resin (C-1), the PGMEA contact angle becomes favorable even at a low exposure amount, and in particular, by increasing the content ratio, PGMEA The contact angle is increased. Since the alkali-soluble resin (C-1) has a benzene ring in the main chain, hydrophobicity tends to increase, and in particular, having two or more crosslinking groups in the side chain increases the crosslinking density, so that the liquid repellent easily remains on the membrane surface even after development, It is thought that high ink repellency was expressed.

Moreover, the minimum contact|adherence line width was able to be made small by containing alkali-soluble resin (C-1) evidently from the comparison of Examples 1-9 of Table 2, and Comparative Example 1. When alkali-soluble resin (C-1) has two or more crosslinking groups in a side chain, a crosslinking density becomes high and it is thought that peeling at the time of image development of the line formed at the time of exposure was suppressed.

When a fluorine-based surfactant having no crosslinking group was used instead of the liquid-repellent agent as in Comparative Example 3, ink repellency became insufficient. Since it does not have a crosslinking group, surfactant eluted to the outside of a coating film at the time of image development, and it is thought that it is because the residual amount of surfactant in the film|membrane surface after image development fell. On the other hand, when a liquid repellent having an ethylenic double bond serving as a crosslinking group was used as in Examples 1 to 9, elution at the time of development was suppressed.

As is clear from Examples 8 and 9 of Table 2, the photosensitive resin composition of this invention was able to make a favorable PGMEA contact angle and a small minimum adhesion line width compatible also in the post-baking of 150 degrees C or less. By using both the liquid repellent which has a crosslinking group, and alkali-soluble resin (C-1), it is thought that these performances were compatible.

One ; Green Luminescent Nanocrystalline Particles
2 ; Red Luminescent Nanocrystalline Particles
10 ; Board
20 ; septum
30 ; red pixel
40 ; green pixel
50 ; blue pixel
100 ; color filter

Claims (11)

A photosensitive resin composition comprising (A) an ethylenically unsaturated compound, (B) a photoinitiator, (C) an alkali-soluble resin, and (D) a liquid repellent,
Said (C) alkali-soluble resin contains alkali-soluble resin (C-1) which has a partial structure represented by the following general formula (c1),
Said (D) liquid repellent contains the fluorine atom containing resin which has a crosslinking group, The photosensitive resin composition characterized by the above-mentioned.

(In formula (c1), R ^c11 represents a hydrogen atom or a methyl group.
R ^c12 represents a divalent hydrocarbon group which may have a substituent.
n represents the integer of 2 or 3.
The benzene ring in Formula (c1) may be further substituted by arbitrary substituents.
* denotes each bond.) The method of claim 1,
The photosensitive resin composition whose content rate of the said alkali-soluble resin (C-1) in said (C) alkali-soluble resin is 60 mass % or more. 3. The method according to claim 1 or 2,
The photosensitive resin composition containing further (E) a coloring agent. 4. The method of claim 3,
The photosensitive resin composition whose content rate of the said (E) coloring agent is 50 mass % or less in the total solid of the photosensitive resin composition. 5. The method according to claim 3 or 4,
The photosensitive resin composition in which the said (E) coloring agent contains at least 1 type selected from the group which consists of a red pigment and an orange pigment, and at least 1 type chosen from the group which consists of a blue pigment and a purple pigment. 6. The method according to any one of claims 3 to 5,
The photosensitive resin composition in which the said (E) coloring agent contains a purple pigment. Hardened|cured material which hardened|cured the photosensitive resin composition in any one of Claims 1-6. A barrier rib composed of the cured product according to claim 7. The organic electroluminescent element provided with the partition of Claim 8. The color filter comprising the luminescent nanocrystal particle provided with the partition of Claim 8. The image display apparatus provided with the partition of Claim 8.

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