KR20220044888A - Black photosensitive resin composition, method of manufacturing patterned cured product, patterned cured product and black matrix - Google Patents

Abstract

An objective of the present invention is to provide a black photosensitive resin composition capable of forming a light-shielding cured product having high solvent resistance and pattern shape with excellent linearity even when a baking temperature is low, a method for producing a patterned cured product using the black photosensitive resin composition, a patterned cured product formed from a cured product of the black photosensitive resin composition, and a black matrix formed from the cured product of the black photosensitive resin composition. The black photosensitive resin composition comprises an alkali-soluble resin (A), a photo-polymerizable monomer (B), a photo-polymerization initiator (C), a light-shielding agent (D), and a polyfunctional thiol compound (E). The light-shielding agent (D) is composed of a specific organic black pigment (D1) and a pigment (D2) other than the organic black pigment (D1). The content of the light-shielding agent (D) in the total solid content is 25 % by mass or more to 50 % by mass or less, and the proportion of the organic black pigment (D1) to the total amount of the organic black pigment (D1) and the pigment (D2) is 40 % by mass or more to 80% by mass or less.

Description

A black photosensitive resin composition, the manufacturing method of a patterned hardened|cured material, a patterned hardened|cured material, and a black matrix TECHNICAL FIELD

The present invention relates to a black photosensitive resin composition, a method for producing a patterned cured product, a patterned cured product, and a black matrix.

In a panel for a display device such as a liquid crystal display device, a patterned light-shielding film such as a black matrix or a black column spacer is usually formed. Various photosensitive compositions containing a light-shielding black pigment and a photoinitiator used in order to form a light-shielding film|membrane with respect to such a use are proposed.

As such a photosensitive composition, for example, a binder resin, a compound having at least one ethylenically unsaturated double bond in a molecule, a photoinitiator, a black pigment, a solvent, and a black photosensitive resin composition containing a thiol compound have been proposed (patents). See document 1).

[Patent Document 1] Japanese Patent Laid-Open No. 2004-325734

By the way, light-shielding cured films, such as a black matrix, may be formed in the image display apparatus in which the material with low heat resistance, such as an organic electroluminescent display, was used. For this reason, it is preferable in the black photosensitive resin composition that the light-shielding hardened|cured material can be formed by baking at lower temperature.

On the other hand, light-shielding cured films, such as a black matrix formed using the black photosensitive resin composition, may be applied by the layer formation process of forming the other functional layer in contact with the said cured film after formation of the said cured film. In such a layer formation process, it is typically performed using the composition which melt|dissolved components, such as resin, in the solvent. For this reason, if the black matrix etc. formed using the black photosensitive resin composition do not have the tolerance to the said solvent, this layer formation process WHEREIN: With respect to light-shielding cured films, such as a black matrix, a film thickness reduces, Swelling and deformation may occur, or properties such as light-shielding properties may decrease. It is preferable that the light-shielding hardened|cured material which has high solvent tolerance can be formed in the black photosensitive resin composition from said situation.

However, in the conventional black photosensitive resin composition, such as the black photosensitive resin composition of patent document 1, when a baking temperature is low, there exists a problem that it is difficult to form the hardened|cured material which has high solvent tolerance.

Moreover, it is calculated|required that light-shielding cured films, such as a black matrix, have the pattern shape excellent in linearity in many cases.

However, in conventional black photosensitive resin compositions, such as the black photosensitive resin composition described in patent document 1, when a baking temperature is low, it is often not possible to form the cured film which has a pattern shape excellent in straightness.

The present invention has been made in view of the above problems, and a black photosensitive resin composition capable of forming a light-shielding cured product having a pattern shape having high solvent tolerance and excellent straightness even when a baking temperature is low, and the black It is an object to provide a method for producing a patterned cured product using the photosensitive resin composition, a patterned cured product consisting of a cured product of the aforementioned black photosensitive resin composition, and a black matrix consisting of a cured product of the aforementioned black photosensitive resin composition do it with

The present inventors include an alkali-soluble resin (A), a photopolymerizable monomer (B), a photoinitiator (C), a light-shielding agent (D), and a polyfunctional thiol compound (E), and the light-shielding agent (D) is a specific It consists of pigments (D2) other than an organic black pigment (D1) and an organic black pigment (D1), Content of the light-shielding agent (D) in total solid is 25 mass % or more and 50 mass % or less, An organic black pigment (D1) and the ratio of the organic black pigment (D1) with respect to the total of the pigment (D2), by using the black photosensitive resin composition which is 40 mass % or more and 80 mass % or less, finds that the said subject can be solved, and this came to the conclusion of the invention. Specifically, the present invention provides the following.

A 1st aspect of this invention contains alkali-soluble resin (A), a photopolymerizable monomer (B), a photoinitiator (C), a light-shielding agent (D), and a polyfunctional thiol compound (E), A black photosensitive resin composition comprising:

The light-shielding agent (D) consists of pigments (D2) other than an organic black pigment (D1) and an organic black pigment (D1),

An organic black pigment (D1) is a following formula (d1):

(In the formula (d1), X ^d represents a double bond, and each is independently an E or Z form as a geometric isomer, and R ^d1 is each independently a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, Represent chlorine atom, fluorine atom, carboxyl group or sulfo ^{group.R d2} each independently represents hydrogen atom, methyl group or phenyl ^{group.R d3} each independently represents hydrogen atom, methyl group or chlorine atom. .)

At least one selected from lactam-based pigments and perylene-based pigments represented by

Content of the light-shielding agent (D) in the total solid of the black photosensitive resin composition is 25 mass % or more and 50 mass % or less,

It is a black photosensitive resin composition whose ratio of the organic black pigment (D1) with respect to the sum total of an organic black pigment (D1) and a pigment (D2) is 40 mass % or more and 80 mass % or less.

A second aspect of the present invention comprises the steps of applying the black photosensitive resin composition according to the first aspect to form a coating film;

A process of exposing the coating film positionally and selectively;

A process of developing the coating film after exposure;

It is a manufacturing method of the patterned hardened|cured material including the process of heating the coating film after image development.

A 3rd aspect of this invention is a patterned hardened|cured material which consists of hardened|cured material of the black photosensitive resin composition which concerns on 1st aspect.

A 4th aspect of this invention is a black matrix which consists of hardened|cured material of the black photosensitive resin composition which concerns on 1st aspect.

According to the present invention, a black photosensitive resin composition capable of forming a light-shielding cured product having a pattern shape having high solvent resistance and excellent linearity even when the baking temperature is low, and a patterned product using the black photosensitive resin composition The black matrix which consists of the manufacturing method of hardened|cured material, the patterned hardened|cured material which consists of hardened|cured material of the said black photosensitive resin composition, and the hardened|cured material of the said black photosensitive resin composition can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated based on suitable embodiment. In addition, in this specification, about the range shown using "-", it defines as a range including the numerical value of both ends or ratio.

«Black photosensitive resin composition»

A black photosensitive resin composition contains alkali-soluble resin (A), a photopolymerizable monomer (B), a photoinitiator (C), a light-shielding agent (D), and a polyfunctional thiol compound (E). And the light-shielding agent (D) consists of pigments (D2) other than an organic black pigment (D1) and an organic black pigment (D1). An organic black pigment (D1) is at least 1 sort(s) chosen from the lactam type pigment and perylene type pigment which are represented by a following formula (d1). Content of the light-shielding agent (D) in the total solid of the black photosensitive resin composition is 25 mass % or more and 50 mass % or less. The ratio of the organic black pigment (D1) with respect to the sum total of an organic black pigment (D1) and a pigment (D2) is 40 mass % or more and 80 mass % or less.

(In the formula (d1), X ^d represents a double bond, and each is independently an E or Z form as a geometric isomer, and R ^d1 is each independently a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, Represent chlorine atom, fluorine atom, carboxyl group or sulfo group.R ^d2 each independently represent hydrogen atom, methyl group or phenyl ^{group.R d3} each independently represent hydrogen atom, methyl group or chlorine atom. .)

For example,

A process of forming a coating film by coating;

a process of positionally selectively exposing the coating film;

A step of developing the coating film after exposure;

In a method including a step of heating a coating film after development, by using such a black photosensitive resin composition as a material for forming a coating film, as shown in Examples to be described later, in the step of heating (baking) the coating film after development Even when the heating temperature in the case is low, that is, even when the baking temperature is low, a patterned cured product having high solvent tolerance and having a pattern shape excellent in straightness can be formed. For example, even if the baking temperature is 120° C. or less, and further 100° C. or less or 95° C. or less, a light-shielding patterned cured product having a pattern shape having high solvent resistance and excellent straightness can be formed.

On the other hand, when the black photosensitive resin composition does not contain the polyfunctional thiol compound (E), or when the lactam-based pigment and perylene-based pigment represented by formula (d1) as the light-shielding agent (D) are not included, the black When content of the light-shielding agent (D) in the total solid of the photosensitive resin composition is not 25 mass % or more and 50 mass % or less, when it is not the said black photosensitive resin composition, when a baking temperature is low, solvent tolerance It is difficult to form a light-shielding cured product having this excellent pattern shape and excellent straightness.

Moreover, the said black photosensitive resin composition provides the light-shielding patterned hardened|cured material by passing through a predetermined process. For example, OD value (optical density) per 1 micrometer in thickness of the hardened|cured material of the said black photosensitive resin composition is 1.0 or more, Preferably it is 1.4 or more, More preferably, it is 1.9 or more.

Hereinafter, essential or arbitrary components are demonstrated about the black photosensitive resin composition.

<Alkali-soluble resin (A)>

The black photosensitive resin composition contains alkali-soluble resin (A) (it is also called (A) component hereafter.). Alkali developability can be provided to black photosensitive resin composition by mix|blending alkali-soluble resin (A) with black photosensitive resin composition.

Here, in this specification, alkali-soluble resin refers to resin provided with the functional group (For example, phenolic hydroxyl group, a carboxy group, a sulfonic acid group, etc.) which gives alkali solubility in a molecule|numerator.

It is preferable that alkali-soluble resin (A) contains resin which contains a photopolymerizable group like an ethylenically unsaturated double bond in a molecule|numerator. In this case, when forming a cured product (cured film) using the black photosensitive resin composition, between the alkali-soluble resin (A) and the polyfunctional thiol compound (E), or between the alkali-soluble resin (A) and the photopolymerizable monomer ( Crosslinking occurs between B) and the polyfunctional thiol compound (E). For this reason, it is easy to form the hardened|cured material which has high solvent resistance even if the baking temperature at the time of forming hardened|cured material is a low temperature, such as 120 degrees C or less, and 100 degrees C or less, or 95 degrees C or less, for example.

As a typical example of a photopolymerizable group, the functional group which has unsaturated double bonds, such as a vinyl group, an allyl group, and a (meth)acryloyl group, is mentioned, for example.

It is preferable that alkali-soluble resin (A) contains resin (a-1) which has a cardo structure in a molecule|numerator. The cardo structure will be described later in detail.

When resin which has a cardo structure in a molecule|numerator is used, it is easy to obtain the black photosensitive resin composition excellent in resolution, and it is easy to form the hardened|cured material which does not flow excessively by heating using the black photosensitive resin composition.

[Resin (a-1) having a cardo structure]

As the resin (a-1) having a cardo structure (hereinafter also referred to as cardo resin (a-1)), a resin having a cardo structure in the molecule and having predetermined alkali solubility can be used. The cardo structure refers to a skeleton in which the second cyclic structure and the third cyclic structure are bonded to one ring carbon atom constituting the first cyclic structure. In addition, the 2nd annular structure and the 3rd annular structure may be the same structure or different structures may be sufficient as them.

As a typical example of the cardo structure, the skeleton in which two aromatic rings (for example, a benzene ring) couple|bonded with the 9th-position carbon atom of a fluorene ring is mentioned.

It does not specifically limit as cardo resin (a-1), Conventionally well-known resin can be used. Especially, resin represented by a following formula (a-1) is preferable. Resin represented by a following formula (a-1) has a (meth)acryloyl group in a molecule|numerator as shown by a following formula (a-2). For this reason, resin represented by a following formula (a-1) corresponds to resin containing a photopolymerizable group in a molecule|numerator.

In formula (a-1), X ^a represents group represented by following formula (a-2). m1 represents an integer of 0 or more and 20 or less.

In the formula (a-2), R ^a1 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R ^a2 each independently represents a hydrogen atom or a methyl group, R ^a3 each independently represents a linear or branched alkylene group, m2 represents 0 or 1, and W ^a represents a group represented by the following formula (a-3).

In formula (a-2), R ^a3 is preferably an alkylene group having 1 or more and 20 or less carbon atoms, more preferably an alkylene group having 1 or more and 10 or less carbon atoms, and alkyl having 1 or more and 6 or less carbon atoms. A lene group is particularly preferred, and an ethane-1,2-diyl group, a propane-1,2-diyl group, and a propane-1,3-diyl group are most preferred.

Ring A in Formula (a-3) represents the aliphatic ring which may have an aromatic ring and the substituent which may be condensed. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring.

Examples of the aliphatic ring include monocycloalkane, bicycloalkane, tricycloalkane and tetracycloalkane.

Specific examples thereof include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, and adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane.

An aromatic hydrocarbon ring or an aromatic heterocyclic ring may be sufficient as the aromatic ring which may be condensed to an aliphatic ring, and an aromatic hydrocarbon ring is preferable. Specifically, a benzene ring and a naphthalene ring are preferable.

The following group is mentioned as a suitable example of the bivalent group represented by Formula (a-3).

The divalent group X ^a in the formula (a-1) is introduced into the cardo resin (a-1) by reacting the tetracarboxylic dianhydride giving the residue Z ^a with a diol compound represented by the following formula (a-2a). do.

In formula (a-2a), R ^a1 , R ^a2 , R ^a3 , and m2 are as described for formula (a-2). The ring A in the formula (a-2a) is as described for the formula (a-3).

The diol compound represented by Formula (a-2a) can be manufactured with the following method, for example.

First, a hydrogen atom in the phenolic hydroxyl group of a diol compound represented by the following formula (a-2b) is replaced with a group represented by -R ^a3 -OH according to a conventional method as needed, followed by epichlorohydrin or the like It glycidylates and obtains the epoxy compound represented by a following formula (a-2c).

Then, the diol compound represented by Formula (a-2a) can be obtained by making the epoxy compound represented by Formula (a-2c) react with acrylic acid or methacrylic acid.

In formulas (a-2b) and (a-2c), R ^a1 , R ^a3 , and m2 are as described for formula (a-2). The ring A in the formulas (a-2b) and (a-2c) is as described for the formula (a-3).

In addition, the manufacturing method of the diol compound represented by Formula (a-2a) is not limited to said method.

The following diol compounds are mentioned as a suitable example of the diol compound represented by Formula (a-2b).

In the formula (a-1), R ^a0 is a hydrogen atom or a group represented by -CO-Y ^a -COOH. Here, Y ^a represents the residue remove|excluding the acid anhydride group (-CO-O-CO-) from dicarboxylic acid anhydride. Examples of dicarboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylene methylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, Anhydrous glutaric acid etc. are mentioned.

In addition, in said Formula (a-1), Z ^a represents the residue which removed two acid anhydride groups from tetracarboxylic dianhydride. As an example of tetracarboxylic dianhydride, tetracarboxylic dianhydride represented by following formula (a-4), pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl ether tetracarboxylic acid 2 Anhydride etc. are mentioned.

In addition, in said formula (a-1), m1 represents the integer of 0 or more and 20 or less.

(In formula (a-4), R ^a4 , R ^a5 , and R ^a6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, m3 represents an integer of 0 or more and 12 or less.)

The alkyl group which can be selected as R ^a4 in formula (a-4) is a C1-C10 alkyl group. By setting the number of carbon atoms included in the alkyl group within this range, the heat resistance of the resulting carboxylic acid ester can be further improved. When R ^a4 is an alkyl group, the number of carbon atoms is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, and still more preferably 1 or more and 4 or less from the viewpoint of easily obtaining a cardo resin excellent in heat resistance. and 1 or more and 3 or less are particularly preferable.

When R ^a4 is an alkyl group, the alkyl group may be linear or branched.

R ^a4 in formula (a-4) is more preferably a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms, each independently from the viewpoint of easily obtaining a cardo resin excellent in heat resistance. R ^a4 in the formula (a-4) is more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group.

It is preferable that several R ^a4 in Formula (a-4) is the same group since preparation of highly purified tetracarboxylic dianhydride is easy.

m3 in Formula (a-4) represents the integer of 0 or more and 12 or less. When the value of m3 is 12 or less, purification of tetracarboxylic dianhydride can be facilitated.

From the viewpoint of easy purification of tetracarboxylic dianhydride, the upper limit of m 3 is preferably 5, more preferably 3 .

From the point of the chemical stability of tetracarboxylic dianhydride, 1 is preferable and, as for the minimum of m3, 2 is more preferable.

As for m3 in Formula (a-4), 2 or 3 is especially preferable.

The alkyl group having 1 to 10 carbon atoms which can be selected as R ^a5 and R ^a6 in the formula (a-4) is the same as the alkyl group having 1 to 10 carbon atoms that can be selected as R ^a4 .

R ^a5 and R ^a6 represent a hydrogen atom or a carbon atom number of 1 or more and 10 or less (preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, more Preferably it is 1 or more and 4 or less, Especially preferably, it is 1 or more and 3 or less), it is preferable that it is an alkyl group, and it is especially preferable that it is a hydrogen atom or a methyl group.

As tetracarboxylic dianhydride represented by Formula (a-4), it is norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''- norbornane-5,5'', for example. ,6,6''-tetracarboxylic dianhydride (alias "norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2''-norbornane-5,5'', 6, 6''-tetracarboxylic dianhydride"), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-(methylnorbornane)-5,5'', 6, 6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid Dianhydride (alias "norbornane-2-spiro-2'-cyclohexanone-6'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic dianhydride" ), methylnorbornane-2-spiro-α-cyclohexanone-α'-spiro-2''-(methylnorbornane)-5,5'', 6,6''-tetracarboxylic dianhydride, Norbornane-2-spiro-α-cyclopropanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2- Spiro-α-cyclobutanone-α′-spiro-2′′-norbornane-5,5′′,6,6′′-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclohep Thanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclooctanone-α'-spiro -2''-norbornane-5,5'', 6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclononanone-α'-spiro-2''-nor Bornane-5,5'', 6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclodecanone-α'-spiro-2''-norbornane-5,5 '',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloundecanone-α'-spiro-2''-norbornane-5,5'',6,6 ''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclododecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid 2 Anhydride, norbornane-2-spiro-α-cyclotridecanone- α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclotetradecanone-α'-spiro- 2''-norbornane-5,5'', 6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentadecanone-α'-spiro-2''-nor Bornane-5,5'', 6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclopentanone)-α'-spiro-2''-norbornane- 5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclohexanone)-α'-spiro-2''-norbornane-5,5 '', 6,6''-tetracarboxylic dianhydride, etc. are mentioned.

1000 or more and 40000 or less are preferable, as for the mass average molecular weight of cardo resin (a-I), 1500 or more and 30000 or less are more preferable, 2000 or more and 10000 or less are still more preferable. By setting it as said range, sufficient heat resistance and mechanical strength can be acquired in hardened|cured material, obtaining favorable developability.

In this specification, a mass average molecular weight (Mw) is a measured value by polystyrene conversion of gel permeation chromatography (GPC).

Although content of resin (a-1) which has a cardo structure in alkali-soluble resin (A) is not specifically limited, 50 mass % or more is preferable, 70 mass % or more is more preferable, 90 mass % or more is further desirable.

Alkali-soluble resin (A) may contain alkali-soluble resin other than resin (a-1) which has a cardo structure.

5 mass % or more and 55 mass % or less are preferable, and, as for content of alkali-soluble resin (A) in the total solid of the black photosensitive resin composition, 10 mass % or more and 45 mass % are more preferable. By setting it as said range, it is easy to obtain the black photosensitive resin composition excellent in developability.

In addition, in this specification, solid content is the mass of the black photosensitive resin composition except the mass of the organic solvent.

<Photopolymerizable monomer (B)>

The black photosensitive resin composition contains a photopolymerizable monomer (B). As a photopolymerizable monomer (B), the compound which has an ethylenically unsaturated group is preferable. There exist a monofunctional compound and a polyfunctional compound in the compound which has such an ethylenically unsaturated group.

Examples of the monofunctional compound include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxy Methyl (meth)acrylamide, N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid , citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate , 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylic Late, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) Acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl ( and meth)acrylate and half (meth)acrylate of a phthalic acid derivative. These monofunctional compounds can be used individually or in combination of 2 or more types.

On the other hand, as the polyfunctional compound, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di( Meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaeryth Ritol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, di Pentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2 -Hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid Diglycidyl ester di(meth)acrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (ie, tolylene diisocyanate, trimethylhexamethylene diisocyanate, or hexamethylene diisocyanate) polyfunctional products such as a reaction product of 2-bedoxyethyl (meth)acrylate), methylene bis(meth)acrylamide, (meth)acrylamide methylene ether, and a condensate of a polyhydric alcohol and N-methylol (meth)acrylamide A compound, triacryl formal, etc. are mentioned. These polyfunctional compounds can be used individually or in combination of 2 or more types.

Moreover, as a compound which has an ethylenically unsaturated group, the polyfunctional (meth)acrylate represented by following formula (b1) is also mentioned.

In addition, in this specification, "(meth)acrylate" means both "acrylate" and "methacrylate", and "(meth)acryl" is both "acryl" and "methacrylic" , and "(meth)acryloyloxy" means both "acryloyloxy" and "methacryloyloxy".

(In formula (b1), R ^b1 is a hydrogen atom or a (meth)acryloyl group, and R ^b2 is each independently a hydrogen atom or a methyl group.)

Among the compounds having these ethylenically unsaturated groups, the polyfunctional (meth)acrylate represented by the formula (b1) from the viewpoint of solvent resistance is preferable.

Although content of the photopolymerizable monomer (B) in the total solid of the black photosensitive resin composition is 1 mass % or more and 30 mass % or less, for example, 5 mass % or more and 20 mass % or less are preferable. By setting it as 5 mass % or more and 20 mass % or less, it is easy to obtain the patterned hardened|cured material which has higher solvent tolerance and is excellent in linearity.

<Photoinitiator (C)>

It does not specifically limit as a photoinitiator (C), A conventionally well-known photoinitiator can be used.

As a photoinitiator (C), an oxime ester compound is mentioned.

As an oxime ester compound, the compound which has a partial structure represented by a following formula (c1) is preferable.

(in formula (c1),

n1 is 0 or 1,

R ^c2 is a monovalent organic group,

R ^c3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent,

* is a bonding hand.)

It is preferable that the compound which has a partial structure represented by Formula (c1) has a carbazole skeleton, a fluorene skeleton, a diphenyl ether skeleton, and a phenyl sulfide skeleton.

It is preferable that the compound which has a partial structure represented by Formula (c1) has one or two partial structures represented by Formula (c1).

Examples of the compound having a partial structure represented by the formula (c1) include compounds represented by the following formula (c2).

(in formula (c2), R ^c1 is a group represented by the following formula (c3), (c4), or (c5),

n1 is 0 or 1,

R ^c2 is a monovalent organic group,

R ^c3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.)

(In formula (c3), R ^c4 and R ^c5 are each independently a monovalent organic group,

n2 is an integer of 0 or more and 3 or less,

When n2 is 2 or 3, a plurality of R ^c5 may be the same or different, and a plurality of R ^c5 may be bonded to each other to form a ring.

* is a bonding hand.)

(in formula (c4), R ^c6 and R ^c7 are each independently a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom,

R ^c6 and R ^c7 may combine with each other to form a ring,

R ^c7 and the benzene ring in the fluorene skeleton may combine with each other to form a ring,

R ^c8 is a nitro group or a monovalent organic group,

n3 is an integer of 0 or more and 4 or less,

* is a bonding hand.)

(in formula (c5), R ^c9 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group;

A is S or O,

n4 is an integer of 0 or more and 4 or less,

* is a bonding hand.)

In formula (c3), R ^c4 is a monovalent organic group. R ^c4 can be selected from various organic groups as long as the object of the present invention is not impaired. As the organic group, a carbon atom-containing group is preferable, and a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms is more preferable. The number of carbon atoms in the carbon atom-containing group is not particularly limited, and 1 or more and 50 or less are preferable, and 1 or more and 20 or less are more preferable.

Suitable examples of R ^c4 include an alkyl group which may have a substituent having 1 to 20 carbon atoms, a cycloalkyl group which may have a substituent having 3 to 20 carbon atoms, and a substituent which may have 2 to 20 carbon atoms Saturated aliphatic acyl group, alkoxycarbonyl group which may have a substituent having 2 or more and 20 or less carbon atoms, phenyl group which may have a substituent, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, may have a substituent A phenylalkyl group having 7 or more and 20 or less carbon atoms, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, and 11 or more and 20 or less carbon atoms which may have a substituent A naphthylalkyl group, the heterocyclyl group which may have a substituent, the heterocyclylcarbonyl group which may have a substituent, etc. are mentioned.

In R ^c4 , an alkyl group having 1 or more and 20 or less carbon atoms is preferable. Linear or branched form may be sufficient as the said alkyl group. From the viewpoint of good solubility of the compound represented by the formula (c3) in the photosensitive resin composition, the number of carbon atoms in the alkyl group as R ^c4 is preferably 2 or more, more preferably 5 or more, and particularly preferably 7 or more. Moreover, in the photosensitive resin composition, 15 or less are preferable and, as for the carbon atom number of the alkyl group as ^Rc4 , 15 or less are more preferable from the point of compatibility with the compound represented by Formula (c3), and another component being favorable. Do.

When R ^c4 has a substituent, suitable examples of the substituent include a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aliphatic acyl group having 2 to 20 carbon atoms, carbon An aliphatic acyloxy group having 2 to 20 atoms, a phenoxy group, a benzoyl group, a benzoyloxy group, a group represented by -PO(OR) ₂ (R is an alkyl group having 1 to 6 carbon atoms), a halogen atom, a cyano group , a heterocyclyl group, and the like.

When R ^c4 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, O, or a heterocyclyl group obtained by condensing such monocyclic rings or such a monocyclic ring and a benzene ring. When the heterocyclyl group is a condensed ring, it is assumed that the number of rings is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. As a heterocycle constituting such a heterocyclyl group, furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyridine Midin, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, pr and talazine, cinnoline, quinoxarine, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran.

When R ^c4 is a heterocyclyl group, examples of the substituent which the heterocyclyl group may have include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, and a nitro group.

Suitable specific examples of R ^c4 described above include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, neopentyl group, pentan-3-yl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and 2-ethylhexyl group.

Moreover, since the solubility of the compound represented by Formula (c3) in the photosensitive resin composition is favorable, n-octyl group and 2-ethylhexyl group are preferable, and 2-ethylhexyl group is more preferable.

In formula (c3), R ^c5 is a monovalent organic group. R ^c5 can be selected from various organic groups within a range that does not impair the object of the present invention. As the organic group, a carbon atom-containing group is preferable, and a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms is more preferable. The number of carbon atoms in the carbon atom-containing group is not particularly limited, and 1 or more and 50 or less are preferable, and 1 or more and 20 or less are more preferable.

Examples of the monovalent organic group suitable as R ^c5 include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, an optionally substituted phenyl group, and an optionally substituted phenoxy group. Period, the benzoyl group which may have a substituent, the phenoxycarbonyl group which may have a substituent, the benzoyloxy group which may have a substituent, the phenylalkyl group which may have a substituent, the naphthyl group which may have a substituent, the naphth which may have a substituent Toxy group, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthoyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, heterocyclyl group which may have a substituent, a substituent A heterocyclylcarbonyl group which may have, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group, HX ₂ C- or H ₂ XC- and a substituent including a group represented by (however, each of X is independently a halogen atom) and the like.

When R ^c5 is an alkyl group, 1 or more and 20 or less are preferable and, as for the number of carbon atoms of an alkyl group, 1 or more and 6 or less are more preferable. Further, when R ^c5 is an alkyl group, it may be linear or branched. Specific examples when R ^c5 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group , sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n- A decyl group, an isodecyl group, etc. are mentioned. In addition, when R ^c5 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^c5 is an alkoxy group, 1 or more and 20 or less are preferable and, as for the number of carbon atoms of an alkoxy group, 1 or more and 6 or less are more preferable. Further, when R ^c5 is an alkoxy group, it may be linear or branched. Specific examples when R ^c5 is an alkoxy group include a methoxy group, an ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group , tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, and the like. In addition, when R ^c5 is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a meth Toxypropyloxy group, etc. are mentioned.

When R ^c5 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms in the cycloalkyl group or the cycloalkoxy group is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less. Specific examples when R ^c5 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples of the case where R ^c5 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ^c5 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, and more preferably 2 or more and 7 or less. Specific examples when R ^c5 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n-hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n- A pentadecanoyl group, n-hexadecanoyl group, etc. are mentioned. Specific examples in the case where R ^c5 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, and 2,2-dimethylpropanoyloxy group. Period, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, n -tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group, etc. are mentioned.

When R ^c5 is an alkoxycarbonyl group, 2 or more and 20 or less are preferable, and, as for the number of carbon atoms of the alkoxycarbonyl group, 2 or more and 7 or less are more preferable. Specific examples when R ^c5 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyl group Oxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec -octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, isodecyloxycarbonyl group, etc. are mentioned.

When R ^c5 is a phenylalkyl group, the number of carbon atoms in the phenylalkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. Moreover, when R<^c5> is a naphthylalkyl group, 11 or more and 20 or less are preferable and, as for the carbon atom number of a naphthylalkyl group, 11 or more and 14 or less are more preferable. Specific examples of the case where R ^c5 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ^c5 is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-(α-naphthyl)ethyl group, and a 2-(β-naphthyl)ethyl group. When R ^c5 is a phenylalkyl group or a naphthylalkyl group, R ^c5 may further have a substituent on the phenyl group or the naphthyl group.

When R ^c5 is a heterocyclyl group, the heterocyclyl group may further have a substituent as in the case where R ^c4 is a heterocyclyl group in the formula (c3).

When R ^c5 is a heterocyclylcarbonyl group, the heterocyclyl group included in the heterocyclylcarbonyl group is the same as when R ^c5 is a heterocyclyl group.

When R ^c5 is an amino group substituted with an organic group of 1 or 2, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 2 to 21 carbon atoms. A saturated aliphatic acyl group of A naphthoyl group, a C11-C20 naphthylalkyl group which may have a substituent, a heterocyclyl group, etc. are mentioned. Specific examples of these suitable organic groups are the same as those of R ^c5 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n-butyl Amino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-buta noylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group can be heard

When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^c5 further have a substituent, as the substituent, a substituent including a group represented by HX ₂ C- or H ₂ XC- (for example, HX ₂ C- or a halogenated alkoxy group including a group represented by H ₂ XC-, a halogenated alkyl group including a group represented by HX ₂ C- or H ₂ XC-), an alkyl group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms An alkoxy group, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, an alkyl group having 1 to 6 carbon atoms a monoalkylamino group having a, dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a benzoyl group, a halogen, a nitro group, and a cyano group. there is. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^c5 further have a substituent, the number of the substituents is not limited within a range that does not impair the object of the present invention, and preferably 1 or more and 4 or less. . When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^c5 have a plurality of substituents, the plurality of substituents may be the same or different.

Examples of the substituent in the case where the benzoyl group contained in R ^c5 further has a substituent include an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a 2-thenoyl group (thiophene- 2-ylcarbonyl group), a furan-3-ylcarbonyl group, and a phenyl group.

A fluorine atom, a chlorine atom, a bromine atom etc. are mentioned as a halogen atom represented by X, It is preferable that it is a fluorine atom.

Examples of the substituent containing a group represented by HX ₂ C- or H ₂ XC- include a halogenated alkoxy group containing a group represented by HX ₂ C- or H ₂ XC-, a halogenated group including a group represented by HX ₂ C- or H ₂ XC- and a group having an alkoxy group, a halogenated alkyl group including a group represented by HX ₂ C- or H ₂ XC-, a group having a halogenated alkyl group including a group represented by HX ₂ C- or H ₂ XC-, and the like, and HX ₂ C - or a group having a halogenated alkoxy group containing a group represented by H ₂ XC-, or a group having a halogenated alkoxy group containing a group represented by HX ₂ C- or H ₂ XC-.

Examples of the group having a halogenated alkyl group containing a group represented by HX ₂ C- or H ₂ XC- include an aromatic group substituted with a halogenated alkyl group containing a group represented by HX ₂ C- or H ₂ XC- (eg, a phenyl group, naphthyl group), a cycloalkyl group substituted with a halogenated alkyl group containing a group represented by HX ₂ C- or H ₂ XC- (eg, cyclopentyl group, cyclohexyl group, etc.), and the like, and HX ₂ C It is preferable that it is an aromatic group substituted with the halogenated alkyl group containing the group represented by - or _H2XC- .

Examples of the group having a halogenated alkoxy group containing a group represented by HX ₂ C- or H ₂ XC- include an aromatic group substituted with a halogenated alkoxy group containing a group represented by HX ₂ C- or H ₂ XC- (eg, a phenyl group, naphthyl group), an alkyl group substituted with a halogenated alkoxy group containing a group represented by HX ₂ C- or H ₂ XC- (eg, methyl group, ethyl group, n-propyl group, i-propyl group, etc.), HX ₂ C - or a cycloalkyl group substituted with a halogenated alkoxy group containing a group represented by H ₂ XC- (eg, a cyclopentyl group, a cyclohexyl group, etc.), etc., which are represented by HX ₂ C- or H ₂ XC- It is preferable that it is an aromatic group substituted with the halogenated alkoxy group containing a group.

Moreover, as R<^c5> , a cycloalkyl alkyl group, the phenoxy alkyl group which may have a substituent on the aromatic ring, and the phenylthioalkyl group which may have a substituent on the aromatic ring are preferable. The substituent which the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent which the phenyl group contained in R ^<c5> may have.

Among the monovalent organic groups, R ^c5 is preferably an alkyl group, a cycloalkyl group, an optionally substituted phenyl group, or a cycloalkyl alkyl group or a phenylthioalkyl group optionally having a substituent on the aromatic ring. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is most preferable. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable and a 2-methylphenyl group is more preferable. 5 or more and 10 or less are preferable, as for carbon atom number of the cycloalkyl group contained in a cycloalkyl alkyl group, 5 or more and 8 or less are more preferable, 5 or 6 are especially preferable. 1 or more and 8 or less are preferable, as for carbon atom number of the alkylene group contained in a cycloalkyl alkyl group, 1 or more and 4 or less are more preferable, 2 is especially preferable. Among the cycloalkyl alkyl groups, a cyclopentylethyl group is preferable. 1 or more and 8 or less are preferable, as for carbon atom number of the alkylene group contained in the phenylthioalkyl group which may have a substituent on an aromatic ring, 1 or more and 4 or less are more preferable, 2 is especially preferable. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, 2-(4-chlorophenylthio)ethyl group is preferable.

In the group represented by formula (c3), when a plurality of R ^c5 is present and a plurality of R ^c5 are bonded to each other to form a ring, examples of the ring to be formed include a hydrocarbon ring and a heterocycle. As a hetero atom contained in a heterocyclic ring, N, O, and S are mentioned, for example. As the ring formed by bonding a plurality of R ^c5 to each other, an aromatic ring is particularly preferable. An aromatic hydrocarbon ring or an aromatic heterocyclic ring may be sufficient as such an aromatic ring. As such an aromatic ring, an aromatic hydrocarbon ring is preferable. In the formula (c3), specific examples in the case where a plurality of R ^c5 are bonded to each other to form a benzene ring are shown below.

In the group represented by the formula (c4), R ^c8 is a nitro group or a monovalent organic group. R ^c8 is bonded to a 6-membered aromatic ring different from the aromatic ring bonded to the group represented by -(CO) _n1 - on the condensed ring in the formula (c4). In formula (c4), the bonding position of R ^c8 is not particularly limited. When the group represented by the formula (c4) has one or more R ^c8 , since the compound represented by the formula (c4) can be easily synthesized, one of the one or more R ^c8 is bonded to the 7th position of the fluorene skeleton it is preferable That is, when the group represented by the formula (c4) has one or more R ^c8 , the group represented by the formula (c4) is preferably represented by the following formula (c6). When there are a plurality of R ^c8 , the plurality of R ^c8 may be the same or different.

(In formula (c6), R ^c6 , R ^c7 , R ^c8 , and n3 are the same as R ^c6 , R ^c7 , R ^c8 , n3 in formula (c4), respectively.)

When R ^c8 is a monovalent organic group, R ^c8 is not particularly limited as long as the object of the present invention is not impaired. As the organic group, a carbon atom-containing group is preferable, and a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms is more preferable. The number of carbon atoms in the carbon atom-containing group is not particularly limited, and 1 or more and 50 or less are preferable, and 1 or more and 20 or less are more preferable.

Suitable examples of the case where R ^c8 is a monovalent organic group include the same groups as the preferred examples of the monovalent organic group as R ^c5 in the formula (c3).

In formula (c4), R ^c6 and R ^c7 each represent a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ^c6 and R ^c7 may combine with each other to form a ring. Among these groups, as R ^c6 and R ^c7 , a chain alkyl group which may have a substituent is preferable. When R ^c6 and R ^c7 are a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

When R ^c6 and R ^c7 are a chain alkyl group having no substituent, the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. Specific examples when R ^c6 and R ^c7 are a chain alkyl group include a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group , isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isono A nyl group, an n-decyl group, an isodecyl group, etc. are mentioned. In addition, when R ^c6 and R ^c7 are an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^c6 and R ^c7 are a chain alkyl group having a substituent, the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. In this case, the number of carbon atoms in the substituent is not included in the number of carbon atoms in the chain alkyl group. It is preferable that the chain|strand-chain alkyl group which has a substituent is linear.

The substituent which the alkyl group may have is not specifically limited in the range which does not impair the objective of this invention. Suitable examples of the substituent include an alkoxy group, a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group. Specific examples of the cycloalkyl group are the same as suitable examples in the case where R ^c8 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group. Specific examples of the heterocyclyl group are the same as suitable examples in the case where R ^c8 is a heterocyclyl group. When R ^c8 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and linear is preferable. 1 or more and 10 or less are preferable and, as for the carbon atom number of the alkoxy group contained in an alkoxycarbonyl group, 1 or more and 6 or less are more preferable.

When the chain alkyl group has a substituent, the number of the substituents is not particularly limited. The preferred number of substituents changes depending on the number of carbon atoms in the chain alkyl group. The number of substituents is typically 1 or more and 20 or less, 1 or more and 10 or less are preferable, and 1 or more and 6 or less are more preferable.

When R ^c6 and R ^c7 are a chain alkoxy group having no substituent, the number of carbon atoms in the chain alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. Specific examples in the case where R ^c6 and R ^c7 are a chain alkoxy group include a methoxy group, an ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert- Butyloxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec -octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, etc. are mentioned. In addition, when R ^c6 and R ^c7 are an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a meth Toxypropyloxy group, etc. are mentioned.

When R ^c6 and R ^c7 are a chain alkoxy group having a substituent, the substituent which the alkoxy group may have is the same as when R ^c6 and R ^c7 are a chain alkyl group.

When R ^c6 and R ^c7 are a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group. When R ^c6 and R ^c7 are a cyclic organic group, the substituent which the cyclic organic group may have is the same as when R ^c6 and R ^c7 are a chain alkyl group.

When R ^c6 and R ^c7 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group, a group formed by bonding a plurality of benzene rings through a carbon-carbon bond, or a group formed by condensation of a plurality of benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensing a plurality of benzene rings, the number of rings of the benzene ring included in the aromatic hydrocarbon group is not particularly limited, and preferably 3 or less, more preferably 2 or less, and 1 is particularly desirable. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.

When R ^c6 and R ^c7 are an aliphatic cyclic hydrocarbon group, the alicyclic hydrocarbon group may be monocyclic or polycyclic. Although the number of carbon atoms of an aliphatic cyclic hydrocarbon group is not specifically limited, 3 or more and 20 or less are preferable, and 3 or more and 10 or less are more preferable. Examples of the monocyclic cyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, and a tricyclodecyl group. , a tetracyclododecyl group, and an adamantyl group.

When R ^c6 and R ^c7 are heterocyclyl groups, the same groups as the heterocyclyl group as R ^c5 in formula (c3) can be mentioned.

R ^c6 and R ^c7 may combine with each other to form a ring. The group consisting of a ring formed by R ^c6 and R ^c7 is preferably a cycloalkylidene group. When R ^c6 and R ^c7 combine to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5- to 6-membered ring, more preferably a 5-membered ring.

When forming a ring with R ^c7 and the benzene ring of a fluorene skeleton, the said ring may be an aromatic ring, or an aliphatic ring may be sufficient as it.

When the group formed by bonding R ^c6 and R ^c7 is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of the ring which may be condensed with the cycloalkylidene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, A pyrazine ring, a pyrimidine ring, etc. are mentioned.

Among R ^c6 and R ^c7 described above, examples of suitable groups include groups represented by the formula -A ¹ -A ² . In the formula, A ¹ is a straight-chain alkylene group, and A ² is, for example, an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

1 or more and 10 or less are preferable and, as for carbon atom number of the linear alkylene group of A ¹ , 1 or more and 6 or less are more preferable. When ^A2 is an alkoxy group, linear or branched form may be sufficient as an alkoxy group, and linear form is preferable. 1 or more and 10 or less are preferable and, as for carbon atom number of an alkoxy group, 1 or more and 6 or less are more preferable. When ^A2 is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable, and a fluorine atom, a chlorine atom, and a bromine atom are more preferable. When A2 is ^a halogenated alkyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable and, as for the halogen atom contained in a halogenated alkyl group, a fluorine atom, a chlorine atom, and a bromine atom are more preferable. The halogenated alkyl group may be linear or branched, and linear is preferable. When A ² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic groups that R ^c6 and R ^c7 have as a substituent. When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group which R ^c6 and R ^c7 have as a substituent.

Suitable specific examples of R ^c6 and R ^c7 include an alkyl group such as an ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy group -n-heptyl group, 8-methoxy-n-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-phene alkoxyalkyl groups such as a tyl group, a 6-ethoxy-n-hexyl group, a 7-ethoxy-n-heptyl group, and an 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n-pentyl group, 6-cyano-n-hexyl group, 7-cyano group cyanoalkyl groups such as -n-heptyl and 8-cyano-n-octyl; 2-phenyl ethyl group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, and a phenylalkyl group such as an 8-phenyl-n-octyl group; 2-cyclohexyl ethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl group -n-heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pene cycloalkyl alkyl groups such as a tyl group, a 6-cyclopentyl-n-hexyl group, a 7-cyclopentyl-n-heptyl group, and an 8-cyclopentyl-n-octyl group; 2-Methoxycarbonyl-ethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycar Bornyl-n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonyl-ethyl group, 3-ethoxycarbonyl-n-propyl group group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxycarbonyl-n-heptyl group, and alkoxycarbonyl alkyl groups such as 8-ethoxycarbonyl-n-octyl group; 2-chloro ethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo- n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5; and halogenated alkyl groups such as 5-heptafluoro-n-pentyl group.

As R ^c6 and R ^c7 , suitable groups among the above are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenyl ethyl group, 2-cyclohexyl group Ethyl group, 2-methoxycarbonyl-ethyl group, 2-chloro ethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-hepta It is a fluoro-n-pentyl group.

In formula (c5), it is especially preferable that A is S from the point which is easy to obtain the photoinitiator excellent in sensitivity.

In formula (c5), R ^c9 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group.

When R ^c9 in Formula (c5) is a monovalent organic group, it can select from various organic groups within the range which does not impair the objective of this invention. As the organic group, a carbon atom-containing group is preferable, and a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms is more preferable. The number of carbon atoms in the carbon atom-containing group is not particularly limited, and 1 or more and 50 or less are preferable, and 1 or more and 20 or less are more preferable.

Suitable examples in the case where R ^c9 is an organic group in the formula (c5) include the same groups as the monovalent organic group as R ^c5 in the formula (c3).

Among R ^c9 , a benzoyl group; naphthoyl group; a benzoyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; nitro group; The benzofuranylcarbonyl group which may have a substituent is preferable, and a benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4-(piperazin-1-yl)phenylcarbonyl group; A 4-(phenyl)phenylcarbonyl group is more preferable.

In formula (c5), n4 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1. When n4 is 1, it is preferable that the bonding position of R ^c9 is para to the hand at which the phenyl group to which R ^c9 is bonded is bonded to an oxygen atom or a sulfur atom.

In formulas (c1) and (c2), the monovalent organic group as R ^c2 is not particularly limited as long as the object of the present invention is not impaired. As the organic group, a carbon atom-containing group is preferable, and a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms is more preferable. The number of carbon atoms in the carbon atom-containing group is not particularly limited, and 1 or more and 50 or less are preferable, and 1 or more and 20 or less are more preferable.

Preferable examples of the monovalent organic group as R ^c2 include the same groups as the monovalent organic group as R ^c5 in the formula (c3). Specific examples of these groups are the same as those described for R ^c5 in formula (c3).

Moreover, as R< ^c2 >, a cycloalkyl alkyl group, the phenoxy alkyl group which may have a substituent on the aromatic ring, and the phenylthioalkyl group which may have a substituent on the aromatic ring are preferable. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents in the case where the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^c5 in the formula (c3) further have a substituent.

Among the organic groups, R ^c2 may have a substituent including the group represented by HX ₂ C- or H ₂ XC-, an alkyl group, a cycloalkyl group, a phenyl group optionally having a substituent, or a cycloalkyl alkyl group or a substituent on the aromatic ring. A phenyl thioalkyl group is preferred. The number of carbon atoms of the alkyl group, the phenyl group which may have a substituent, the cycloalkyl group contained in the cycloalkyl alkyl group, the number of carbon atoms of the alkylene group contained in the cycloalkyl alkyl group, the cycloalkyl alkyl group, the phenylthio which may have a substituent on the aromatic ring About the number of carbon atoms of the alkylene group contained in the alkyl group, or the phenylthioalkyl group which may have a substituent on the aromatic ring, it is the same as R ^c5 of Formula (c3).

Moreover, as R ^c2 , the group represented by -A ³ -CO-OA ⁴ is preferable. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. ^A4 is a monovalent organic group, and it is preferable that it is a monovalent|monohydric hydrocarbon group.

When A ³ is an alkylene group, the alkylene group may be linear or branched, and linear is preferable. When A ³ is an alkylene group, 1 or more and 10 or less are preferable, as for the number of carbon atoms of an alkylene group, 1 or more and 6 or less are more preferable, and their 1 or more and 4 or less are still more preferable.

Preferable examples of A ⁴ include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. As a suitable specific example of A ⁴ , a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, phenyl group , a naphthyl group, a benzyl group, a phenethyl group, an α-naphthylmethyl group, and a β-naphthylmethyl group.

Preferable specific examples of the group represented by -A ³ -CO-OA ⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, and 2-n-butyloxycarbonyl group. Ethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group , 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl- n-propyl group, 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group, 3-phenoxycarbonyl-n-propyl group, etc. are mentioned.

Moreover, as R ^c2 , a group represented by the following formula (c7) or (c8) is preferable.

(in formulas (c7) and (c8), R ^c10 and R ^c11 are each independently a monovalent organic group;

n5 is an integer of 0 or more and 4 or less,

when R ^c10 and R ^c11 exist at adjacent positions on the benzene ring, R ^c10 and R ^c11 may combine with each other to form a ring;

R ^c12 is a monovalent organic group,

n6 is an integer of 1 or more and 8 or less,

n7 is an integer of 1 or more and 5 or less,

n8 is an integer greater than or equal to 0 (n7+3).)

The organic group as R ^c10 and R ^c11 in formula (c7) is the same as R ^c8 in formula (c4). R ^c10 is preferably a halogenated alkoxy group including a group represented by HX ₂ C- or H ₂ XC-, a halogenated alkyl group including a group represented by HX ₂ C- or H ₂ XC-, an alkyl group or a phenyl group. When R ^c10 and R ^c11 combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. As the group represented by the formula (c7), suitable examples of the group in which R ^c10 and R ^c11 form a ring include a naphthalen-1-yl group, a 1,2,3,4-tetrahydronaphthalen-5-yl group, and the like. can

In said formula (c7), n5 is an integer of 0 or more and 4 or less, It is preferable that it is 0 or 1, It is more preferable that it is 0.

In the formula (c8), R ^c12 is an organic group. Examples of the organic group include the same groups as the organic group described for R ^c8 in the formula (c4). Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. 1 or more and 10 or less are preferable, as for the number of carbon atoms of an alkyl group, 1 or more and 5 or less are more preferable, and their 1 or more and 3 or less are especially preferable. As R ^c12 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like are preferably exemplified, and among these, a methyl group is more preferable.

In the formula (c8), n7 is an integer of 1 or more and 5 or less, an integer of 1 or more and 3 or less is preferable, and 1 or 2 is more preferable. In the formula (c8), n8 is 0 or more (n7+3) or less, preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0.

In the formula (c8), n6 is an integer of 1 or more and 8 or less, preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and particularly preferably 1 or 2.

In formula (c2), R ^c3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. When R ^c3 is an aliphatic hydrocarbon group, a phenyl group, a naphthyl group, etc. are preferably exemplified as the substituent which may be included.

In formulas (c1) and (c2), R ^c3 represents a hydrogen atom, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-cyclopentyl ethyl group, 2-cyclobutyl ethyl group, and cyclohexyl methyl group. , a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group, etc. are illustrated preferably, Among these, a methyl group or a phenyl group is more preferable.

Preferable specific examples of the compound represented by the formula (c2) and having a group represented by the formula (c3) as R ^c1 include the following compounds.

Preferable specific examples of the compound represented by the formula (c2) and having a group represented by the formula (c4) as R ^c1 include the following compounds.

Preferable specific examples of the compound represented by the formula (c2) and having a group represented by the formula (c5) as R ^c1 include the following compounds.

Examples of the photoinitiator (C) other than the oxime ester compound include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-methyl-1-[4-(methylthio) Phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-dimethylaminophenyl) butan-1-one, 2-(4-methylbenzyl)-2-di Ethylamino-1-(4-morpholinophenyl)butan-1-one, 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1-[4-(hexyl) ?-amino ketone compounds such as phenyl]-2-morpholinopropan-1-one and 2-ethyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one; 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxye oxy) phenyl-(2-hydroxy-2-propyl) ketone and 1-hydroxycyclohexyl phenyl ketone α-hydroxyketone-based photopolymerization initiators; benzoin-based photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzyl methyl ketal; Benzophenone, benzoylbenzoic acid, methylbenzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl, 4'-methyldiphenyl sulfide, 4,4'-bisdiethylaminobenzophenone, etc. benzophenone-based photopolymerization initiator; thioxanthone-based photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, and 2,4-diisopropylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis( Trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piphenyl-4,6-bis(trichloromethyl)- s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s- Triazine, 2-(4-Methoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6 -triazine, 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine, 2-[4-(4-methoxystyryl)phenyl]-4,6-bis(trichloro triazine-based photopolymerization initiators such as romethyl)-1,3,5-triazine; carbazole-based photopolymerization initiator; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis (2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl ) -4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetra Phenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole , 2,2'-bis (2-bromophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromo Phenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-tribromophenyl)-4,4',5 Biimidazole-type photoinitiators, such as 5'-tetraphenyl-1,2'-biimidazole; The benzimidazoline-type photoinitiator etc. which are represented by a following formula are illustrated.

A photoinitiator can be used individually or in combination of 2 or more types. By using in combination of 2 or more types, it is easy to use effectively the light ray of the wavelength of the wide range contained in exposure light, and it is easy to adjust the sensitivity of the black photosensitive resin composition to an appropriate range.

0.5 mass % or more and 15 mass % or less are preferable, and, as for content of the photoinitiator (C) in the total solid of the black photosensitive resin composition, 1 mass % or more and 10 mass % or less are more preferable.

When using together photoinitiators other than the oxime ester compound, the ratio of the mass of the oxime ester compound to the mass of the photoinitiator (C) is preferably 50 mass% or more, more preferably 50 mass% or more and 99 mass% or less and 70 mass % or more and 97 mass % or less are especially preferable, and 80 mass % or more and 95 mass % or less are the most preferable.

When the photoinitiator (C) contains the oxime ester compound in an amount within such a range, it is difficult to form a patterned cured product having a wider width than a desired width in particular.

<Light-shielding agent (D)>

The black photosensitive resin composition contains a light-shielding agent (D). And the light-shielding agent (D) consists of an organic black pigment (D1) and pigments (D2) other than an organic black pigment (D1) (Hereinafter, it also describes simply as "pigment (D2)"). The light-shielding agent (D) may contain 1 type or 2 or more types of organic black pigments (D1). In addition, even if the light-shielding agent (D) contains 1 type of pigment (D2), it may contain it 2 or more types.

[Organic Black Pigment (D1)]

An organic black pigment (D1) is at least 1 sort(s) chosen from the lactam type pigment represented by a following formula (d1), and a perylene type pigment.

[Lactam pigment]

A lactam pigment is a compound represented by a following formula (d1).

In the formula (d1), X ^d represents a double bond and each independently represents an E or Z form as a geometric isomer, and R ^d1 is each independently a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, or a chlorine atom. an atom, a fluorine atom, a carboxy group, or a sulfo group. R ^d2 each independently represents a hydrogen atom, a methyl group, or a phenyl group. R ^d3 each independently represents a hydrogen atom, a methyl group, or a chlorine atom.

The compound represented by a formula (d) can be used individually or in combination of 2 or more types.

From the viewpoint of easy production of the compound represented by formula (d), R ^d1 is preferably bonded to the 6th position of the dihydroindolone ring, and R ^d3 is preferably bonded to the 4th position of the dihydroindolone ring. From the same viewpoint, R ^d1 , R ^d2 , and R ^d3 are preferably a hydrogen atom.

The compound represented by the formula (d) has EE, ZZ, and EZ isomers as geometric isomers, but any single compound of these may be used, or a mixture of these geometric isomers may be used.

The compound represented by a formula (d) can be manufactured by the method of international publication 2000/24736 and international publication 2010/081624, for example.

In order to disperse|distribute a lactam type pigment favorably in the black photosensitive resin composition, it is preferable that the average particle diameters of a lactam type pigment are 10 nm or more and 1000 nm or less.

[Perylene-based pigment]

It will not specifically limit, if it consists of a compound which has a perylene skeleton as a perylene type pigment, and is a pigment which shows black.

Specific examples of the perylene-based pigment include a perylene-based pigment represented by the following formula (d2), a perylene-based pigment represented by the following formula (d3), and a perylene-based pigment represented by the following formula (d4). As a commercial item, product names K0084 and K0086 by BASF Corporation, Pigment Black 21, 30, 31, 32, 33, 34, etc. can be used preferably as a perylene type pigment.

In formula (d2), R ^d11 and R ^d12 each independently represent an alkylene group having 1 to 3 carbon atoms, and R ^d13 and R ^d14 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, or acetyl represents the flag.

In formula (d3), R ^d15 and R ^d16 each independently represent an alkylene group having 1 or more and 7 or less carbon atoms.

In formula (d4), R ^d17 and R ^d18 are each independently a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and may contain a heteroatom of N, O, S, or P. When R ^d17 and R ^d18 are an alkyl group, the alkyl group may be linear or branched.

The compound represented by the above formula (d2), the compound represented by the formula (d3), and the compound represented by the formula (d4) are disclosed in, for example, Japanese Patent Application Laid-Open Nos. 62-1753 and 63-26784. It can be synthesized using the methods described. That is, perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines are used as raw materials, and the heating reaction is performed in water or an organic solvent. Then, the target product can be obtained by recrystallizing the obtained preparation in sulfuric acid or recrystallizing it in water, an organic solvent, or a mixed solvent thereof.

In order to disperse the perylene pigment satisfactorily in the black photosensitive resin composition and form a cured product having low transmittance to light in a wide wavelength range, the volume average particle diameter of the perylene pigment is preferably 10 nm or more and 1000 nm or less. and 10 nm or more and 500 nm or less are more preferable, and 10 nm or more and 200 nm or less are particularly preferable.

Moreover, when the volume particle diameter of a perylene type pigment is in said range, arithmetic mean roughness Ra is low and it is easy to form the hardened|cured material which has a smooth surface stably.

[Pigment (D2)]

The pigment (D2) is a pigment other than the organic black pigment (D1). That is, black pigments other than the organic black pigment (D1) and chromatic pigments correspond to the pigment (D2).

[Black pigment other than organic black pigment (D1)]

Examples of the black pigment other than the organic black pigment (D1) include carbon black, titanium oxynitride, titanium nitride, fine particles containing a silver-tin (AgSn) alloy as a main component, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, A metal oxide, such as silver, a complex oxide, a metal sulfide, a metal sulfate, or a metal carbonate, etc. are mentioned. In addition, in this specification, titanium oxide is also contained in titanium oxynitride. It is preferable that a pigment (D2) contains carbon black as black pigments other than an organic black pigment (D1).

As carbon black, although well-known carbon blacks, such as channel black, furnace black, thermal black, and lamp black, can be used, It is preferable to use channel black excellent in light-shielding property.

The carbon black may be subjected to a surface treatment selected from a coating treatment with an organic substance and a treatment for introducing an acidic group.

[Colored pigment]

As a chromatic pigment, various pigments can be used irrespective of an organic substance or an inorganic substance. As a chromatic pigment, a blue pigment, a purple pigment, a yellow pigment, an orange pigment, a green pigment, etc. are mentioned, for example.

As a specific example of a blue pigment, C.I. Pigment Blue 1 (hereinafter, "C.I. Pigment Blue" is the same, and only the numbers are described.), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64, and 66 can be heard

As a specific example of a purple pigment, C.I. Pigment Violet 1 (hereinafter, "C.I. Pigment Violet" is the same, and only the numbers are described.), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50 are mentioned.

As a specific example of a yellow pigment, C.I. Pigment Yellow 1 (hereinafter, "C.I. Pigment Yellow" is the same, and only the numbers are described.), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60 , 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119 , 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, and 185 can be heard

As a specific example of an orange pigment, C.I. Pigment Orange 1 (hereinafter, "C.I. Pigment Orange" is the same, and only the numbers are described.), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51 , 55, 59, 61, 63, 64, 71, and 73.

As a specific example of a green pigment, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37, C.I. Green pigments, such as Pigment Green 58, are mentioned.

Forms of light-shielding agents (D) such as organic black pigments (D1) and pigments (D2) used for preparation of the black photosensitive resin composition, specifically lactam pigments, perylene pigments, carbon black, titanium oxynitride and titanium nitride is not particularly limited. The light-shielding agent (D) may be used as powder, and may be used as a dispersion liquid. The light-shielding agent (D), Preferably, it is used for preparation of a black photosensitive resin composition as a dispersion liquid.

As a dispersion liquid, you may use the dispersion liquid containing 2 or more types of light-shielding agents (D). Moreover, you may use 2 or more types of dispersion liquids containing different types of light-shielding agents, respectively.

As the dispersion medium, for example, propylene glycol monomethyl ether acetate, cellosolve acetate, 3-methoxy butyl acetate, methoxy propyl acetate, 2-methoxy ethyl acetate 3-ethoxyethyl propionate, propylene glycol monomethyl ether Organic solvents, such as propionate, water, etc. can be used.

In order to make favorable the dispersibility of the dispersion|distribution in the dispersion liquid of a light-shielding agent (D), and the light-shielding agent (D) in black photosensitive resin composition, you may use a dispersing agent.

As a dispersing agent, it is preferable to use the polymer dispersing agent of a polyethyleneimine type, a urethane resin type, and an acrylic resin type.

In these, the dispersing agent of a urethane resin system is preferable at the point which solubility with respect to a developing solution is favorable and adhesion of the residue to the board|substrate, developing equipment, piping etc. after image development is hard to occur.

When using a dispersing agent, content of the dispersing agent in the black photosensitive resin composition is 5 mass % or more and 50 mass % or less with respect to content of a light-shielding agent (D), For example, 10 mass % or more and 40 mass % or less desirable.

In addition, corrosive gas resulting from the dispersant may be generated from the cured product. For this reason, it is an example of a preferable aspect that the light-shielding agent (D) is also disperse-processed without using a dispersing agent.

The viscosity of the dispersion of the light-shielding agent (D) is not particularly limited. The viscosity of the dispersion is a value measured at 25°C by a cone plate viscometer, and is preferably 3 mPa·s or more and 200 mPa·s or less.

As for the particle diameter of the light-shielding agent (D) in a dispersion liquid, 80 nm or more and 300 nm or less are preferable as a dispersion average particle diameter. The dispersion average particle diameter can be measured using a laser diffraction particle size distribution meter.

Total solid content of black photosensitive resin composition WHEREIN: Content of a light-shielding agent (D) is 25 mass % or more and 50 mass % or less. In addition, when an organic black pigment (D1) contains the lactam type pigment represented by Formula (d1), the total solid of the black photosensitive resin composition WHEREIN: Content of a light-shielding agent (D) is 30 mass % or more and 50 mass % It is preferable that they are 40 mass % or more and 50 mass % or less are more preferable.

In addition, the ratio of the organic black pigment (D1) with respect to the sum total of an organic black pigment (D1) and a pigment (D2) is 40 mass % or more and 80 mass % or less. In addition, when the organic black pigment (D1) contains the lactam pigment represented by formula (d1), the ratio of the organic black pigment (D1) to the total of the organic black pigment (D1) and the pigment (D2) is It is preferable that they are 60 mass % or more and 80 mass % or less, and it is more preferable that they are 70 mass % or more and 80 mass % or less.

An alkali-soluble resin (A), a photopolymerizable monomer (B), a photoinitiator (C), a light-shielding agent (D), and a polyfunctional thiol compound (E) to be described later, further satisfying the above range By setting it as a black photosensitive resin composition, even when a baking temperature is low, it has high solvent tolerance, and the light-shielding hardened|cured material which has a pattern shape excellent in straightness can be obtained.

<Polyfunctional thiol compound (E)>

The black photosensitive resin composition contains a polyfunctional thiol compound (E) as an essential component. Alkali-soluble resin (A), a photopolymerizable monomer (B), a photoinitiator (C), and the light-shielding agent (D) of the said specific mixing|blending, The black photosensitive resin composition containing a polyfunctional thiol compound (E) By setting it as this, even when a baking temperature is low, it has high solvent tolerance, and the light-shielding hardened|cured material which has the pattern shape excellent in straightness can be obtained.

The polyfunctional thiol compound (E) is preferably a secondary thiol.

It is preferable that the polyfunctional secondary thiol compound represented by following formula (e1) is included as a polyfunctional thiol compound (E).

(In formula (e1), R ^e1 is an alkyl group, ^Re2 is a trivalent chain aliphatic hydrocarbon group, ^Re3 is an n-valent aliphatic hydrocarbon group which may contain a hetero atom, and n is an integer of 2 or more and 4 or less. )

In formula (e1), the alkyl group as R ^e1 may be linear or branched. 1 or more and 10 or less are preferable, and, as for the number of carbon atoms of ^Re1 , 1 or more and 4 or less are more preferable. Preferable examples of R ^e1 include a methyl group, an ethyl group and a propyl group.

In the formula (e1), the trivalent chain aliphatic hydrocarbon group as R ^e2 may be linear or branched. 1 or more and 10 or less are preferable, and, as for the number of carbon atoms of ^Re2 , 1 or more and 4 or less are more preferable. Preferred examples of ^Re2 include groups in which two hydrogen atoms are removed from the alkyl group of a methyl group, an ethyl group, a propyl group, or a butyl group.

In formula (e1), the n-valent aliphatic hydrocarbon group which may contain a hetero atom as R ^e3 may be linear or branched. 1 or more and 10 or less are preferable, and, as for the carbon atom number of ^Re3 , 3 or more and 8 or less are more preferable. Preferred examples of ^Re3 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a group obtained by removing 1, 2 or 3 hydrogen atoms from a heptyl group.

A nitrogen atom, an oxygen atom, and a sulfur atom are mentioned as a hetero atom which R ^<e3> may contain.

The following compound is mentioned as a specific example of the polyfunctional secondary thiol compound represented by Formula (e1).

It is preferable that they are 0.1 mass % or more and 5.0 mass % or less, and, as for content of the polyfunctional thiol compound (E) in total solid of the black photosensitive resin composition, it is more preferable that they are 1.0 mass % or more and 3.0 mass % or less.

<Polyfunctional epoxy compound (F)>

The black photosensitive resin composition may contain the polyfunctional epoxy compound (F). When the black photosensitive resin composition further contains the polyfunctional epoxy compound (F), good curing at a low temperature of the black photosensitive resin composition is easier.

In this specification, a polyfunctional epoxy compound (F) is an epoxy compound which has two or more epoxy groups in 1 molecule.

As a polyfunctional epoxy compound (F), the various polyfunctional epoxy compound conventionally mix|blended with the black photosensitive resin composition can be used. Moreover, you may contain the polyfunctional epoxy compound (F) and the hardening|curing agent according to the kind of polyfunctional epoxy compound (F) as needed. When using a hardening|curing agent, it is preferable to use the latent hardening|curing agent which causes the action|action as a hardening|curing agent by baking from the point of long-term stability of the black photosensitive resin composition.

A polyfunctional epoxy compound (F) is a compound whose molecular weight (Mw) is 2000 or less, Preferably it is a 1500 or less compound. It is preferable that a polyfunctional epoxy compound is not a polymer or an oligomer, but is a compound of a monomer, or a compound which does not have two or more repeating units.

As an example of a polyfunctional epoxy compound (F), Bifunctional epoxy, such as a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S type epoxy compound, a bisphenol AD type epoxy compound, a naphthalene type epoxy compound, and a biphenyl type epoxy compound compound; 9,9-bis[4-(glycidyloxy)phenyl]-9H-fluorene, 9,9-bis[4-[2-(glycidyloxy)ethoxy]phenyl]-9H-fluorene; 9,9-bis[4-[2-(glycidyloxy)ethyl]phenyl]-9H-fluorene, 9,9-bis[4-(glycidyloxy)-3-methylphenyl]-9H-flu Orene, 9,9-bis[4-(glycidyloxy)-3,5-dimethylphenyl]-9H-fluorene, and 9,9-bis(6-glycidyloxynaphthalen-2-yl)- Epoxy group-containing fluorene compounds, such as 9H-fluorene; glycidylamine-type epoxy compounds such as tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidylmethxylenediamine, and tetraglycidylbisaminomethylcyclohexane; Phloroglycinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[ 4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane, and 1,3-bis[4-[1-[4-(2,3-epoxypropoxy) trifunctional epoxy such as epoxy) phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol compound; tetrafunctional epoxy compounds such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidoxy biphenyl;

As another example of a polyfunctional epoxy compound (F), the polyfunctional alicyclic epoxy compound which has an alicyclic epoxy group is mentioned. Specific examples of such an alicyclic epoxy compound include 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane metadioxane, bis(3,4-epoxycyclohexylmethyl)adi Pate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, ε -Caprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, trimethylcaprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), di(3, ethylene glycol) 4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), and a polyfunctional epoxy compound having a tricyclodecene oxide group, the following formulas (F1-1) to (F1-5) The compound shown is mentioned.

These alicyclic epoxy compounds may be used individually or may be used in mixture of 2 or more types.

(In formula (F1-1), Z represents a single bond or a linking group (a divalent group having one or more atoms). R ^F1 to R ^F18 are each independently a group consisting of a hydrogen atom, a halogen atom, and an organic group It is a group selected from.)

Examples of the linking group Z include a divalent hydrocarbon group, -O-, -O-CO-, -S-, -SO-, -SO ₂ -, -CBr ₂ -, -C(CBr ₃ ) ₂ -, and a divalent group selected from the group consisting of -C(CF ₃ ) ₂ -, and -R ^F19 -O-CO-, and a group in which a plurality of these groups are bonded.

As a divalent hydrocarbon group which is the linking group Z, a C1-C18 linear or branched alkylene group, a divalent alicyclic hydrocarbon group, etc. are mentioned, for example. As a C1-C18 linear or branched alkylene group, a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, trimethylene group, etc. are mentioned, for example. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, and 1,3-cyclohexylene group. cycloalkylene groups (including a cycloalkylidene group), such as group, 1, 4- cyclohexylene group, and a cyclohexylidene group, etc. are mentioned.

R ^F19 is an alkylene group having 1 or more and 8 or less carbon atoms, and is preferably a methylene group or an ethylene group.

(In formula (F1-2), R ^F1 to R ^F12 are a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.)

(In formula (F1-3), R ^F1 to R ^F10 are a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R ^F2 and R ^F8 may be bonded to each other.)

(In formula (F1-4), R ^F1 to R ^F12 are a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R ^F2 and R ^F10 may be bonded to each other.)

(In formula (F1-5), R ^F1 to R ^F12 are a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.)

In formulas (F1-1) to (F1-5), when R ^F1 to R ^F18 are an organic group, the organic group is not particularly limited as long as the object of the present invention is not impaired, and even if it is a hydrocarbon group, a carbon atom and a halogen atom It may be a group consisting of, or a group containing a hetero atom such as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom together with a carbon atom and a hydrogen atom. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.

The organic group is preferably a hydrocarbon group, a group consisting of a carbon atom, a hydrogen atom and an oxygen atom, a halogenated hydrocarbon group, a group consisting of a carbon atom, an oxygen atom and a halogen atom, and a group consisting of a carbon atom, a hydrogen atom, an oxygen atom, and a halogen atom. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group including an aromatic skeleton and an aliphatic skeleton. 1 or more and 20 or less are preferable, as for the carbon atom number of an organic group, 1 or more and 10 or less are more preferable, 1 or more and 5 or less are especially preferable.

Specific examples of the hydrocarbon group include a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n- Heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexa chain alkyl groups such as decyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group; chain alkenyl groups such as a vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n-butenyl group, 2-n-butenyl group, and 3-n-butenyl group; cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group; Phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, α-naphthyl group, β-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl group, biphenyl-2-yl group, anthryl group an aryl group such as a group and a phenanthryl group; and aralkyl groups such as benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, α-naphthylethyl group, and β-naphthylethyl group.

Specific examples of the halogenated hydrocarbon group include a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, 2,2, 2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, and perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, purple halogenated chain alkyl groups such as a luoronyl group and a perfluorodecyl group; 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group, and 4-bro halogenated cycloalkyl groups such as a mocyclohexyl group; 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, halogenated aryl groups such as 3,5-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-fluorophenyl group, 3-fluorophenyl group and 4-fluorophenyl group; 2-chlorophenylmethyl group, 3-chlorophenylmethyl group, 4-chlorophenylmethyl group, 2-bromophenylmethyl group, 3-bromophenylmethyl group, 4-bromophenylmethyl group, 2-fluorophenylmethyl group, 3-fluoro halogenated aralkyl groups such as a phenylmethyl group and a 4-fluorophenylmethyl group.

Specific examples of the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom include hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxy-n-propyl group, and 4-hydroxy-n-butyl group chain alkyl group; halogenated cycloalkyl groups such as a 2-hydroxycyclohexyl group, a 3-hydroxycyclohexyl group, and a 4-hydroxycyclohexyl group; 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2,3-dihydroxyphenyl group, 2,4-dihydroxyphenyl group, 2,5-dihydroxyphenyl group, 2,6-di hydroxyaryl groups such as a hydroxyphenyl group, a 3,4-dihydroxyphenyl group, and a 3,5-dihydroxyphenyl group; hydroxyaralkyl groups such as a 2-hydroxyphenylmethyl group, a 3-hydroxyphenylmethyl group, and a 4-hydroxyphenylmethyl group; Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group Group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-tridecyloxy group, n-tetradecyl group chain alkoxy groups such as siloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, and n-icosyloxy group; vinyloxy group, 1-propenyloxy group, 2-n-propenyloxy group (aryloxy group), 1-n-butenyloxy group, 2-n-butenyloxy group, 3-n-butenyloxy group, etc. a chain alkenyloxy group; Phenoxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group, α-naphthyloxy group, β-naphthyloxy group, biphenyl-4-yloxy group, biphenyl-3-yloxy group, bi aryloxy groups such as phenyl-2-yloxy group, anthryloxy group, and phenanthryloxy group; aralkyloxy groups such as benzyloxy group, phenethyloxy group, α-naphthylmethyloxy group, β-naphthylmethyloxy group, α-naphthylethyloxy group, and β-naphthylethyloxy group; Methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 3-methoxy-n-propyl group, 3-ethoxy-n -propyl group, 3-n-propoxy-n-propyl group, 4-methoxy-n-butyl group, 4-ethoxy-n-butyl group, 4-n-propoxy-n-butyl group, etc. alkoxyalkyl group; Methoxymethoxy group, ethoxymethoxy group, n-propoxymethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propoxyethoxy group, 3-methoxy-n- propoxy group, 3-ethoxy-n-propoxy group, 3-n-propoxy-n-propoxy group, 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, and alkoxyalkoxy groups such as 4-n-propoxy-n-butyloxy group; alkoxyaryl groups such as a 2-methoxyphenyl group, a 3-methoxyphenyl group, and a 4-methoxyphenyl group; alkoxyaryloxy groups such as a 2-methoxyphenoxy group, a 3-methoxyphenoxy group, and a 4-methoxyphenoxy group; aliphatic acyl groups such as a formyl group, an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, and a decanoyl group; aromatic acyl groups such as a benzoyl group, an α-naphtholyl group, and a β-naphtholyl group; Methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, n-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexylcarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, and chain alkyloxycarbonyl groups such as n-decyloxycarbonyl group; aryloxycarbonyl groups such as phenoxycarbonyl group, α-naphthoxycarbonyl group, and β-naphthoxycarbonyl group; aliphatic acyloxy groups such as formyloxy group, acetyloxy group, propionyloxy group, butanoyloxy group, pentanoyloxy group, hexanoyloxy group, heptanoyloxy, octanoyloxy, nonanoyloxy, and decanoyloxy; aromatic acyloxy groups such as benzoyloxy group, α-naphthoyloxy group, and β-naphthoyloxy group.

R ^F1 to R ^F18 are each independently preferably a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms, particularly mechanical properties Since it is easy to form this excellent hardened|cured material, it is more preferable that R ^F1 -R ^F18 are all hydrogen atoms.

In Formulas (F1-2) to (F1-5), R ^F1 to R ^F12 are the same as R ^F1 to R ^F12 in Formula (F1-1). In formulas (F1-2) and (F1-4), as a divalent group formed when R ^F2 and R ^F10 are bonded to each other, for example, -CH ₂ -, -C(CH ₃ ) ₂ - can be mentioned. Examples of the divalent group formed when R ^F2 and R ^F8 are bonded to each other in the formula (F1-3) include -CH ₂ - and -C(CH ₃ ) ₂ -.

Among the alicyclic epoxy compounds represented by formula (F1-1), specific examples of suitable compounds include alicyclic epoxy compounds represented by the following formulas (F1-1a), (F1-1b), and (F1-1c); 2,2-bis(3,4-epoxycyclohexan-1-yl)propane [=2,2-bis(3,4-epoxycyclohexyl)propane] etc. are mentioned.

Among the alicyclic epoxy compounds represented by formula (F1-2), specific examples of suitable compounds include bicyclononadiene diepoxide and dicyclononadiene diepoxide represented by the following formula (F1-2a). .

S-spiro[3-oxatricyclo[3.2.1.0 ^2,4 ]octane-6,2'-oxirane] etc. are mentioned as a specific example of a suitable compound among the alicyclic epoxy compounds represented by Formula (F1-3). can

Specific examples of suitable compounds among the alicyclic epoxy compounds represented by formula (F1-4) include 4-vinylcyclohexene dioxide, dipentene dioxide, limonene dioxide, and 1-methyl-4-(3-methyloxirane- 2-yl)-7-oxabicyclo[4.1.0]heptane and the like.

Among the alicyclic epoxy compounds represented by Formula (E1-5), 1,2,5,6-diepoxycyclooctane etc. are mentioned as a specific example of a suitable compound.

Furthermore, the compound represented by a following formula (F-1) can be used suitably as a polyfunctional epoxy compound (F).

(In Formula (F-1), X ^f1 , X ^f2 , and X ^f3 are each independently a hydrogen atom or an organic group which may contain an epoxy group, and an epoxy group which X ^f1 , X ^f2 , and X ^f3 have The total number of is greater than or equal to 2.),

As the compound represented by the formula (F-1), a compound represented by the following formula (F1-6) is preferable.

(In formula (F1-6), R ^f20 to R ^f22 are linear, branched or cyclic alkylene groups, allylene groups, -O-, -C(=O)-, -NH-, and combinations thereof. E ¹ to E ³ are epoxy group, oxetanyl group, ethylenically unsaturated group, alkoxysilyl group, isocyanate group, blocked isocyanate group, thiol group, carboxyl group, hydroxyl group and succinic anhydride It is at least one kind of substituent or hydrogen atom selected from the group consisting of a group, provided that at least two of E ¹ to E ³ are groups having an epoxy group.)

In formula (F1-6), at least two of the groups represented by R ^f20 and E ¹ , R ^f21 and E ² , and R ^f22 and E ³ are, for example, groups each represented by the following formula (F1-6a) It is preferable, and it is more preferable that all are groups respectively represented by a following formula (F1-6a). It is preferable that the groups represented by several formula (F1-6a) couple|bonded with one compound are the same group.

-LC ^a (F1-6a)

(In formula (F1-6a), L is a linear, branched or cyclic alkylene group, an allylene group, -O-, -C(=O)-, -NH-, and a group consisting of combinations thereof, and C ^a is an epoxy group. In formula (F1-6a), L and C ^a may combine to form a cyclic structure.)

In the formula (F1-6a), the linear, branched or cyclic alkylene group as L is preferably an alkylene group having 1 to 10 carbon atoms, and the allylene group as L is 5 or more to 10 carbon atoms. The following allylene groups are preferable. In the formula (F1-6a), L is a linear alkylene group having 1 to 3 carbon atoms, a phenylene group, -O-, -C(=O)-, -NH-, and a group consisting of these combinations Preferably, at least one of a linear C1-C3 alkylene group such as a methylene group and a phenylene group, or at least one of -O-, -C(=O)- and NH- Groups in combination with species are preferred.

In the formula (F1-6a), when L and C ^a are bonded to form a cyclic structure, for example, a branched alkylene group and an epoxy group are bonded to form a cyclic structure (structure having an alicyclic epoxy group) When forming , an organic group represented by the following formula (F1-6b) or (F1-6c) is exemplified.

(In formula (F1-6b), R ^f23 is a hydrogen atom or a methyl group.)

Hereinafter, although the example of the epoxy compound which has an oxiranyl group or an alicyclic epoxy group is shown as an example of a compound represented by Formula (F1-6), it is not limited to these.

Moreover, as a compound which can be used suitably as a polyfunctional epoxy compound (F), the siloxane compound which has two or more epoxy groups in a molecule|numerator (Hereinafter, it writes also simply as a "siloxane compound.") is mentioned.

A siloxane compound is a compound which has a siloxane skeleton comprised by the siloxane bond (Si-O-Si), and two or more glycidyl groups or alicyclic epoxy groups in a molecule|numerator. Incidentally, the alicyclic epoxy group is an alicyclic group in which two carbon atoms as adjacent cyclic atoms in the alicyclic group are bonded through an oxygen atom. That is, the alicyclic epoxy group has an epoxy group containing a 3-membered ring composed of two carbon atoms and one oxygen atom on an aliphatic ring.

Examples of the siloxane skeleton in the siloxane compound include cyclic siloxane skeleton and cargo-type or ladder-type polysilsesquinoxane skeleton.

As the siloxane compound, a compound having a cyclic siloxane skeleton represented by the following formula (F1-7) (hereinafter sometimes referred to as “cyclic siloxane”) is preferable.

In formula ( ^F1-7 ), R f24 and R ^f25 represent a monovalent group or an alkyl group containing an epoxy group. However, in the compound represented by the formula (F1-7), at least two of x1 R ^{f24 and x1 R f25 are} monovalent groups containing an epoxy group. In addition, x1 in Formula (F1-7) represents an integer of 3 or more. In addition, R ^{f24 and R f25 in} the compound represented by Formula (F1-7) may be same or different. In addition, a plurality of R ^f24 may be the same or different. A plurality of R ^{f25 may} also be the same or different.

The glycidyl ether group represented by -DOR ^f26 [D represents an alkylene group, R ^f26 represents a glycidyl group] is preferable as the group containing one atom containing the epoxy group. Examples of the D (alkylene group) include a linear or branched alkylene group having 1 to 18 carbon atoms, such as a methylene group, a methyl methylene group, a dimethyl methylene group, a dimethylene group, and a trimethylene group. can

Moreover, the alicyclic epoxy group containing group represented by -DR ^f27 is also preferable. R ^f27 is an epoxycycloalkyl group. D is an alkylene group, as described above. A preferable example of the alkylene group as D is also as described above. As the epoxycycloalkyl group as R ^f27 , a 2,3-epoxycyclopentyl group, a 3,4-epoxycyclohexyl group, and a 2,3-epoxycyclohexyl group are preferable. The group represented by -DR ^f27 is preferably a 2-(3,4-epoxycyclohexyl)ethyl group.

Preferred examples of the alkyl group as R ^{f24 and R f25 include} , for example, a methyl group, an ethyl group, a propyl group, and an isopropyl group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms, particularly preferably is a linear or branched alkyl group having 1 or more and 3 or less carbon atoms).

x1 in the formula (F1-7) represents an integer of 3 or more, and among these, an integer of 3 or more and 6 or less is preferable from the viewpoint of excellent crosslinking reactivity when forming a cured product.

The number of epoxy groups that the siloxane compound has in the molecule is two or more, and from the viewpoint of excellent crosslinking reactivity when forming a cured product, 2 or more and 6 or less are preferable, and particularly preferably 2 or more and 4 or less.

In addition to the siloxane compound represented by formula (F1-7), the black photosensitive resin composition is an alicyclic epoxy group containing cyclic siloxane, the alicyclic epoxy group containing silicone resin of Unexamined-Japanese-Patent No. 2008-248169, and Unexamined-Japanese-Patent No. 2008-19422 You may contain the compound which has siloxane frame|skeleton, such as organopolysilsesquinoxane resin which has at least two epoxy functional groups in 1 molecule of description.

As a siloxane compound, the cyclic siloxane etc. which have 2 or more epoxy groups in a molecule|numerator which are more specifically represented by a following formula are mentioned. In addition, as a siloxane compound, "X-40-2670", "X-40-2701", "X-40-2728", "X-40-2738", "X-40-2740" are, for example, a brand name, for example. (above, the product made by Shin-Etsu Chemical Co., Ltd.) etc. can be used.

1 mass % or more and 15 mass % or less are preferable in the total solid of the black photosensitive resin composition, and, as for content of the polyfunctional epoxy compound (F) in the black photosensitive resin composition, 1.5 mass % or more and 12 mass % or less are more preferable. and 2 mass % or more and 10 mass % or less are especially preferable.

<(S) organic solvent>

It is preferable that the black photosensitive resin composition contains the (S) organic solvent for dilution. (S) Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol. monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl (poly)alkylene glycol monoalkyl ethers such as ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; (poly)alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-hydroxy-2-methylpropionate ethyl, 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3-ethoxypropionate methyl, 3-ethoxypropionate ethyl, ethoxypropionate ethyl, ethyl hydroxyacetate, 2 -hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, Isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, other esters such as n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; Amides, such as N-methylpyrrolidone, N,N- dimethylformamide, and N,N- dimethylacetamide, etc. are mentioned.

Among these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, other ethers, lactic acid alkyl esters, and other esters described above are preferable. One other ether, the other esters mentioned above, is more preferable. These solvents can be used individually or in combination of 2 or more types.

(S) The quantity used as solid content concentration of 1 mass % or more and 50 mass % or less of the black photosensitive resin composition is preferable, and, as for content of the organic solvent, the quantity used as 5 mass % or more and 40 mass % or less is more preferable.

<Other ingredients>

The black photosensitive resin composition may contain various additives as needed. As an additive, adhesion promoters, such as a sensitizer, a hardening accelerator, a filler, a dispersing agent, a silane coupling agent, antioxidant, aggregation inhibitor, a thermal-polymerization inhibitor, an antifoamer, surfactant, etc. are mentioned.

<The preparation method of the black photosensitive resin composition>

The black photosensitive resin composition is prepared by mixing said each component with a stirrer. In addition, you may filter using the membrane filter etc. which can pass a light-shielding agent (D) so that the prepared black photosensitive resin composition may become a uniform thing.

«Production method of patterned cured product, patterned cured product and black matrix»

By using the black photosensitive resin composition demonstrated above, the patterned hardened|cured material can be manufactured.

The patterned cured product typically comprises:

A step of forming a coating film by applying the above-described black photosensitive resin composition;

A process of exposing the coating film positionally and selectively;

A step of developing the coating film after exposure;

The coating film after image development is manufactured by the method including the process of heating.

Hereinafter, each process is demonstrated. The process of apply|coating the black photosensitive resin composition and forming a coating film is written down as a "coating film formation process." A position-selective exposure of a coating film is described as an "exposure process". The process of developing the coating film after exposure is described as a "development process". The process of heating the coating film after image development is described as a "heating process".

<coating film forming process>

In the coating film forming step, the black photosensitive resin composition is applied onto a substrate on which a pattern is to be formed, a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater. Apply using an applicator.

The type of the substrate is not particularly limited, and various substrates used in optical devices such as a liquid crystal display device, an organic EL display device, and an organic TFT array can be suitably used. As the substrate, for example, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), polyester film, poly Polymer substrates such as carbonate films and polyimide films, TFT array substrates, PDP electrode plates, glass and transparent plastic substrates, conductive substrates such as ITO and metal, insulating substrates, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon Semiconductor substrates, such as these, etc. are mentioned. Further, for example, in the case of forming a laminated structure on a substrate, any layer that becomes an underlying structure already formed on the substrate is included in the concept as a substrate to which the black photosensitive resin composition is applied. In addition, the shape of a base material is not specifically limited, either, A plate shape may be sufficient, and roll shape may be sufficient. The substrate may have irregularities on the surface by, for example, various patterns. In addition, as said base material, a light transmissive or non-light transmissive base material can be selected.

After apply|coating the photosensitive resin composition, a solvent is removed by drying as needed, and a coating film is formed.

Incidentally, drying is preferably performed at a low temperature of, for example, 100° C. or less, preferably 80° C. or less, so that thermosetting of the photosensitive resin composition does not proceed excessively. Drying may be performed under reduced pressure atmosphere as needed.

The film thickness of the coating film is not particularly limited. As thickness of a coating film, 0.05 micrometer or more is preferable and 1 micrometer or more is more preferable. Although there is no upper limit in particular of the thickness of a coating film, For example, 50 micrometers or less may be sufficient and 20 micrometers or less may be sufficient. 10 micrometers or less are preferable, as for the thickness of a coating film, 5 micrometers or less are more preferable, and 2 micrometers or less are still more preferable.

<Exposure process>

In an exposure process, the coating film formed in the coating film formation process is selectively exposed. In the exposure step, the coating film is subjected to exposure by position-selectively irradiating active energy rays such as i-line (365 nm) and excimer laser light according to the shape of a desired pattern. The position-selective exposure is performed, for example, through a mask having a shape corresponding to the pattern shape of the cured product.

For exposure, a light source emitting 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 also changes with the composition of the black photosensitive resin composition, for example, about 10 mJ/cm ² or more and 600 mJ/cm ² or less is preferable.

<Development process>

The developing process WHEREIN: The unexposed part of the coating film exposed by the exposure process is developed with developing solutions, such as an alkali 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 monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

<Heating process>

In a heating process, the coating film after image development is heated (baked). Thereby, the developed coating film can heat-harden and can form the patterned hardened|cured material.

Bake temperature can be 120 degrees C or less, for example, 100 degrees C or less, Furthermore, it can be 95 degrees C or less. Although the minimum of a baking temperature is not specifically limited as long as hardening of a coating film advances favorably, 80 degreeC or more is preferable. Bake time is not specifically limited, It is performed until hardening of a coating film fully advances. Typically, 15 to 60 minutes of baking time are preferable.

Thus, even when a baking temperature is low, it has high solvent tolerance, and the light-shielding patterned hardened|cured material which has the pattern shape excellent in straightness can be formed. For this reason, the patterned hardened|cured material formed using the above-mentioned black photosensitive resin composition is a device in which a material with particularly low heat resistance is used, for example, an image display device in which a material with particularly low heat resistance such as an organic EL display is used. WHEREIN: It is used suitably as light shielding materials, such as a black matrix.

[Example]

Hereinafter, although an Example is shown and this invention is further specifically demonstrated, the scope of the present invention is not limited to these Examples.

[Examples 1 to 7 and Comparative Examples 1 to 4]

In an Example and a comparative example, resin A1 which is alkali-soluble cardo resin was used as alkali-soluble resin (A) ((A) component). Resin A1 is resin obtained by the following preparation example 1.

(Preparation Example 1)

First, in a 500 ml four-neck flask, 235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethyl ammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid were put, and this It was dissolved by heating at 90-100 ° C while blowing air at a rate of 25 ml/min. Next, the solution was gradually heated while still in a cloudy state, and heated to 120° C. to completely dissolve it. At this time, although the solution gradually became transparent and viscous, stirring was continued as it was. During this time, the acid value was measured and heating and stirring was continued until it became less than 1.0 mgKOH/g. It took 12 hours for the acid value to reach the target. And it cooled to room temperature, and obtained the bisphenol fluorene type epoxy acrylate which is colorless and transparent and is represented by the following formula of solid state.

Next, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the bisphenol fluorene type epoxy acrylate obtained in this way and dissolved, and then 80.5 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 1 g of tetraethyl ammonium bromide were mixed, and the temperature was gradually raised to react at 110 to 115° C. for 4 hours. After confirming disappearance of an acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, it was made to react at 90 degreeC for 6 hours, and resin A1 was obtained. The disappearance of the acid anhydride group was confirmed by IR spectrum.

In Examples and Comparative Examples, the following B1 and B2 were used as the photopolymerizable monomer (B) (component (B)). Incidentally, B2 is high-purity glycerin diacrylate and glycerin triacrylate.

B1: dipentaerythritol hexaacrylate (DPHA)

B2: glycerin triacrylate (polyfunctional (meth)acrylate represented by formula (b1) in which R ^b1 is an acryloyl group and R ^b2 is a hydrogen atom, Toagosei Co., Ltd. product name: Aronix M930)

In Examples and Comparative Examples, as the photopolymerization initiator (C) (component (C)), compounds C1 of the following formula, and C2: ethanone-1-[9-ethyl-6-(2-methylbenzoyl) -9H-carbazol-3-yl]-1-(O-acetyloxime) (Irgacure OXE02, manufactured by BASF Japan) was used.

In Examples and Comparative Examples, as the light-shielding agent (D) (component (D)), the following D1-1 and D1-2 as the organic black pigment (D1), and pigments other than the organic black pigment (D1) ( D2-1 as D2) was used.

D1-1: Lactam-based pigment of the following structure

D1-2: Perylene-based pigment of the following structure

D2-1: carbon black (volume average particle diameter 150 nm or less)

In Examples and Comparative Examples, the following E1 and E2 were used as the polyfunctional thiol (E) (component (E)).

E1: Trimethylolpropane tris(3-mercaptobutylate) (the following structure. Showa Denko Co., Ltd. product name: Karenz MT TPMB)

E2: pentaerythritol tetrakis (3-mercaptobutylate (the following structure. Showa Denko Co., Ltd. product name: Karenz MT PE1)

In Examples and Comparative Examples, the compound F1 of the following formula was used as the polyfunctional epoxy compound (F) (component (F)).

Examples 1-7 and the black photosensitive resin composition of Comparative Examples 1-4 were prepared as follows.

A black dispersion using a urethane-based resin dispersant in an amount of 30 mass % with respect to the component (D) and (D) component of the kind described in Table 1 was separately prepared, and the black dispersion and the kind (A) of the kind described in Table 1 In the black photosensitive resin composition obtained using the component, (B) component, (C) component, (E) component, and (F) component, the mass ratio of the solvent is 20 3-methoxybutyl acetate The black color of Examples 1 to 7 and Comparative Examples 1 to 4 was uniformly dissolved and dispersed so that the mass% and 80 mass% of propylene glycol monomethyl ether acetate, the solid content concentration including the urethane resin dispersant was 15 mass%. The photosensitive resin composition was prepared. In addition, the black photosensitive resin composition of each prepared example WHEREIN: The mass part of each component is as described in Table 1.

Using the black photosensitive resin composition of each obtained Example and a comparative example, the following method evaluated OD value, solvent tolerance, and the straightness of a pattern. The results are shown in Table 2.

[Evaluation of OD value]

After apply|coating a black photosensitive composition on a 10 cm ² glass substrate (Dow Corning make, Eagle XG, the same hereinafter), it dried at 80 degreeC for 120 second. Then, the coating film was irradiated with i-line (365 nm) at an exposure dose of 60 mJ/cm ² . And baking was performed at 90 degreeC for 30 minute(s) on a hot plate. The film thickness of the formed film (cured product) was 0.8 µm, 1.0 µm, and 1.2 µm. About this film (hardened|cured material), the OD value in each film thickness was measured using D200-II (made by Macbeth), and the OD value per 1 micrometer was computed from the slope of a linear approximation formula.

[Evaluation of solvent resistance]

The black photosensitive compositions of Examples and Comparative Examples were applied on a 10 cm ² glass substrate using a spin coater, and prebaked at 80° C. for 120 seconds to form a coating film. Next, using a proximity exposure apparatus (product name: TME-150RTO, manufactured by Topcon Co., Ltd.), the exposure gap is 50 µm, and the line width is 20 µm, the space width is 20 µm, and a line-and-space pattern is applied through the formed negative mask. The film was irradiated with i-rays (365 nm). The exposure amount was 100 mJ/cm ² . The coated film after exposure was developed with a 0.04 mass % KOH aqueous solution at 26°C for 50 seconds, and then heated (baked) at 90°C for 30 minutes to form a line-and-space pattern (patterned cured product) having a thickness of 1.5 µm.

The value of T2/T1 when T1 is the thickness of the formed patterned cured product and T2 is the thickness after immersing the patterned cured product in propylene glycol monomethyl ether acetate (PGMEA) for 100 seconds, the value of T2/T1 is 0.95 The case of 1 or less was made into (circle), the case of 0.90 or more and less than 0.95 as (circle), and the case of less than 0.90 was made into x, and solvent resistance was evaluated. Write the results in Table 1.

[Evaluation of straightness of pattern]

The patterned hardened|cured material formed by carrying out similarly to [evaluation of solvent resistance] was observed with the optical microscope, and the straightness of a pattern was evaluated. As for the straightness of the pattern, the case where there was no wobble at the edge of the line was evaluated as (circle), and the case where there was wobble was evaluated as x.

According to Examples 1-7, a photopolymerizable monomer (B), a photoinitiator (C), a light-shielding agent (D), and a polyfunctional thiol compound (E) are included, and the light-shielding agent (D) is a specific organic black pigment ( D1) and a pigment (D2) other than the organic black pigment (D1), the content of the light-shielding agent (D) in the total solid content is 25 mass% or more and 50 mass% or less, the organic black pigment (D1) and the pigment The black photosensitive resin composition in which the ratio of the organic black pigment (D1) to the total of (D2) is 40 mass % or more and 80 mass % or less It turns out that the light-shielding hardened|cured material which has a pattern shape is provided. Especially, Example 4 containing much content of the lactam type pigment represented by Formula (d1), Example 5 containing a perylene type pigment, and Example 6 containing polyfunctional (meth)acrylate represented by Formula (b1) Silver and solvent resistance were particularly high.

On the other hand, according to Comparative Examples 1 to 4, when a black photosensitive composition not containing the polyfunctional thiol compound (E) or a black photosensitive composition not containing a specific organic black pigment (D1) in a specific compounding amount is used, high It turns out that it is difficult to form the hardened|cured material which makes the pattern shape which is excellent in solvent resistance and straightness compatible.

Claims (10)

A black photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photoinitiator (C), a light-shielding agent (D), and a polyfunctional thiol compound (E)
The light-shielding agent (D) consists of an organic black pigment (D1) and a pigment (D2) other than the organic black pigment (D1),
The organic black pigment (D1) has the following formula (d1):
[Formula 1]

(In the formula (d1), X ^d represents a double bond, and each is independently an E or Z form as a geometric isomer, and R ^d1 is each independently a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, Represent chlorine atom, fluorine atom, carboxyl group or sulfo ^{group.R d2} each independently represent hydrogen atom, methyl group or phenyl ^{group.R d3} each independently represent hydrogen atom, methyl group or chlorine atom. .)
At least one selected from lactam-based pigments and perylene-based pigments represented by
Content of the said light-shielding agent (D) in the total solid of the said black photosensitive resin composition is 25 mass % or more and 50 mass % or less,
The black photosensitive resin composition in which the ratio of the said organic black pigment (D1) with respect to the sum total of the said organic black pigment (D1) and the said pigment (D2) is 40 mass % or more and 80 mass % or less. The method according to claim 1,
The black photosensitive resin composition in which the said pigment (D2) contains at least 1 sort(s) chosen from carbon black, titanium oxynitride, titanium nitride, a blue pigment, a purple pigment, a yellow pigment, an orange pigment, and a green pigment. The method according to claim 1,
The photopolymerization initiator (C) has the following formula (c2):
[Formula 2]

(in formula (c2), R ^c1 is a group represented by the following formula (c3), (c4), or (c5),
n1 is 0 or 1,
R ^c2 is a monovalent organic group,
R ^c3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.)
[Formula 3]

(In formula (c3), R ^c4 and R ^c5 are each independently a monovalent organic group,
n2 is an integer of 0 or more and 3 or less,
When n2 is 2 or 3, a plurality of R ^c5 may be the same or different, and a plurality of R ^c5 may be bonded to each other to form a ring.
* is a bonding hand.)
[Formula 4]

(in formula (c4), R ^c6 and R ^c7 are each independently a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom,
R ^c6 and R ^c7 may combine with each other to form a ring,
R ^c7 and the benzene ring in the fluorene skeleton may combine with each other to form a ring,
R ^c8 is a nitro group or a monovalent organic group,
n3 is an integer of 0 or more and 4 or less,
* is a bonding hand.)
[Formula 5]

(in formula (c5), R ^c9 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group;
A is S or O,
n4 is an integer of 0 or more and 4 or less,
* is a bonding hand.)
A black photosensitive resin composition comprising a photoinitiator represented by The method according to claim 1,
The photopolymerizable monomer (B) has the following formula (b1):
[Formula 6]

(In formula (b1), R ^b1 is a hydrogen atom or a (meth)acryloyl group, and R ^b2 is each independently a hydrogen atom or a methyl group.)
A black photosensitive resin composition comprising a polyfunctional (meth)acrylate represented by The method according to claim 1,
The polyfunctional thiol compound (E) has the following formula (e1):
[Formula 7]

(In formula (e1), R ^e1 is an alkyl group, ^Re2 is a trivalent chain aliphatic hydrocarbon group, ^Re3 is an n-valent aliphatic hydrocarbon group which may contain a hetero atom, and n is an integer of 2 or more and 4 or less. )
A black photosensitive resin composition comprising a polyfunctional secondary thiol compound represented by The method according to claim 1,
Furthermore, the black photosensitive resin composition containing a polyfunctional epoxy compound (F). A process of forming a coating film by applying the black photosensitive resin composition of any one of claims 1 to 6;
a step of positionally selectively exposing the coating film;
a step of developing the coating film after exposure;
The manufacturing method of the patterned hardened|cured material including the process of heating the said coating film after image development. 8. The method of claim 7,
The heating process is performed at a temperature of 100° C. or less, a method for producing a patterned cured product. The patterned hardened|cured material which consists of a hardened|cured material of the black photosensitive resin composition of any one of Claims 1-6. The black matrix which consists of hardened|cured material of the black photosensitive resin composition of any one of Claims 1-6.