JP6706453B2 - Negative photosensitive resin composition, cured product and laminate - Google Patents

Description

The present invention relates to a negative photosensitive resin composition, a cured product and a laminate.

Photosensitive resin compositions that can be easily cured in a short time by applying light energy are used in various fields such as insulating materials, adhesives, coating agents and sealants. In particular, for use as a permanent film of a liquid crystal display or the like, there is a demand for a photosensitive resin composition which is excellent in transparency and heat resistance and can be directly patterned by photolithography.

Examples of components of such a photosensitive resin composition include polysiloxane compounds. It is known that polysiloxane compounds have high transparency and heat resistance. Examples of the technique using the polysiloxane-based compound include the techniques described in Patent Documents 1 and 2.

Patent Document 1 has at least one photopolymerizable functional group in one molecule, and has at least one selected from the group consisting of a specific structure, a phenolic hydroxyl group, and a carboxyl group in the same molecule. A curable composition containing the polysiloxane compound is described.

Patent Document 2 contains (A) a polyoxyalkylene polymer having a reactive silicon group having a specific structure in the molecule, (B) a compound having a cyclic ether group, and (C) a photoacid generator. A curable composition having a gel fraction of 50% or more 1 hour after irradiation with active energy rays is described.

By the way, Patent Documents 1 and 2 describe that a silane coupling agent may be used in order to improve the adhesiveness or surface curability.

International Publication No. 2009/075233 (Published June 18, 2009) Japanese Unexamined Patent Application Publication No. 2012-144693 (Published August 2, 2012)

In applications such as liquid crystal displays as a permanent film, not only is the photosensitive resin composition excellent in transparency and heat resistance, but also excellent adhesion (adhesion to the substrate) and resistance to wet etching in the manufacturing process. There is a demand for a photosensitive resin composition having chemical properties and capable of being directly patterned by photolithography.

However, the above-mentioned conventional techniques have room for improvement in adhesion to a substrate and chemical resistance. Further, an additive such as a silane coupling agent added to provide adhesion may have an unfavorable influence on the patterning property depending on the type or the amount added. For example, Patent Document 1 described above describes that a large amount of the silane coupling agent may adversely affect the curability and the physical properties of the cured product.

The present invention has been made in view of the above problems, and an object thereof is to realize a photosensitive resin composition having excellent adhesion to a substrate and chemical resistance without impairing patterning properties. is there.

The present inventors have conducted extensive studies in order to achieve the above-mentioned object, and as a result, by adding a compound having a specific structure to a polysiloxane compound having a photopolymerizable functional group and an alkali-soluble functional group, patterning properties can be improved. The inventors have found that a photosensitive resin composition having excellent adhesion to a substrate and chemical resistance can be realized without impairing the above, and have completed the present invention. That is, the present invention has the following configurations.

[1] (A) A polysiloxane compound having at least one photopolymerizable functional group and at least one alkali-soluble functional group in one molecule, and (B) the following formulas (Y1) to (Y3).

(In the formula, R ⁴³ represents a divalent organic group having 1 to 3 carbon atoms, R ⁴⁴ represents a monovalent organic group having 1 to 3 carbon atoms, and R ⁴⁵ represents a monovalent organic group having 1 to 3 carbon atoms. Represents an organic group or hydrogen atom)
And at least one compound represented by any of the above.

[2] The alkali-soluble functional group has the following formulas (X1) to (X3)

The negative photosensitive resin composition according to [1], which is at least one member selected from the group consisting of each structure represented by, a phenolic hydroxyl group, and a carboxyl group.

[3] The negative photosensitive resin composition as described in [1] or [2], wherein at least one of the photopolymerizable functional groups is an alicyclic epoxy group or a glycidyl group.

[4] Any one of [1] to [3], wherein the polysiloxane compound is a compound in which the photopolymerizable functional group and the alkali-soluble functional group are introduced by a silicon-carbon bond. The negative photosensitive resin composition as described in 1.

[5] The negative photosensitive resin composition as described in any one of [1] to [4], which contains a photoacid generator.

[6] A cured product obtained by curing the negative photosensitive resin composition according to any one of [1] to [5].

[7] A laminate comprising a substrate and a cured film obtained by curing the negative photosensitive resin composition according to any one of [1] to [5].

[8] The laminate according to [7], wherein the base material has a silicon nitride layer on the surface.

The present invention has an effect that it is possible to provide a photosensitive resin composition having excellent adhesion to a substrate and chemical resistance without impairing patterning properties.

Embodiments of the present invention will be described in detail below. Unless otherwise specified in the present specification, “A to B” representing a numerical range means “A or more (including A and larger than A) and B or less (including B and smaller than B)”.

[1. Negative-type photosensitive resin composition]
The negative photosensitive resin composition is (A) a polysiloxane compound having at least one photopolymerizable functional group and at least one alkali-soluble functional group in one molecule, and (B) a specific structure. And at least one compound having Hereinafter, the polysiloxane compound having at least one photopolymerizable functional group and at least one alkali-soluble functional group in one molecule of the above (A) is simply referred to as “component (A)”, and the above (B) At least one compound having a specific structure may be simply referred to as “component (B)”.

The negative photosensitive resin composition exhibits excellent adhesion and chemical resistance because it contains the above two components.

Incidentally, it was not known what effect the above-mentioned component (B) has on the patterning property when added to the negative photosensitive resin composition. Further, depending on the type and/or the addition amount of the conventional silane coupling agent, when added to the negative photosensitive resin composition, the patterning property may be unfavorably affected. On the other hand, surprisingly, the present inventors have found that when the component (B) having a specific structure to be described later is used together with the component (A), the patterning property is not impaired and the adhesion to the substrate is improved. It was also found that a negative photosensitive resin composition having excellent chemical resistance can be realized.

<1-1. Ingredient (A)>
The negative photosensitive resin composition contains a polysiloxane compound as the component (A).

In the present specification, the "polysiloxane compound" is not particularly limited as long as it is a compound having a siloxane unit Si-O-Si. The higher the content of T units (XSiO _3/2 ) or Q units (SiO _4/2 ) among the siloxane units in the polysiloxane compound, the higher the hardness of the obtained cured product, and the more excellent the heat resistance reliability is. .. In addition, the higher the content of M units (X ₃ SiO _1/2 ) or D units (X ₂ SiO _2/2 ) among the siloxane units in the polysiloxane compound, the more flexible and low the obtained cured product is. It is stress.

The polysiloxane compound has at least one photopolymerizable functional group in one molecule. In the present specification, the photopolymerizable functional group, when the active energy ray is irradiated from the outside, an acidic active substance generated by the photoacid generator, or a radical species or a cation species generated by the photopolymerization initiator. Means a functional group that polymerizes and crosslinks. Examples of active energy rays include visible light, ultraviolet rays, infrared rays, X rays, α rays, β rays, γ rays and i rays. The reaction system and the crosslinking system by the photopolymerizable functional group are not particularly limited.

Among them, at least one of the photopolymerizable functional groups is an epoxy group or a crosslinkable silicon group (sometimes referred to as “hydrolyzable silyl group”) from the viewpoint of reactivity and stability of the polysiloxane compound. It is preferably a (meth)acryloyl group or a vinyloxy group. Among the above epoxy groups, an alicyclic epoxy group or a glycidyl group is preferable from the viewpoint of stability, and an alicyclic epoxy group is particularly preferable in terms of excellent cationic polymerizability by light and heat.

Examples of the crosslinkable silicon group include hydrolyzable silicon groups such as an alkoxysilyl group, an acetoxysilyl group, a phenoxysilyl group, a silanol group and a chlorosilyl group. From the viewpoint of availability and stability of the compound, the crosslinkable silicon group is preferably an alkoxysilyl group. Examples of the alkoxysilyl group include those whose silicon-bonded functional group is a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a sec-butoxy group or a tert-butoxy group. .. From the viewpoint that the residual component after curing hardly remains, the functional group bonded to silicon is preferably a methoxy group or an ethoxy group.

From the viewpoint of reactivity, the alkoxysilyl group is preferably an alkoxysilylethyl group or an alkoxysilylpropyl group, specifically, (alkoxysilylethyl)dimethylsilyl group, (alkoxysilylethyl)diphenylsilyl group. , (Alkoxysilylpropyl)dimethylsilyl group or (alkoxysilylpropyl)diphenyl group.

The polysiloxane compound may have at least one photopolymerizable functional group in one molecule, but preferably has two or more and more preferably has three or more. When the number of photopolymerizable functional groups is 3 or more, a cured product having a high crosslink density can be obtained, and the cured product has an advantage of excellent heat resistance. Each photopolymerizable functional group may be the same or two or more different functional groups.

Further, the polysiloxane compound has at least one kind of alkali-soluble functional group in the same molecule, in addition to at least one photopolymerizable functional group. In the present specification, the alkali-soluble functional group means a functional group that imparts alkali solubility to the compound. Since the polysiloxane compound has an alkali-soluble functional group in the same molecule in addition to the photopolymerizable functional group, it can be dissolved in an alkaline aqueous solution. Therefore, the negative photosensitive resin composition containing the polysiloxane compound can be applied as an alkali-developable resist material.

Particularly from the viewpoint of reactivity, the alkali-soluble functional group has the following formulas (X1) to (X3).

In the group consisting of each structure represented by, a phenolic hydroxyl group and a carboxyl group (hereinafter, each structure represented by the formulas (X1) to (X3), the phenolic hydroxyl group and the carboxyl group may be referred to as an “acidic group”). It is preferably at least one selected from

In other words, the polysiloxane compound preferably has at least one of the acidic groups as an alkali-soluble functional group. That is, the polysiloxane compound may be a compound having any of the structures represented by formulas (X1) to (X3), a compound having a phenolic hydroxyl group, or a carboxyl group. The compound may have.

The alkali-soluble functional group is preferably any one of the structures represented by the formulas (X1) to (X3) or a carboxyl group from the viewpoint that the obtained cured product is less likely to be colored after heating. Further, from the viewpoint of obtaining a cured product having low thermal decomposability at high temperature, the alkali-soluble functional group is particularly preferably any of the structures represented by the above formulas (X1) to (X3).

Each structure represented by the above formulas (X1) to (X3) is similar to the structure of the component (B) described below in that it has an isocyanuric ring. Therefore, when the polysiloxane-based compound has any of the structures represented by the formulas (X1) to (X3), the compatibility with the component (B) is good, which is preferable.

The addition amount of the component (A) to 100% by weight of the negative photosensitive resin composition containing no solvent is preferably 30 to 99.9% by weight, more preferably 50 to 99% by weight, It is more preferably 70 to 99% by weight. When the addition amount of the component (A) is 30% by weight or more, excellent heat resistance and transparency are obtained, which is preferable. When the added amount of the component (A) is 99.9% by weight or less, the effect of the component (B) can be sufficiently exhibited, which is preferable.

The method for introducing the photopolymerizable functional group and the alkali-soluble functional group into the polysiloxane compound is not particularly limited, but the photopolymerizable by a chemically stable silicon-carbon bond (Si-C bond) is used. A method using a hydrosilylation reaction capable of introducing the functional group and the alkali-soluble functional group into the polysiloxane compound is preferable.

In other words, the polysiloxane compound is preferably an organically modified compound obtained by a hydrosilylation reaction. That is, the polysiloxane compound is preferably a compound in which the alkali-soluble functional group and the photopolymerizable functional group are introduced by a silicon-carbon bond.

Examples of suitable polysiloxane-based compounds include the following three modes. In the present specification, the "SiH group" may be referred to as the "hydrosilyl group".

A first preferred embodiment includes products obtained by hydrosilylation reactions using the following compounds (α1), (β) and (γ1) as starting materials:
(Α1) One or more carbon-carbon double bonds reactive with a SiH group in one molecule, each structure represented by the formulas (X1) to (X3), a phenolic hydroxyl group and a carboxyl group. An organic compound having at least one acidic group selected from the group consisting of,
(Β) A polysiloxane compound having at least two SiH groups in one molecule,
(Γ1) A compound having, in one molecule, at least one carbon-carbon double bond having reactivity with a SiH group and at least one photopolymerizable functional group.

A second preferred embodiment includes products obtained by hydrosilylation reactions using the following compounds (α1), (α2), (β) and (γ1) as starting materials:
(Α1) At least one carbon-carbon double bond having reactivity with a SiH group in one molecule, each structure represented by the above formulas (X1) to (X3), a phenolic hydroxyl group and a carboxyl group An organic compound having at least one acidic group selected from the group consisting of,
(Α2) a compound having at least one carbon-carbon double bond having reactivity with a SiH group in one molecule,
(Β) A polysiloxane compound having at least two SiH groups in one molecule,
(Γ1) A compound having, in one molecule, at least one carbon-carbon double bond having reactivity with a SiH group and at least one photopolymerizable functional group.

A third preferred embodiment includes products obtained by hydrosilylation reactions using the following compounds (α3), (α4) and (γ2) as starting materials:
(Α3) a compound having at least two carbon-carbon double bonds reactive with a SiH group in one molecule,
(Α4) At least one SiH group in each molecule, and at least one acidic group selected from the group consisting of the structures represented by the formulas (X1) to (X3), a phenolic hydroxyl group, and a carboxyl group. And a compound having,
(Γ2) A compound having at least one photopolymerizable functional group and at least one SiH group in one molecule.

In other words, the polysiloxane compound is preferably a copolymer of some compounds selected from the compounds (α1) to (α4), (β), (γ1) and (γ2).

Hereinafter, the above-mentioned preferred embodiments of the polysiloxane compound will be described.

(Compound (α1))
The compound (α1) includes at least one carbon-carbon double bond having reactivity with a SiH group in each molecule, each structure represented by the formulas (X1) to (X3), and a phenolic hydroxyl group. There is no particular limitation as long as it is an organic compound having at least one acidic group selected from the group consisting of and a carboxyl group.

The compound (α1) is not a compound containing a siloxane unit (Si—O—Si) such as polysiloxane-organic block copolymer and polysiloxane-organic graft copolymer, but is composed of C, H, N, O, S and halogen. A compound containing only constituent elements selected from the group is preferable. When the compound (α1) does not contain a siloxane unit, gas permeability is good, and repelling is less likely to occur, which is preferable.

The position of the carbon-carbon double bond reactive with the SiH group in the compound (α1) is not particularly limited and may be anywhere in the molecule.

The group containing the carbon-carbon double bond that is reactive with the SiH group is not particularly limited, but is vinyl group, allyl group, methallyl group, acryl group, methacryl group, 2-hydroxy-3-(allyloxy)propyl. Group, 2-allylphenyl group, 3-allylphenyl group, 4-allylphenyl group, 2-(allyloxy)phenyl group, 3-(allyloxy)phenyl group, 4-(allyloxy)phenyl group, 2-(allyloxy)ethyl group Group, 2,2-bis(allyloxymethyl)butyl group, 3-allyloxy-2,2-bis(allyloxymethyl)propyl group, vinyl ether group and the like. From the viewpoint of reactivity, the group containing a carbon-carbon double bond is preferably a vinyl group or an allyl group.

The compound (α1) only needs to have at least one carbon-carbon double bond reactive with the SiH group in one molecule, but since the obtained cured product has a high crosslink density, it has high heat resistance reliability. From this viewpoint, it is preferable to have two or more carbon-carbon double bonds in one molecule, and it is more preferable to have three or more carbon-carbon double bonds in one molecule.

The compound (α1) is not particularly limited, but from the viewpoint of little coloring at high temperature, the following general formulas (Ia) to (Ic) having an isocyanuric ring are included.

(In the formula, R ² represents a monovalent organic group having 1 to 50 carbon atoms, and each R ² may be different or the same, and at least one R ² has a reactivity with a SiH group. Having a carbon-carbon double bond)
It is preferable to use at least one compound represented by any of the above.

Examples of the organic group include a hydrocarbon group (which may be partially substituted with oxygen) and an epoxy group. From the viewpoint of availability, the organic group is preferably a phenyl group, a methyl group, an ethyl group, a propyl group, a benzyl group or a glycidyl group. The group containing a carbon-carbon double bond having reactivity with the SiH group is preferably an allyl group or a vinyl group.

From the viewpoint of availability, the compound (α1) is diallyl isocyanuric acid, monoallyl isocyanuric acid, vinylphenol, allylphenol, the following general formula (IIa) or (IIb).

Compounds represented by, butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid or undecylenic acid are preferred. Among these, the compound (α1) is preferably diallyl isocyanuric acid, monoallyl isocyanuric acid, diallyl bisphenol A, diallyl bisphenol S, vinylphenol or allylphenol from the viewpoint of particularly high heat resistance. Further, from the viewpoint of transparency of the cured product, it is particularly preferable that the compound (α1) is diallyl isocyanuric acid or monoallyl isocyanuric acid.

As the compound (α1), one type may be used, or two or more types may be used in combination.

(Compound (α2))
The compound (α2) is a compound which does not correspond to the compound (α1) and the compound (γ1) described later and has at least one carbon-carbon double bond having reactivity with a SiH group in one molecule. It is not particularly limited.

From the viewpoint of high heat resistance of the obtained cured product, the compound (α2) is preferably a polysiloxane having at least one alkenyl group. Specific examples of the polysiloxane having at least one alkenyl group include alkenyl group-containing polysiloxanes having a linear structure, polysiloxanes having an alkenyl group at the molecular end, and cyclic siloxane compounds having an alkenyl group. The polysiloxane having at least one alkenyl group is not particularly limited by the structure, but considering heat resistance, light resistance, chemical stability, etc., it is a polysiloxane having a polyhedral skeleton containing an alkenyl group. Preferably.

Examples of the alkenyl group-containing polysiloxane having the above linear structure include a copolymer of a dimethylsiloxane unit, a methylvinylsiloxane unit and a terminal trimethylsiloxy unit, a diphenylsiloxane unit, a methylvinylsiloxane unit and a terminal trimethylsiloxy unit. Examples thereof include a polymer, a copolymer of a methylphenylsiloxane unit, a methylvinylsiloxane unit and a terminal trimethylsiloxy unit, and a polysiloxane whose end is blocked by a dimethylvinylsilyl group.

The polysiloxane having an alkenyl group at the molecular end is at least selected from the group consisting of polysiloxanes whose ends are blocked with dimethylalkenyl groups, and dimethylalkenylsiloxane units, SiO ₂ units, SiO _3/2 units, and SiO units. An example is polysiloxane composed of one siloxane unit.

Examples of the cyclic siloxane compound containing an alkenyl group include 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1, 3,5,7-Tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-1,3,3 5-Trimethylcyclosiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane and 1,3,5,7,9,11-hexavinyl-1,3 , 5,7,9,11-hexamethylcyclosiloxane and the like are exemplified.

The polysiloxane having a polyhedral skeleton containing an alkenyl group is preferably a polysiloxane in which the number of Si atoms contained in the polyhedral skeleton is 6 to 24. Specific examples of the polysiloxane include silsesquioxane having a polyhedral skeleton represented by the following general formula (III) (here, the case where Si atom number=8 is shown as a representative example).

In the above formulas, R ^{10 to} R ¹⁷ are alkenyl groups (vinyl group, allyl group, butenyl group, hexenyl group, etc.), (meth)acryloyl group, epoxy group, mercapto group or amino group-containing organic group, alkyl group. (Methyl group, ethyl group, propyl group, butyl group, etc.), cycloalkyl group (cyclohexyl group, etc.), aryl group (phenyl group, tolyl group, etc.), or part of the hydrogen atoms bonded to the carbon atoms of these groups. Alternatively, it is the same or different monovalent hydrocarbon group selected from a group (chloromethyl group, trifluoropropyl group, cyanoethyl group, etc.) in which all are substituted with a halogen atom or a cyano group, or a hydrogen atom. The hydrocarbon group preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. The hydrocarbon group may be unsubstituted or may be substituted.

However, at least one of R ^{10 to} R ¹⁷ in the compound (α2) is an alkenyl group which is a reactive group of the hydrosilylation reaction. The alkenyl group is preferably a vinyl group from the viewpoint of heat resistance.

The silsesquioxane having the polyhedral skeleton is, for example, RSiX ₃ (wherein R corresponds to each of the above R ^{10 to} R ¹⁷ , and X represents a hydrolyzable functional group such as a halogen atom or an alkoxy group). It is obtained by a hydrolysis condensation reaction of a silane compound represented by

Alternatively, a trisilanol compound having three silanol groups in the molecule is synthesized by a hydrolysis condensation reaction of RSiX ₃ , and then the same or different trifunctional silane compound is reacted to perform ring closure to have a polyhedral skeleton. A method of synthesizing silsesquioxane is also known.

As a more preferable compound (α2), silylated silicic acid having a polyhedral skeleton represented by the following general formula (IV) is exemplified (here, the case where Si atom number=8 is shown as a representative example). In the silylated silicic acid having the polyhedral skeleton, since the Si atom forming the polyhedral skeleton and the alkenyl group that is a reactive group are bonded via a siloxane bond, the obtained cured product becomes rigid. Not too much. Therefore, a good cured product can be obtained by using the silylated silicic acid having the polyhedral skeleton.

In the above formulas, R ^{18 to} R ⁴¹ are alkenyl groups (vinyl group, allyl group, butenyl group, hexenyl group, etc.), (meth)acryloyl group, epoxy group, mercapto group or amino group-containing organic group, alkyl group. (Methyl group, ethyl group, propyl group, butyl group, etc.), cycloalkyl group (cyclohexyl group, etc.), aryl group (phenyl group, tolyl group, etc.), or part of the hydrogen atoms bonded to the carbon atoms of these groups. Alternatively, it is the same or different hydrocarbon group selected from a group (chloromethyl group, trifluoropropyl group, cyanoethyl group, etc.) in which all are substituted with a halogen atom or a cyano group, or a hydrogen atom. However, at least one of R ^{18 to} R ⁴¹ in the compound (α2) is an alkenyl group which is a reactive group of the hydrosilylation reaction. The alkenyl group is preferably a vinyl group from the viewpoint of heat resistance.

The method for synthesizing the silicate having a polyhedral skeleton is not particularly limited, and a known method can be used. Specific examples of the synthesis method include a method in which tetraalkoxysilane is hydrolyzed and condensed in the presence of a base such as quaternary ammonium hydroxide. Examples of the tetraalkoxysilane include tetraethoxysilane, tetramethoxysilane and tetrabutoxysilane. Examples of the quaternary ammonium hydroxide include 2-hydroxyethyltrimethylammonium hydroxide and tetramethylammonium hydroxide. Further, in the present invention, a silicate having the same polyhedral skeleton can be obtained from a substance containing silica, such as rice hulls, instead of tetraalkoxylane.

In the present synthetic method, a silicate having a polyhedral skeleton is obtained by a hydrolysis condensation reaction of tetraalkoxysilane, and the obtained silicate is reacted with a silylating agent such as an alkenyl group-containing silyl chloride. It is possible to obtain a polysiloxane in which the Si atom forming the polyhedral skeleton and the alkenyl group which is a reactive group are bonded via a siloxane bond.

The number of Si atoms contained in the polyhedral skeleton is preferably 6 to 24, and more preferably 6 to 10. Further, polysiloxanes having polyhedral skeletons having different numbers of Si atoms may be used as a mixture. In addition, in the compound (α2), the number of alkenyl groups contained in one molecule is preferably at least 1, more preferably at least 2, and further preferably at least 3. From the viewpoint of heat resistance and light resistance, the organic group existing on the Si atom is preferably at least one of a vinyl group and a methyl group.

In addition, from the viewpoint of high adhesion to the base material, as the compound (α2), an organic compound having at least one carbon-carbon double bond reactive with a SiH group in one molecule is used. You can also The organic compound mentioned here can be classified into an organic polymer compound and an organic monomer compound.

Examples of the organic polymer-based compound include polyether-based, polyester-based, polyarylate-based, polycarbonate-based, saturated hydrocarbon-based, unsaturated hydrocarbon-based, polyacrylic acid ester-based, polyamide-based, phenol-formaldehyde-based (phenol resin Type) or a polyimide type compound can be used.

Examples of the organic monomer compounds include phenolic compounds, bisphenolic compounds, aromatic hydrocarbon compounds such as benzene and naphthalene; aliphatic hydrocarbon compounds such as linear and alicyclic compounds, heterocyclic compounds, and the like. And the like.

Specific examples of the compound (α2) which is an organic compound include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, penta Erythritol tetraallyl ether, 1,1,2,2-tetraallyloxyethane, diarylidene pentaerythritol, diallyl monomethyl isocyanuric acid, triallyl cyanurate, triallyl isocyanurate, diallyl monobenzyl isocyanurate, 1,2, 4-trivinylcyclohexane, 1,4-butanediol divinyl ether, nonanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, bisphenol Diallyl ether of S, divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-bis(allyloxy)adamantane, 1,3-bis(vinyloxy)adamantane, 1 ,3,5-Tris(allyloxy)adamantane, 1,3,5-Tris(vinyloxy)adamantane, dicyclopentadiene, vinylcyclohexene, 1,5-hexadiene, 1,9-decadiene, diallyl ether, bisphenol A diallyl ether , 2,5-diallylphenol allyl ether, and their oligomers, 1,2-polybutadiene (1,2 ratio 10-100%, preferably 1,2 ratio 50-100%), novolacphenol allyl Examples thereof include ethers, allylated polyphenylene oxide, and those in which all of the glycidyl groups of conventionally known epoxy resins are replaced with allyl groups.

As the compound (α2), a low molecular weight compound, which is difficult to be expressed by being divided into a skeleton portion and an alkenyl group (carbon-carbon double bond reactive with SiH group), can also be used. Specific examples of these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene, cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene and other fatty acids. Group cyclic polyene compound system, and substituted cycloaliphatic olefin compound system such as vinylcyclopentene and vinylcyclohexene.

From the viewpoint of particularly high heat resistance and light resistance, the compound (α2) has the following general formula (V):

(In the formula, R ³ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ³ may be different or the same, and at least one R ³ has a reactivity with a SiH group. Having a carbon-carbon double bond)
The compound represented by is preferable.

Examples of the organic group include a hydrocarbon group (which may be partially substituted with oxygen). From the viewpoint that the obtained cured product may have higher heat resistance, the organic group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and 1 to 4 carbon atoms. Is more preferable. Examples of preferable R ³ include a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a benzyl group, a phenethyl group, a vinyl group and an allyl group.

From the viewpoint of availability, preferable specific examples of the compound (α2) which is an organic compound include diallyl monomethyl isocyanuric acid and triallyl isocyanurate.

As the compound (α2), one type may be used, or two or more types may be used in combination.

(Compound (α3))
Among the above compounds (α2), a compound having at least two carbon-carbon double bonds reactive with a SiH group can be used as the compound (α3).

The compound (α3) is not particularly limited as long as it has two or more carbon-carbon double bonds in the above compound (α2). As the compound (α3), one type may be used, or two or more types may be used in combination.

(Compound (α4))
The compound (α4) is at least one selected from the group consisting of at least one SiH group, each structure represented by the formulas (X1) to (X3), a phenolic hydroxyl group and a carboxyl group in one molecule. There is no particular limitation as long as it is a compound having the acidic group of.

The compound (α4) is, for example, a product obtained by a hydrosilylation reaction using the above compound (α1) and a polyfunctional hydrosilane compound as starting materials, and at least one compound is present in the molecule of the product. And the like having a hydrosilyl group can be used.

Examples of the polyfunctional hydrosilane compound include tetramethyldisiloxane, hexamethyltrisiloxane, and other poly or oligosiloxanes whose ends are blocked with dimethylhydrogensilyl groups, and 1,3,5,7-tetrahydrogen- 1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen- 3,7-Dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-1,3,5-trimethylcyclosiloxane, 1,3,5,7,9- Pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane and 1,3,5,7,9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclo Examples include cyclic siloxanes containing a hydrosilyl group, such as siloxanes, but are not limited thereto.

(Compound (β))
The compound (β) is not particularly limited as long as it is a polysiloxane compound having at least two SiH groups in one molecule, and examples thereof include compounds described in WO 96/15194 and at least one molecule. Those having two SiH groups can be used.

Specific examples of the compound (β) include a hydrosilyl group-containing polysiloxane having a linear structure, a polysiloxane having a hydrosilyl group at the molecular end, and a cyclic polysiloxane compound having a hydrosilyl group, and the structure is particularly limited. Not a thing. Considering heat resistance, light resistance, chemical stability and the like, the compound (β) is preferably a polysiloxane having a polyhedral skeleton containing a hydrosilyl group.

Examples of the hydrosilyl group-containing polysiloxane having a linear structure include a copolymer of a dimethylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, a diphenylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit. Examples thereof include copolymers, copolymers of methylphenylsiloxane units with methylhydrogensiloxane units and terminal trimethylsiloxy units, and polysiloxanes whose ends are blocked with dimethylhydrogensilyl groups.

Examples of the polysiloxane having a hydrosilyl group at the molecular end include a polysiloxane whose end is blocked by a dimethylhydrogensilyl group, as well as a dimethylhydrogensiloxane unit (H(CH ₃ ) ₂ SiO _1/2 unit). And a polysiloxane having at least one siloxane unit selected from the group consisting of a SiO ₂ unit, a SiO _3/2 unit, and a SiO unit.

Examples of the cyclic polysiloxane compound containing a hydrosilyl group include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 1-propyl-3,5,7-tri. Hydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5 -Trihydrogen-1,3,5-trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane and 1,3,5,5 Examples include 7,9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclosiloxane and the like.

The polysiloxane having a polyhedral skeleton containing a hydrosilyl group is preferably a polysiloxane in which the number of Si atoms contained in the polyhedral skeleton is 6 to 24. Specific examples of the polysiloxane include silsesquioxane having a polyhedral skeleton represented by the following general formula (III) (here, the case where Si atom number=8 is shown as a representative example).

In the above formula, R ^{10 to} R ¹⁷ are the same as R ^{10 to} R ^{17 in the} polysiloxane having a polyhedral skeleton containing an alkenyl group exemplified as the compound (α2). However, in the compound (β), at least one of R ^{10 to} R ¹⁷ is a hydrosilyl group that is a reactive group of the hydrosilylation reaction.

The method for synthesizing the silsesquioxane having the polyhedral skeleton is the same as the method for synthesizing the silsesquioxane having the polyhedral skeleton exemplified as the compound (α2).

As a more preferable compound (β), silylated silicic acid having a polyhedral skeleton represented by the following general formula (IV) is exemplified (here, the case where Si atom number=8 is shown as a representative example). In the compound, since the Si atom forming the polyhedral skeleton and the reactive group are bonded via the siloxane bond, the obtained cured product does not become too rigid. Therefore, a good cured product can be obtained by using the compound.

In the above formula, R ^{18 to} R ⁴¹ are the same as R ^{18 to} R ⁴¹ in the silylated silicic acid having a polyhedral skeleton exemplified as the compound (α2). However, among these R ^{18 to} R ⁴¹ , at least one is a hydrosilyl group that is a reactive group of the hydrosilylation reaction.

The synthesis method of the silicate having a polyhedral skeleton is not particularly limited, and the same synthesis method as the synthesis method of the silicate having a polyhedral skeleton exemplified as the compound (α2) can be used.

In the present synthetic method, a silicate having a polyhedral skeleton is obtained by a hydrolysis-condensation reaction of tetraalkoxysilane, and the obtained silicate is reacted with a silylating agent such as a hydrosilyl group-containing silyl chloride. Thus, it becomes possible to obtain a polysiloxane in which a Si atom forming a polyhedral structure and a hydrosilyl group which is a reactive group are bonded via a siloxane bond.

The number of Si atoms contained in the polyhedral skeleton is preferably 6 to 24, and more preferably 6 to 10. Further, polysiloxanes having polyhedral skeletons having different numbers of Si atoms may be used as a mixture.

Further, in the compound (β), the number of hydrosilyl groups contained in one molecule is at least 2, and more preferably at least 3. From the viewpoint of heat resistance and light resistance, the group existing on the Si atom is preferably at least one of a hydrogen atom and a methyl group.

From the viewpoint of availability and good reactivity with the compounds (α1), (α2) and (γ1), the compound (β) has the following general formula (VI):

(In the formula, R ⁴ and R ⁵ represent an organic group having 1 to 6 carbon atoms and may be the same or different, n is an integer of 1 to 10 and m is an integer of 0 to 10)
It is preferable that the cyclic organopolysiloxane represented by the following formula has at least 3 SiH groups in one molecule.

Examples of the organic group include a hydrocarbon group (which may be partially substituted with oxygen). The hydrocarbon group is preferably a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a cyclohexyl group, a norbornyl group or a phenyl group, and from the viewpoint of availability, a methyl group, a propyl group. It is more preferably a group, a hexyl group or a phenyl group.

The substituents R ⁴ and R ⁵ in the compound represented by the general formula (VI) are preferably ones composed of an element selected from the group consisting of C, H and O, and are hydrocarbon groups. More preferably, it is more preferably a methyl group.

The compound represented by the general formula (VI) is 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane from the viewpoint of easy availability and reactivity. Preferably.

As the compound (β), one type may be used, or two or more types may be used in combination.

(Compound (γ1))
The compound (γ1) is particularly limited as long as it is a compound having at least one carbon-carbon double bond reactive with a SiH group and at least one photopolymerizable functional group in one molecule. Not done. The photopolymerizable functional group mentioned here is the same as the photopolymerizable functional group contained in the component (A), and the preferred embodiments are also the same.

The group containing a carbon-carbon double bond having reactivity with the SiH group in the compound (γ1) is a carbon-carbon double group having reactivity with the SiH group in the compounds (α1) and (α2) described above. The same group as the group containing a bond is preferable.

Specific examples of the compound (γ1) having an epoxy group as a photopolymerizable functional group include 1-vinyl-3,4-epoxycyclohexane, vinylcyclohexene oxide, allyl glycidyl ether, diallyl monoglycidyl isocyanurate and monoallyl diglycidyl isocyanate. Nurate and the like can be mentioned. From the viewpoint of excellent photopolymerization reactivity, the compound (γ1) is particularly preferably vinylcyclohexene oxide, which is a compound having an alicyclic epoxy group.

Specific examples of the compound (γ1) having a crosslinkable silicon group (hydrolyzable silyl group) as a photopolymerizable functional group include halogenated silanes such as trichlorovinylsilane, methyldichlorovinylsilane, dimethylchlorovinylsilane and phenyldichlorovinylsilane; Alkoxysilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, methyldiethoxyvinylsilane, methyldimethoxyvinylsilane and phenyldimethoxyvinylsilane; Acyloxysilanes such as methyldiacetoxyvinylsilane and phenyldiacetoxyvinylsilane; Bis(dimethylketoximate)methyl Examples thereof include, but are not limited to, ketoxymate silanes such as vinylsilane and bis(cyclohexylketoximate)methylvinylsilane. Of these, alkoxysilanes can be particularly preferably used as the compound (γ1). When the photopolymerizable functional group in the compound (γ1) is a crosslinkable silicon group, there is an advantage that the obtained cured product has excellent heat resistance.

Further, from the viewpoint of easy availability, the compound (γ1) is represented by the following general formula (VII)

(In the formula, R ⁶ and R ⁷ represent an organic group having 1 to 6 carbon atoms, n represents an integer of 1 to 3, and m represents an integer of 0 to 10.)
The compound represented by is preferable. Among them, the compound (γ1) is particularly preferably trimethoxyvinylsilane, triethoxyvinylsilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, methoxydimethylvinylsilane or ethoxydimethylvinylsilane from the viewpoint that the by-products after the reaction are easily removed. Preferably.

Examples of the compound (γ1) having an acryloyl group or a methacryloyl group as a photopolymerizable functional group include allyl (meth)acrylate, vinyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth). Acrylate, (meth)acrylic acid-modified allyl glycidyl ether (manufactured by Nagase Chemtex, trade name: Denacol acrylate DA111), and vinyl group or allyl group and the following general formula (VIII)

(R ⁴² in the formula represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 16)
Examples thereof include a compound having one or more organic groups represented by in the same molecule.

For example, as the compound (γ1), in the general formula (V), at least one R ^{3 in} the formula is a group represented by the general formula (VIII), and at least one R ³ is Examples of the compound include a group having a carbon-carbon double bond having reactivity with a SiH group (a vinyl group, an allyl group, or the like). Further, from the viewpoint of high selectivity in hydrosilylation, the compound (γ1) is preferably a compound having a methacryloyl group and an allyl group or a vinyl group in the same molecule, and from the viewpoint of availability (meth) It is more preferably at least one of allyl acrylate and vinyl (meth)acrylate, and further preferably at least one of allyl methacrylate and vinyl methacrylate.

Further, in the hydrosilylation reaction, two or more kinds of compounds (γ1) can be used together regardless of the kind of the photopolymerizable functional group.

(Compound (γ2))
The compound (γ2) is not particularly limited as long as it has at least one photopolymerizable functional group and at least one SiH group that is a reactive group for hydrosilylation reaction in one molecule. Examples of the photopolymerizable functional group include the epoxy group, the crosslinkable silicon group (hydrolyzable silyl group) and the acryloyl group as described above.

The compound (γ2) is a product obtained by a hydrosilylation reaction using any one of the compounds exemplified as the above compound (γ1) and a polyfunctional hydrosilane compound as a starting material, and at least one compound is present in the molecule. The product having a hydrosilyl group can be used. The polyfunctional hydrosilane compounds exemplified as starting materials for the hydrosilylation reaction to obtain the compound (α4) can be similarly used as the polyfunctional hydrosilane compound herein.

In particular, from the viewpoint that the cured product has excellent heat resistance, the compound (γ2) is preferably a compound having a hydrolyzable silyl group (crosslinkable silicon group). Specific examples of the compound (γ2) having a hydrolyzable silyl group (crosslinkable silicon group) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and phenyldichlorosilane; Alkoxysilanes such as methoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane and phenyldimethoxysilane; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; bis(dimethylketoxymate)methylsilane and Examples thereof include, but are not limited to, ketoxymate silanes such as bis(cyclohexyl ketoximate)methylsilane. Of these, alkoxysilanes can be particularly preferably used as the compound (γ2).

(Hydrosilylation catalyst)
As a catalyst for polymerizing a compound selected from the compounds (α1) to (α4), (β) and (γ1) to (γ2) by a hydrosilylation reaction, a known hydrosilylation catalyst may be used.

From the viewpoint of catalytic activity, the hydrosilylation catalyst is preferably chloroplatinic acid, a platinum-olefin complex, a platinum-vinylsiloxane complex, or the like. Moreover, as these catalysts, 1 type may be used and 2 or more types may be used together.

The addition amount of the hydrosilylation catalyst is not particularly limited, but from the viewpoint of allowing the hydrosilylation reaction to proceed smoothly, the lower limit of the addition amount is the carbon-carbon double bond having reactivity with the SiH group charged at the time of reaction. It is preferably 10 ⁻⁸ mol, more preferably 10 ⁻⁶ mol, relative to 1 mol of a group containing (hereinafter sometimes simply referred to as “alkenyl group”), and the upper limit of the addition amount is 1 mol of the alkenyl group. With respect to, it is preferably 10 ⁻¹ mol, more preferably 10 ⁻² mol.

Further, a co-catalyst can be used in combination with the hydrosilylation catalyst. Examples of cocatalysts include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethylmalate, 2-hydroxy-2-methyl-1-butyne, 1-ethynyl-1-cyclohexanol and the like. The acetylene alcohol-based compounds of, as well as sulfur-based compounds such as elemental sulfur. The addition amount of the cocatalyst is not particularly limited, but the lower limit of the addition amount to 1 mol of the hydrosilylation catalyst is preferably 10 ⁻² mol, more preferably 10 ⁻¹ mol, and the upper limit of the addition amount is preferably 10 ² mol. , And more preferably 10 moles.

(Hydrosilylation reaction)
Although various methods can be mentioned as the order and method of the reaction, from the viewpoint that the synthetic steps are simple, all the compounds are charged in one pot to carry out the hydrosilylation reaction, and finally unreacted compounds are removed. The method is preferred.

From the viewpoint that it is difficult to contain a low molecular weight compound, an excess alkenyl group-containing compound (compound (α1), (α2) or (α3)) and SiH group-containing compound (compound (β) or (α4)), or After performing a hydrosilylation reaction using an excess SiH group-containing compound (compound (β) or (α4)) and an alkenyl group-containing compound (compound (α1), (α2) or (α3)) as a starting material More preferred is a method in which the unreacted compound is removed once and the hydrosilylation reaction is carried out using the obtained reaction product and the compound (γ1) or the compound (γ2) as a starting material.

The ratio of each compound to be reacted is not particularly limited, but when A is the total amount of alkenyl groups of the compound to be reacted and B is the total amount of SiH groups of the compound to be reacted, it is preferable that 1≦B/A≦30, It is more preferable that 1≦B/A≦10. If 1≦B/A, unreacted alkenyl groups are less likely to remain in the composition, and thus coloring is less likely to occur. If B/A≦30, unreacted SiH groups are less likely to remain, and thus foaming and cracking during curing of the composition are less likely to occur.

The reaction temperature can be set appropriately, but the lower limit of the temperature range is preferably 30° C., more preferably 50° C., and the upper limit of the temperature range is preferably 200° C., more preferably 150° C. If the reaction temperature is low, the reaction time for sufficiently reacting becomes long, and if the reaction temperature is high, it is not practical. The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple stages or continuously if necessary.

The reaction time and the pressure during the reaction can also be set appropriately. Oxygen can be used during the hydrosilylation reaction. The hydrosilylation reaction can be promoted by adding oxygen to the gas phase of the reaction vessel. In order to keep the amount of oxygen added below the explosion limit lower limit, it is necessary to control the oxygen volume concentration in the gas phase to 3% or less. From the viewpoint that the effect of accelerating the hydrosilylation reaction by the addition of oxygen is observed, the oxygen volume concentration in the gas phase part is preferably 0.1% or more, more preferably 1% or more.

A solvent may be used in the hydrosilylation reaction. The solvent that can be used is not particularly limited as long as it does not inhibit the hydrosilylation reaction, and specifically, hydrocarbon solvents such as benzene, toluene, hexane and heptane, tetrahydrofuran, 1,4-dioxane, 1,3- Examples thereof include ether solvents such as dioxolane and diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane. The solvent may be used as a mixed solvent of two or more kinds. More preferably, the solvent is toluene, tetrahydrofuran, 1,3-dioxolane or chloroform. The amount of solvent used can also be set appropriately.

In the method for producing the component (A), various additives can be used depending on the purpose.

(Gelization inhibitor)
The purpose of improving the storage stability of the obtained reaction product, or the hydrosilylation reaction using the compound (α1) (in some embodiments, further the compound (α2)), the compound (β) and the compound (γ1) or (γ2). A gelation inhibitor can be used for the purpose of suppressing deterioration such as thickening due to heat treatment when the solvent and the unreacted compound are removed by devolatilization under reduced pressure after the operation. As the gelation inhibitor, a known gelation inhibitor such as a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound or an organic peroxide can be used. You may use together.

From the viewpoint of good delayed activity and good availability of raw materials, gelling inhibitors include benzothiazole, thiazole, dimethylmalate, 3-hydroxy-3-methyl-1-butyne, 1-ethynyl-1-cyclohexanol. Alternatively, it is preferably triphenylphosphine. That is, a part of the above-mentioned co-catalyst can also be used as a gelation inhibitor.

The addition amount of the gelling inhibitor can be appropriately set, but the lower limit of the addition amount to 1 mol of the hydrosilylation catalyst used is preferably 10 ⁻¹ mol, more preferably 1 mol, and the upper limit of the addition amount is preferably Is 10 ³ mol, more preferably 10 ² mol. If the added amount is too small, the desired storage stability and gelation suppressing effect at the time of devolatilization under reduced pressure cannot be obtained. A large amount of addition may serve as a curing inhibitor during the curing reaction.

Moreover, as these gelation inhibitors, one kind may be used, or two or more kinds may be used in combination.

<1-2. Ingredient (B)>
The negative photosensitive resin composition contains the compound shown below as the component (B). Since the negative photosensitive resin composition contains the component (B), not only the adhesion is improved, but also the chemical resistance is improved without impairing the patterning property. This is the first discovery of the present inventors.

The component (B) is represented by the following formulas (Y1) to (Y3).

(In the formula, R ⁴³ represents a divalent organic group having 1 to 3 carbon atoms, R ⁴⁴ represents a monovalent organic group having 1 to 3 carbon atoms, and R ⁴⁵ represents a monovalent organic group having 1 to 3 carbon atoms. Represents an organic group or hydrogen atom)
It is at least 1 sort(s) of compound represented by either.

Examples of R ⁴³ include a methylene group, an ethylene group and a propylene group. Examples of R ⁴⁴ include a methyl group, an ethyl group and a propyl group. In addition, examples of R ⁴⁵ include a methyl group, an ethyl group, a propyl group, and a hydrogen atom.

From the viewpoint that the patterning property, the adhesion and the chemical resistance can be further improved, the component (B) is preferably a compound represented by the formula (Y1) or (Y2), and the compound represented by the formula (Y1) The compound represented by is more preferable.

The addition amount of the component (B) is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, relative to 100% by weight of the negative photosensitive resin composition containing no solvent. It is more preferably 0.5 to 5% by weight. When the addition amount of the component (B) is 0.01% by weight or more, the adhesion and the chemical resistance can be sufficiently improved, which is preferable. When the addition amount of the component (B) is 20% by weight or less, sufficient patterning property can be secured, which is preferable.

<1-3. Photo acid generator>
The negative photosensitive resin composition may contain a photoacid generator. The photoacid generator is particularly a compound capable of releasing an acidic active substance capable of crosslinking the photopolymerizable functional group of the component (A) by being irradiated with an active energy ray, Not limited.

The pKa of the acid generated by the photo-acid generator is not limited, but is preferably less than 3, more preferably less than 1.

As the photoacid generator, a known photoacid generator can be used. Examples of the photo-acid generator include, but are not particularly limited to, various compounds that are suitable in JP-A No. 2000-1648, JP-A No. 2001-515533, and International Publication No. 2002/83764. The photo-acid generator is preferably a sulfonate ester, a carboxylic acid ester, or an onium salt, and more preferably an onium salt.

As the sulfonate esters, various sulfonic acid derivatives can be used, for example, disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imide sulfonates such as trifluoromethyl sulfonate derivatives, Benzoin sulfonates, 1-oxy-2-hydroxy-3-propyl alcohol sulfonates, pyrogallol trisulfonates and benzyl sulfonates.

Specific examples of the sulfonate esters include diphenyldisulfone, ditosyldisulfone, bis(phenylsulfonyl)diazomethane, bis(chlorophenylsulfonyl)diazomethane, bis(xylylsulfonyl)diazomethane, phenylsulfonylbenzoyldiazomethane, bis(cyclohexylsulfonyl). ) Methane, 1,8-naphthalenedicarboxylic acid imide methyl sulfonate, 1,8-naphthalenedicarboxylic acid imide tosyl sulfonate, 1,8-naphthalenedicarboxylic acid imide trifluoromethyl sulfonate, 1,8-naphthalenedicarboxylic acid imide camphor sulfonate, amber Acid imide phenyl sulfonate, succinimide tosyl sulfonate, succinimide trifluoromethyl sulfonate, succinimide camphor sulfonate, phthalic acid trifluoro sulfonate, cis-5-norbornene-endo-2,3-dicarboxylic acid imide trifluoromethyl Sulfonate, benzoin tosylate, 1,2-diphenyl-2-hydroxypropyl tosylate, 1,2-di(4-methylmercaptophenyl)-2-hydroxypropyl tosylate, pyrogallol methyl sulfonate, pyrogallol ethyl sulfonate, 2,6 -Dinitrophenyl methyl tosylate, ortho-nitrophenyl methyl tosylate, para-nitrophenyl tosylate and the like.

These can be used alone or in combination of two or more. In the present invention, carboxylic acid esters can be similarly used as the photoacid generator.

Generally, sulfonic acid esters and carboxylic acid esters may require a heating step (50°C-100°C) to liberate the acid.

Examples of the onium salt include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl ⁻ ). ₆ ^-), tetraphenylborate, tetrakis (trifluoromethylphenyl) borate, tetrakis (pentafluorophenyl methylphenyl) borate, perchlorate ion (ClO ₄ ^-), trifluoromethanesulfonate ion _(CF 3 SO ₃ ^-), fluoro Examples thereof include sulfonium salts and iodonium salts having anions such as sulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, trinitrobenzenesulfonate anion and trinitrotoluenesulfonate anion.

Examples of the sulfonium salt include triphenylsulfonium hexafluoroacylnate, triphenylsulfonium hexafluoroborate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis(pentafluorobenzyl)borate, methyldiphenylsulfonium tetrafluoroborate, methyldiphenyl Sulfonium tetrakis(pentafluorobenzyl)borate, dimethylphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, diphenylnaphthylsulfonium hexafluoroarsenate, tritoylsulfonium hexafluorophosphate, anisyldiphenylsulfonium Hexafluoroantimonate, 4-butoxyphenyldiphenylsulfonium tetrafluoroborate, 4-butoxyphenyldiphenylsulfonium tetrakis(pentafluorobenzyl)borate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, tris(4-phenoxyphenyl)sulfonium hexafluoro Phosphate, di(4-ethoxyphenyl)methylsulfonium hexafluoroarsenate, 4-acetylphenyldiphenylsulfonium tetrafluoroborate, 4-acetylphenyldiphenylsulfonium tetrakis(pentafluorobenzyl)borate, tris(4-thiomethoxyphenyl)sulfonium hexa Fluorophosphate, di(methoxysulfonylphenyl)methylsulfonium hexafluoroantimonate, di(methoxynaphthyl)methylsulfonium tetrafluoroborate, di(methoxynaphthyl)methylsulfonium tetrakis(pentafluorobenzyl)borate, di(carbomethoxyphenyl)methylsulfonium Hexafluorophosphate, (4-octyloxyphenyl)diphenylsulfonium tetrakis(3,5-bis-trifluoromethylphenyl)borate, tris(dodecylphenyl)sulfonium tetrakis(3,5-bis-trifluoromethylphenyl)borate, 4 -Acetamidophenyldiphenylsulfonium tetrafluoroborate, 4-acetamidophenyldiphenylsulfonium tetrakis(pentafluorobenzyl)borate, dimethylnaphth Tylsulfonium hexafluorophosphate, trifluoromethyldiphenylsulfonium tetrafluoroborate, trifluoromethyldiphenylsulfonium tetrakis(pentafluorobenzyl)borate, phenylmethylbenzylsulfonium hexafluorophosphate, 10-methylphenoxathinium hexafluorophosphate, 5-methyl Thianthrenium hexafluorophosphate, 10-phenyl-9,9-dimethylthioxanthenium hexafluorophosphate, 10-phenyl-9-oxothioxanthenium tetrafluoroborate, 10-phenyl-9-oxothioxanthenium Tetrakis(pentafluorobenzyl)borate, 5-methyl-10-oxothianthrenium tetrafluoroborate, 5-methyl-10-oxothianthrenium tetrakis(pentafluorobenzyl)borate, and 5-methyl-10,10-di Oxo thianthrenium hexafluorophosphate etc. are mentioned. These can be used alone or in combination of two or more.

Examples of the iodonium salt include (4-n-decyloxyphenyl)phenyliodonium hexafluoroantimonate, [4-(2-hydroxy-n-tetradecyloxy)phenyl]phenyliodonium hexafluoroantimonate, [4-(2 -Hydroxy-n-tetradecyloxy)phenyl]phenyliodonium trifluorosulfonate, [4-(2-hydroxy-n-tetradecyloxy)phenyl]phenyliodonium hexafluorophosphate, [4-(2-hydroxy-n-tetra Decyloxy)phenyl]phenyliodonium tetrakis(pentafluorophenyl)borate, bis(4-t-butylphenyl)iodonium hexafluoroantimonate, bis(4-t-butylphenyl)iodonium hexafluorophosphate, bis(4-t- Butylphenyl)iodonium trifluorosulfonate, bis(4-t-butylphenyl)iodonium tetrafluoroborate, bis(dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrafluoroborate, bis(dodecylphenyl)iodonium hexa Fluorophosphate, bis(dodecylphenyl)iodonium trifluoromethyl sulfonate, di(dodecylphenyl)iodonium hexafluoroantimonate, di(dodecylphenyl)iodonium triflate, diphenyliodonium bisulfate, 4,4′-dichlorodiphenyliodonium bisulfate, 4, ,4'-dibromodiphenyliodonium bisulfate, 3,3'-dinitrodiphenyliodonium bisulfate, 4,4'-dimethyldiphenyliodonium bisulfate, 4,4'-bissuccinimidodiphenyliodonium bisulfate, 3-nitrodiphenyliodonium bisulfate Fate, 4,4′-dimethoxydiphenyliodonium bisulfate, bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate, (4-octyloxyphenyl)phenyliodonium tetrakis(3,5-bis-trifluoromethylphenyl)borate is disclosed in U.S. Patent No. 5554664 (Torirukumiru) iodonium tetrakis (pentafluorophenyl) borate _{(CH 3 C 6 H 4)} 2 I- (SO 2 CF 3) 3 , Such as those disclosed in U.S. disclosed in Japanese Patent No. _{5514728 (C 6 H 5) 2} I-B (C 6 F 5) 4, and U.S. Patent No. 5,340,898 and the like. These can be used alone or in combination of two or more.

As the other onium salt, an aromatic diazonium salt can be used, and for example, p-methoxybenzenediazonium hexafluoroantimonate can be used.

The commercially available onium salts include San-Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI-L150, SI-L160, SI-. L110 and SI-L147 (above, Sanshin Chemical Industry Co., Ltd.), UVI-6950, UVI-6970, UVI-6974 and UVI-6990 (above, Union Carbide Co., Ltd.), ADEKA OPTOMER SP-150, SP -151, SP-170, SP-171 and SP-172 (all manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacure 261 (manufactured by Ciba Specialty Chemicals Co., Ltd.), CI-2481, CI-2624, CI-2639 and CI-2064 (all manufactured by Nippon Soda Co., Ltd.), CD-1010, CD-1011 and CD-1012 (all manufactured by Sartomer), DS-100, DS-101, DAM-101, DAM-102, DAM. -105, DAM-201, DSM-301, NAI-100, NAI-101, NAI-105, NAI-106, SI-100, SI-101, SI-105, SI-106, PI-105, NDI-105. , BENZOIN TOSYLATE, MBZ-101, MBZ-301, PYR-100, PYR-200, DNB-101, NB-101, NB-201, BBI-101, BBI-102, BBI-103 and BBI-109 (above, Midori Kagaku Co., Ltd., PCI-061T, PCI-062T, PCI-020T and PCI-022T (above, Nippon Kayaku Co., Ltd.), IBPF and IBCF (Sanwa Chemical Co., Ltd.), UVE1014 ( General Electronics Co., Ltd.), RHODORSIL-PI2074 (manufactured by Rhodia), and the like.

As an anion species, for example, BBI-103 has SbF ₆ ⁻ , BBI-102 and SP-150 have PF ₆ ⁻ , and RHODORSIL-PI2074 has B(C ₆ F ₅ ) ₄ ⁻ .

Further, as the above-mentioned onium salt, J. Polymer Science: Part A: polymer Chemistry, Vol. 31, 1473-1482 (1993), J. Am. Polymer Science: Part A: polymer Chemistry, Vol. It is also possible to use diaryliodonium salts which can be prepared by the method described in 31, 1483-1491 (1993).

The content of the photo-acid generator in the negative photosensitive resin composition is not particularly limited, but from the viewpoint of curability, it is 0.01 to 10 parts by weight with respect to 100 parts by weight of the component (A). Is preferable, and from the viewpoint of the balance of physical properties of the cured product, 0.1 to 5.0 parts by weight is more preferable. If the amount of the photo-acid generator is small, it may take a long time to cure or a sufficiently cured product may not be obtained. Further, when the amount of the photo-acid generator is large, the color remains in the cured product, or the rapid curing causes the coloring or the heat resistance or the light resistance to be impaired, which is not preferable in some cases.

<1-4. Cationic polymerization initiator>
The negative photosensitive resin composition may contain a cationic polymerization initiator. The cationic polymerization initiator is not particularly limited as long as it is an active energy ray cationic polymerization initiator that generates a cationic species or a Lewis acid by an active energy ray, or a thermal cationic polymerization initiator that generates a cationic species or a Lewis acid by heat. It can be used without being used. The photo-polymerizable functional group contained in the component (A) can be cross-linked with the cationic species or the Lewis acid.

Examples of the active energy ray cationic polymerization initiator include metal fluoroboron complex salts and boron trifluoride complex compounds as described in US Pat. No. 3,379,653; bis(perfluoro) as described in US Pat. No. 3,586,616. Alkylsulfonyl)methane metal salts; aryl diazonium compounds as described in US Pat. No. 3,708,296; aromatic onium salts of Group VIa elements as described in US Pat. No. 4,058,400; described in US Pat. No. 4,690,055. Aromatic onium salts of Group Va elements as described above; Dicarbonyl chelates of Group IIIa to Va as described in US Pat. No. 4,680,091; Thiopyrylium salts as described in US Pat. No. 4,139,655; US Pat. Group VIa elements in the form of MF ₆ ^- anions as described in US Pat. No. 4,161,478, where M is selected from phosphorus, antimony and arsenic; arylsulfonium complex salts as described in US Pat. No. 4,231,951; Aromatic iodonium complex salts and aromatic sulfonium complex salts as described in U.S. Pat. No. 4,256,828; R. Bis[4-(diphenylsulfonio)phenyl]sulfide-bishexafluoro as described by Watt et al. in "Journal of Polymer Science, Polymer Chemistry Edition", Vol. 22, p. 1789 (1984). Examples thereof include metal salts (for example, phosphates, arsenates, antimonates, etc.); aromatic iodonium complex salts and aromatic sulfonium complex salts in which the anion is B(C ₆ F ₅ ) ₄ ⁻ .

Preferred cationic active energy ray cationic polymerization initiators include arylsulfonium complex salts, aromatic sulfonium salts and iodonium salts of halogen-containing complex ions, and aromatic onium salts of group II, group V and group VI elements. Some of these salts are FX-512 (3M), UVR-6990 and UVR-6974 (Union Carbide), UVE-1014 and UVE-1016 (General Electric), KI-85. (Manufactured by Degussa) and SP-152 and SP-172 (manufactured by Asahi Denka Co., Ltd.).

Examples of the thermal cationic polymerization initiator include sulfonium salts, ammonium salts, pyridinium salts, phosphonium salts, iodonium salts, trifluoro acid salts, boron trifluoride ether complex compounds, and cationic or protic acid catalysts such as boron trifluoride. Can be mentioned. It can be said that the above-mentioned thermal cationic polymerization initiator is a latent curing catalyst because it has high stability until a cationic species is generated by heating. The thermal cationic polymerization initiator has a polymerization activity which varies depending on the type of substituent and the type of anion of the onium salt, and in particular, for anion, BF ⁻ <AsF ₆ ⁻ <PF ₆ ⁻ <SbF ₆ ⁻ <B. _(C 6 _{F 5) 4} ^- order in polymerization activity is known to be higher. In addition, it is known that an aluminum complex and a silanol compound, an aluminum complex and a specific phenol compound such as bisphenol S serve as a cationic polymerization catalyst.

Among the aromatic onium salts that are also used as the active energy ray cationic polymerization initiator, there are those that generate a cationic species by heat, and these can also be used as the thermal cationic polymerization initiator. Examples thereof include San-Aid SI-60L, SI-80L and SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.), and RHODORSIL PI2074 (manufactured by Rhodia). Among these cationic polymerization initiators, aromatic onium salts are preferable because they are excellent in handleability and the balance between latency and curability.

The amount of the cationic polymerization initiator used is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the component (A). When the amount of the cationic polymerization initiator is small, it may take a long time to cure or a sufficiently cured product may not be obtained. When the amount of the cationic polymerization initiator is large, the color of the initiator may remain in the cured product, may be colored or bulge due to rapid curing, or the heat and light resistance of the cured product may be impaired, which is not preferable in some cases.

<1-5. Radical polymerization initiator>
The negative photosensitive resin composition may contain a radical polymerization initiator. The above radical polymerization initiator is not particularly limited as long as it is an active energy ray radical polymerization initiator that generates a radical species by an active energy ray or a thermal radical polymerization initiator that generates a radical species by heat. The photopolymerizable functional group contained in the component (A) can be crosslinked by the radical species.

Examples of the active energy ray radical polymerization initiator include acetophenone compounds, benzophenone compounds, acylphosphine oxide compounds, oxime ester compounds, benzoin compounds, biimidazole compounds, α-diketone compounds, titanocene compounds, and polynuclear compounds. Quinone compounds, xanthone compounds, thioxanthone compounds, triazine compounds, ketal compounds, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, thiuram compounds and fluoroamine compounds Is mentioned.

Specific examples of the acetophenone compound include 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone and 2-hydroxy-2-methyl. -1-Phenylpropan-1-one, 1-(4'-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2'-hydroxyethoxy)phenyl(2-hydroxy- 2-propyl)ketone, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1-(4'-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2. -Dimethylamino-1-(4'-morpholinophenyl)butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one and 2-hydroxy-1- [4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl]-2-methyl-propan-1-one and the like can be mentioned.

Specific examples of the benzophenone compound include benzyl dimethyl ketone, benzophenone, 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone.

Specific examples of the acylphosphine oxide-based compound include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

Specific examples of the oxime ester compound include 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyloxime)] and ethanone 1-[9-ethyl-6-(2-methyl). Benzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) and the like.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and methyl 2-benzoylbenzoate.

Specific examples of the above-mentioned biimidazole compound include 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetrakis(4-ethoxycarbonylphenyl)-1,2′-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole,2,2'-bis(2,2 4,6-Trichlorophenyl)-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(2,4-dibromophenyl)-4,4',5,5'- Tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetrakis(4-ethoxy) Carbonylphenyl)-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'-tetraphenyl-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'-bi Imidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis(2,4,6) -Tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and the like.

Specific examples of the α-diketone compound include diacetyl, dibenzoyl and methylbenzoyl formate.

Specific examples of the polynuclear quinone compound include anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1,4-naphthoquinone.

Specific examples of the xanthone compounds include xanthone, thioxanthone, 2-chlorothioxanthone, and 2,5-diethyldioxanthone.

Specific examples of the triazine-based compound include 1,3,5-tris(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, and 1; ,3-Bis(trichloromethyl)-5-(4'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-methoxyphenyl)-s-triazine, 1,3- Bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(2'-furylethylidene)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'- Methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4' -Methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-bromo-4'-methylphenyl)-4,6-bis(trichloromethyl)-s-triazine and 2- (2'-thiophenylethylidene)-4,6-bis(trichloromethyl)-s-triazine and the like can be mentioned.

Particularly from the viewpoint of excellent thin film curability, the active energy ray radical polymerization initiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-Hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl]-2-methyl-propan-1-one, 1,2-octanedione 1-[4- (Phenylthio)-2-(O-benzoyloxime)] or ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime). Preferably.

In particular, from the viewpoint that the cured product is excellent in transparency, the active energy ray radical polymerization initiator is 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1. -Phenylpropan-1-one, 1-(4'-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2'-hydroxyethoxy)phenyl (2-hydroxy-2- It is preferably propyl)ketone or 2,2-dimethoxyacetophenone.

Specific examples of the thermal radical polymerization initiator include diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), hydroperoxides (hydrogen peroxide). , Tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyesters (tert-butylperoxy) Acetate, tert-butyl peroxypivalate, etc.), azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.) and persulfates (ammonium persulfate, sodium persulfate, potassium persulfate, etc.) Can be mentioned.

As these radical polymerization initiators, one type may be used, or two or more types may be used in combination.

The amount of the radical polymerization initiator used is preferably 0.1 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the component (A). When the amount of the cationic polymerization initiator is small, the curing tends to be insufficient and the contrast tends not to be obtained at the alkali development. If the amount of the cationic polymerization initiator is large, the cured film itself may be colored, which may not be preferable.

<1-6. Other additives>
(Crosslinking agent)
A cross-linking agent having two or more photopolymerizable functional groups in one molecule may be added to the negative photosensitive resin composition in order to adjust workability, reactivity, adhesiveness and cured product strength. it can. The cross-linking agent is not particularly limited as long as it is selected according to the curing reaction type, and examples thereof include an epoxy compound, an oxetane compound, an alkoxysilane compound and a (meth)acrylate compound.

Specific examples of the epoxy compound and the oxetane compound include novolac phenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, cyclohexylepoxy group-containing polyorganosiloxane (cyclic or chain), glycidyl group-containing polyorgano. Siloxane (cyclic or chain), bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 2,2'-bis(4-glycidyloxycyclohexyl)propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbo Xylate, vinyl cyclohexene dioxide, 2-(3,4-epoxycyclohexyl)-5,5-spiro-(3,4-epoxycyclohexane)-1,3-dioxane, bis(3,4-epoxycyclohexyl) adipate , 1,2-Cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, 1,4-bis{(3-ethyl-3-oxetanyl)methoxy}methyl} Examples thereof include benzene, bis{1-ethyl(3-oxetanyl)}methyl ether, 3-ethyl-3-(phenoxymethyl)oxetane and 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane.

Specific examples of the alkoxysilane compound include tetramethoxy(ethoxy)silane and its condensate, methyltrimethoxy(ethoxy)silane and its condensate, dimethyldimethoxy(ethoxy)silane and its condensate, and the like.

Specific examples of the (meth)acrylate compound include allyl (meth)acrylate, vinyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, (meth)acrylic. Acid-modified allyl glycidyl ether (Nagase Chemtex, trade name: Denacol acrylate DA111), urethane (meth)acrylates, epoxy (meth)acrylates, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate , Ditrimethylolpropane (meth) tetraacrylate, dipentaerythritol hexa(meth) acrylate, butanediol di(meth) acrylate, nonanediol di(meth) acrylate, polypropylene glycol-based (meth) acrylate, bisphenol A di(meth) acrylate , Tris(2-(meth)acryloyloxyethyl)isocyanurate, (meth)acrylate group-containing polyorganosiloxane, and the like.

The amount of the cross-linking agent added may be appropriately set, but is preferably 1 to 50 parts by weight, and more preferably 3 to 25 parts by weight with respect to 100 parts by weight of the component (A). If the addition amount of the cross-linking agent is small, the addition effect is not exhibited, and if the addition amount of the cross-linking agent is large, the physical properties of the cured product may be adversely affected.

(Sensitizer)
The negative photosensitive resin composition may contain a sensitizer. The above-mentioned sensitizer can improve the sensitivity to visible light and the like in the above negative-type photosensitive resin composition, and further, g-line (436 nm), h-line (405 nm), i-line (365 nm), etc. It is possible to add sensitivity to the high wavelength light. By using these sensitizers in combination with the above-mentioned cationic polymerization initiator, radical polymerization initiator, photoacid generator, etc., the curability of the negative photosensitive resin composition can be adjusted. it can.

Examples of the sensitizer include anthracene compounds and thioxanthone compounds.

Specific examples of the anthracene-based compound include anthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-. Diethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 2-tert-butylanthracene, 2,6-di-tert-butylanthracene, 9,10-diphenyl-2,6-di -Tert-butylanthracene and the like can be mentioned. From the viewpoint of easy availability, anthracene compounds such as anthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-diethoxyanthracene are preferable.

As the above-mentioned anthracene compound, anthracene is preferable from the viewpoint of excellent transparency of the cured product, and 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene and 9 from the viewpoint of excellent compatibility with the curable composition. , 10-diethoxyanthracene and the like are preferable.

Specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, and 2,5-diethyldioxanthone.

These sensitizers may be used alone or in combination of two or more.

The content of the sensitizer in the curable composition of the present invention is not particularly limited as long as it can exert the sensitizing effect, but the added initiator (photoacid generator, cationic polymerization initiator or radical polymerization initiation It is preferably 0.01 to 300 mol, more preferably 0.1 to 100 mol, per 1 mol of the agent). When the amount of the sensitizer is small, the sensitizing effect cannot be obtained, and it may take a long time for curing or may adversely affect the developability. On the other hand, when the amount of the sensitizer is large, the color may remain in the cured product, coloring may occur due to rapid curing, or heat resistance or light resistance may be impaired.

(Reactivity modifier)
When the negative photosensitive resin composition is used as a radical curing system, the negative photosensitive resin composition contains a reactivity modifier for the purpose of reactivity adjustment and suppression of curing inhibition by oxygen. Good. Examples of the reactivity modifier include thiol compounds, amine compounds and phosphine compounds.

Specific examples of the thiol compound include tri(3-mercaptopropionyloxy)-ethyl)isocyanurate, trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol-. 3-mercaptopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1. , 3,5-triazine-2,4,6 trione and mercapto group-containing polyorganosiloxane (KF2001 and KF2004 manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

Among the above thiol compounds, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6trione and tri(3) are particularly preferred from the viewpoint of excellent heat resistance. -Mercaptopropionyloxy)-ethyl)isocyanurate and mercapto group-containing polyorganosiloxane (KF2001 and KF2004 manufactured by Shin-Etsu Chemical Co., Ltd.) are preferable.

Specific examples of the phosphine compound include triphenylphosphine and tributylphosphine.

(Adhesion improver)
The negative photosensitive resin composition may contain an adhesion improver. As the adhesiveness improver, in addition to commonly used adhesives, for example, various coupling agents, epoxy compounds, oxetane compounds, phenol resins, coumarone-indene resins, rosin ester resins, terpene-phenol resins, α-methylstyrene. -Vinyltoluene copolymer, polyethylmethylstyrene, aromatic polyisocyanate and the like can be mentioned.

Examples of the coupling agent include silane coupling agents. The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and at least one hydrolyzable silicon group in the molecule. As the group reactive with the organic group, at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group and a carbamate group is preferable from the viewpoint of handleability, and curing From the viewpoints of properties and adhesiveness, an epoxy group, a methacrylic group or an acrylic group is particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group or an ethoxysilyl group is particularly preferable from the viewpoint of reactivity.

Preferred silane coupling agents are 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 2-(3,4- Epoxycyclohexyl)alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Examples thereof include alkoxysilanes having a methacrylic group or an acryl group such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane and acryloxymethyltriethoxysilane.

The addition amount of the silane coupling agent can be appropriately set, but is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 10 parts by weight, relative to 100 parts by weight of the compound having a photopolymerizable functional group. It is more preferably 0.5 to 5 parts by weight. If the added amount is small, the effect of improving the adhesiveness is not exhibited, and if the added amount is large, the curability and the physical properties of the cured product may be adversely affected.

Moreover, as these coupling agents, silane coupling agents, epoxy compounds, etc., one type may be used, or two or more types may be used in combination.

At least one of carboxylic acids and acid anhydrides can be used for improving and/or stabilizing the adhesiveness by the coupling agent or the epoxy compound. The carboxylic acids and acid anhydrides are not particularly limited, but include 2-ethylhexanoic acid, cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, methylcyclohexanedicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylhymic acid, norbornenedicarboxylic acid. Acid, hydrogenated methyl nadic acid, maleic acid, acetylenedicarboxylic acid, lactic acid, malic acid, citric acid, tartaric acid, benzoic acid, hydroxybenzoic acid, cinnamic acid, phthalic acid, trimellitic acid, pyromellitic acid, naphthalenecarboxylic acid, Examples thereof include naphthalenedicarboxylic acid, and single or complex acid anhydrides thereof.

Among these carboxylic acids and acid anhydrides, for example, tetrahydrophthalic acid, methyltetrahydrophthalic acid, and their individual or complex acid anhydrides are preferable from the viewpoint of not impairing the physical properties of the resulting cured product.

The amount of the carboxylic acids and acid anhydrides used may be appropriately set, but is preferably 0.1 to 50 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the coupling agent and the epoxy compound. Is. If the added amount is small, the effect of improving the adhesiveness is not exhibited, and if the added amount is large, the physical properties of the cured product may be adversely affected.

Moreover, as these carboxylic acids and acid anhydrides, 1 type may be used and 2 or more types may be used together.

(Phosphorus compound)
In the case of curing the negative photosensitive resin composition by light or heat, particularly when used in an application requiring transparency, in order to improve the hue after curing by light or heat, the negative It is preferable to add a phosphorus compound to the mold-type photosensitive resin composition.

Specific examples of the phosphorus compound include triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, tris(nonylphenyl)phosphite, diisodecylpentaerythritol diphosphite, tris(2,4-di-t- Butylphenyl)phosphite, cyclic neopentanetetraylbis(octadecylphosphite), cyclic neopentanetetraylbis(2,4-di-t-butylphenyl)phosphite, cyclic neopentanetetraylbis(2 ,6-di-t-butyl-4-methylphenyl)phosphite and bis[2-t-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogenphosphite and the like. Antioxidants selected from phytes, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9 Oxaphosphaphenanthrene oxides such as 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Coloring inhibitors selected from

The amount of the phosphorus compound used is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the component (A). When the amount of the phosphorus compound used is less than 0.01 parts by weight, the effect of improving the hue is reduced. If the amount of the phosphorus compound used exceeds 10 parts by weight, the curability and the physical properties of the cured product may be adversely affected.

(Thermoplastic resin)
Various thermoplastic resins may be added to the negative photosensitive resin composition for the purpose of modifying the properties of the negative photosensitive resin composition. As the thermoplastic resin, for example, a homopolymer of methyl methacrylate or a random of methyl methacrylate and another monomer, a block, or a polymethylmethacrylate resin such as a graft polymer (for example, Optretz manufactured by Hitachi Chemical Co., Ltd.) and Acrylic resin represented by polybutyl acrylate resin such as homopolymer of butyl acrylate or random, block or graft polymer of butyl acrylate and other monomer, bisphenol A, 3,3,5-trimethylcyclohexyl Polycarbonate resins such as polycarbonate resins containing silidene bisphenol etc. as a monomer structure (for example, APEC manufactured by Teijin Ltd.), norbornene derivatives, resins obtained by homopolymerizing or copolymerizing vinyl monomers, and resins obtained by ring-opening metathesis polymerization of norbornene derivatives. Or a cycloolefin resin such as a hydrogenated product thereof (for example, APEL manufactured by Mitsui Chemicals, ZEONOR, ZEONEX manufactured by Nippon Zeon Co., ARTON manufactured by JSR Co., etc.), and an olefin-maleimide resin such as a copolymer of ethylene and maleimide. Resins (such as TI-PAS manufactured by Tosoh Corporation), bisphenols (bisphenol A and bis(4-(2-hydroxyethoxy)phenyl)fluorene) or diols (diethylene glycol etc.), and phthalic acids (terephthalic acid and isophthalic acid) Etc.) or polyester resins such as polyesters polycondensed with aliphatic dicarboxylic acids (for example, O-PET manufactured by Kanebo Co., Ltd.), polyether sulfone resins, polyarylate resins, polyvinyl acetal resins, polyethylene resins, polypropylene resins, polystyrene. In addition to resins, polyamide resins, silicone resins, fluororesins, and the like, rubber-like resins such as natural rubber and EPDM can be cited, but not limited to these.

The thermoplastic resin may have a crosslinkable group. Examples of the crosslinkable group include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group and an alkoxysilyl group. From the viewpoint that the heat resistance of the obtained cured product is likely to be high, the thermoplastic resin preferably has one or more crosslinkable groups in one molecule on average.

The molecular weight of the thermoplastic resin is not particularly limited, but the number average molecular weight is preferably 10,000 or less and preferably 5,000 or less from the viewpoint that compatibility with the polysiloxane compound is likely to be good. Is more preferable. On the other hand, the number average molecular weight is preferably 10,000 or more, and more preferably 100,000 or more, from the viewpoint that the obtained cured product is likely to be tough. The molecular weight distribution is not particularly limited, but from the viewpoint that the viscosity of the mixture is low and the moldability is likely to be good, the molecular weight distribution is preferably 3 or less, more preferably 2 or less, and 1.5 The following is more preferable.

The blending amount of the above-mentioned thermoplastic resin is not particularly limited, but is preferably 5 to 50% by weight, more preferably 10 to 30% by weight, based on the whole negative photosensitive resin composition. If the amount of the thermoplastic resin added is small, the obtained cured product may become brittle. When the amount of the thermoplastic resin added is large, the heat resistance (elastic modulus at high temperature) tends to be low.

A single thermoplastic resin may be used, or a plurality of thermoplastic resins may be used in combination.

The thermoplastic resin may be dissolved in the polysiloxane compound and mixed in a uniform state, may be pulverized and mixed in a particle state, or may be dissolved in a solvent and mixed to be in a dispersed state. .. From the viewpoint that the obtained cured product is more likely to be transparent, it is preferable to dissolve it in a polysiloxane compound and mix it in a uniform state. Also in this case, the thermoplastic resin may be directly dissolved in the polysiloxane compound, may be uniformly mixed by using a solvent, or the like, and thereafter the solvent may be removed to obtain a uniform dispersed state or mixed state. ..

When the thermoplastic resin is dispersed and used, the average particle diameter of the thermoplastic resin can be appropriately set, but the lower limit of the preferable average particle diameter is 10 nm, and the upper limit of the preferable average particle diameter is 10 μm. The particle system may have a distribution, and may have a single dispersion or a plurality of peak particle sizes, but from the viewpoint that the viscosity of the curable composition is low and the moldability tends to be good, the particles are The variation coefficient of diameter is preferably 10% or less.

(Filling material)
A filler may be added to the negative photosensitive resin composition as needed.

Various fillers may be used, for example, silica-based fillers (quartz, fume silica, precipitated silica, silicic acid anhydride, fused silica, crystalline silica, ultrafine amorphous silica, etc.), silicon nitride, Inorganic fillers such as silver powder, alumina, aluminum hydroxide, titanium oxide, glass fiber, carbon fiber, mica, carbon black, graphite, diatomaceous earth, clay, clay, talc, calcium carbonate, magnesium carbonate, barium sulfate and inorganic balloons First of all, a filler generally used or proposed as a filler for a conventional encapsulant, such as an epoxy-based filler, can be mentioned.

(Anti-aging agent)
An antioxidant may be added to the negative photosensitive resin composition. Examples of the antiaging agent include commonly used antiaging agents such as hindered phenol antiaging agents, citric acid, phosphoric acid, and sulfur antiaging agents.

As the hindered phenol-based antiaging agent, various kinds can be used, including Irganox 1010 available from Ciba Specialty Chemicals.

Examples of the sulfur-based antioxidant include mercaptans, mercaptan salts, sulfides (sulfide carboxylic acid esters and hindered phenol sulfides, etc.), polysulfides, dithiocarboxylic acid salts, thioureas, thiophosphates, Examples thereof include sulfonium compounds, thioaldehydes, thioketones, mercaptars, mercaptors, monothio acids, polythio acids, thioamides and sulfoxides.

Moreover, as these antioxidants, 1 type may be used and 2 or more types may be used together.

(Radical inhibitor)
A radical inhibitor may be added to the negative photosensitive resin composition. Examples of the radical inhibitor include 2,6-di-t-butyl-3-methylphenol (BHT), 2,2′-methylene-bis(4-methyl-6-t-butylphenol) and tetrakis(methylene-). Phenolic radical inhibitors such as 3(3,5-di-t-butyl-4-hydroxyphenyl)propionate)methane, and phenyl-β-naphthylamine, α-naphthylamine, N,N′-secondary-butyl-p- Examples include amine radical inhibitors such as phenylenediamine, phenothiazine and N,N'-diphenyl-p-phenylenediamine.

Moreover, as these radical inhibitors, 1 type may be used and 2 or more types may be used together.

(UV absorber)
An ultraviolet absorber may be added to the negative photosensitive resin composition. Examples of the ultraviolet absorber include 2(2′-hydroxy-3′,5′-di-t-butylphenyl)benzotriazole and bis(2,2,6,6-tetramethyl-4-piperidine)sebacate. Is mentioned.

Moreover, as these ultraviolet absorbers, 1 type may be used and 2 or more types may be used together.

(solvent)
When the polysiloxane compound (A) has a high viscosity, it can be used by dissolving it in a solvent. The solvent is not particularly limited, and specifically, a hydrocarbon solvent such as benzene, toluene, hexane and heptane; an ether solvent such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane and diethyl ether. Solvents; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; glycol solvents such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA) and ethylene glycol diethyl ether; chloroform, methylene chloride and 1,2 -Halogen-based solvents such as dichloroethane and the like.

From the viewpoint of hydrosilylation reactivity, toluene, tetrahydrofuran, 1,3-dioxolane, propylene glycol-1-monomethyl ether-2-acetate and chloroform are preferable as the solvent.

The amount of the solvent used can be set appropriately, but the lower limit of the amount used is preferably 0.1 mL, and the upper limit of the amount used is preferably 10 mL, per 1 g of the negative photosensitive resin composition used. When the amount of the solvent used is small, it may be difficult to obtain the effect of using the solvent such as lowering the viscosity. In addition, when the amount of the solvent used is large, the solvent may remain in the material to cause problems such as heat cracks, and it may be disadvantageous in terms of cost and may reduce the industrial utility value.

As these solvents, one kind may be used, or two or more kinds may be used as a mixed solvent.

(Other)
The negative photosensitive resin composition includes a colorant, a release agent, a flame retardant, a flame retardant aid, a surfactant, a defoaming agent, an emulsifier, a leveling agent, an anti-repellent agent, an ion trap agent (antimony-bismuth). Etc.), thixotropic agent, tackifier, storage stability improver, antiozonant, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, heat stabilizer, conductivity The purpose and effect of the present invention include an imparting agent, an antistatic agent, a radiation blocking agent, a nucleating agent, a phosphorus-based peroxide decomposing agent, a lubricant, a pigment, a metal deactivator, a thermal conductivity imparting agent and a physical property adjusting agent. Can be added within a range that does not impair

[2. Preparation method and curing method of negative photosensitive resin composition]
The method for preparing the negative photosensitive resin composition is not particularly limited and can be prepared by various methods. The various components may be mixed and prepared immediately before curing, or all components may be mixed and prepared in advance and stored at low temperature in a single liquid state.

As a light source for photo-curing the negative photosensitive resin composition, a light source that emits the absorption wavelength of the polymerization initiator and the sensitizer used may be used, and usually includes a wavelength in the range of 200 to 450 nm. A light source (for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a high power metal halide lamp, a xenon lamp, a carbon arc lamp or a light emitting diode) can be used.

The exposure dose for photocuring the negative photosensitive resin composition is not particularly limited, but is preferably 1 to 5000 mJ/cm ² , and more preferably 1 to 1000 mJ/cm ² . If the exposure dose is low, the negative photosensitive resin composition may not be cured. If the amount of exposure is large, the color may change due to rapid curing. The curing time range is preferably 30 to 120 seconds, more preferably 1 to 60 seconds. If the curing time is long, the feature of fast curing that photocuring has cannot be utilized.

For the purpose of removing the solvent and improving the physical properties of the cured product, heat may be applied before and after photocuring to perform pre-baking and after-baking. The curing temperature can be set appropriately, but is preferably 60 to 400°C, more preferably 90 to 350°C.

The cured product thus obtained (that is, the cured product obtained by curing the negative photosensitive resin composition) is also included in the present invention.

[3. Laminate)
The negative photosensitive resin composition can be handled in a liquid state, and a thin film can be easily formed by solution coating. Therefore, a laminate can be easily formed by layer-hardening the negative photosensitive resin composition on a substrate. In other words, the laminate has a cured film obtained by curing the negative photosensitive resin composition on the base material.

The said laminated body may be specifically produced by the following methods, for example. First, the negative photosensitive resin composition is applied onto a substrate. Examples of the base material include glasses, polycarbonates, films, silicon wafers on which image pickup devices are formed, patterned colored resin films of LCD or CCD color filters, printing paper, printing fibers and metal plates. Is mentioned. Examples of the coating method include a spin coating method, a roll coating method, a printing method and a bar coating method. The applied film thickness is usually 0.05 to 100 μm, preferably 0.1 to 50 μm, and more preferably 0.5 to 20 μm. Next, a laminate can be obtained by performing exposure with active energy rays.

The substrate may have a silicon nitride layer on the surface. When the base material has a silicon nitride layer on the surface, it is possible to provide a laminate having excellent gas barrier properties and hardness, which is preferable. Further, with the above-mentioned negative photosensitive resin composition, excellent adhesion and chemical resistance can be realized without impairing patterning property even on a substrate having a silicon nitride layer on the surface.

The laminate thus obtained can then be developed with an alkaline developer, as described below.

[4. Alkali development method]
There is no particular limitation on the patterning formation by alkali development, and a desired pattern can be formed by dissolving and removing the unexposed portion by a commonly used developing method such as an immersion method or a spray method.

In addition, the developer used in the alkali development can be used without particular limitation as long as it is a commonly used developer. Specific examples of the developing solution include organic alkali aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solution and choline aqueous solution, potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium carbonate aqueous solution, sodium carbonate aqueous solution and lithium carbonate aqueous solution. An inorganic alkaline aqueous solution and the like can be mentioned. The aqueous solution may contain alcohol, a surfactant and the like in order to adjust the dissolution rate and the like.

The concentration of the aqueous solution is preferably 25% by weight or less, more preferably 10% by weight or less, and further preferably 5% by weight or less, from the viewpoint of easy contrast between exposed and unexposed areas. ..

[5. Use]
The negative photosensitive resin composition and the cured product thereof can be used for various purposes. It can be applied to various applications in which conventional acrylic resin and epoxy resin adhesives are used.

Examples of the applications include transparent materials, optical materials, optical lenses, optical films, optical sheets, adhesives for optical components, optical adhesives for optical waveguide coupling, adhesives for fixing optical waveguide peripheral members, and adhesives for DVD bonding. Agents, adhesives, dicing tapes, electronic materials, insulating materials (including printed circuit boards, wire coatings, etc.), high-voltage insulating materials, interlayer insulating films, TFT passivation films, TFT gate insulating films, TFT interlayer insulating films, Transparent flattening film for TFT, insulation packing, insulation coating, adhesive, high heat resistance adhesive, high heat dissipation adhesive, optical adhesive, LED element adhesive, various substrate adhesive, heat sink adhesive , Paints, UV powder coatings, inks, coloring inks, UV inkjet inks, coating materials (including hard coats, sheets, films, release paper coats, optical disk coats, optical fiber coats, etc.), molding materials (sheets) , Film, FRP, etc.), sealing material, potting material, sealing material, light emitting diode sealing material, optical semiconductor sealing material, liquid crystal sealing agent, display device sealing agent, electrical material sealing material, various Solar cell sealing material, high heat resistant sealing material, resist material, liquid resist material, colored resist, dry film resist material, solder resist material, binder resin for color filter, transparent flattening material for color filter, binder resin for black matrix , Photo spacer material for liquid crystal cell, transparent encapsulating material for OLED element, stereolithography, solar cell material, fuel cell material, display material, recording material, anti-vibration material, waterproof material, moisture-proof material, heat-shrinkable rubber tube, Examples include O-rings, photosensitive drums for copiers, solid electrolytes for batteries, gas separation membranes, concrete protective materials, linings, soil injecting agents, cold storage materials, sealants for sterilization equipment, contact lenses and oxygen permeable membranes. Further, the negative photosensitive resin composition may be used as an additive to other resins.

Among them, the negative photosensitive resin composition is a material that can be used as an alkali-developable transparent resist, and is particularly suitable as a material for FPD. Examples of the FPD material include a TFT passivation film, a TFT gate insulating film, a TFT interlayer insulating film, a TFT transparent flattening film, a color filter binder resin, a color filter transparent flattening material, and a black matrix binder resin. , A liquid crystal cell photo spacer material, an OLED element transparent sealing material, and the like.

The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims, and the embodiments obtained by appropriately combining the technical means disclosed in the different embodiments. Is also included in the technical scope of the present invention.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the following examples.

(Patterning property evaluation)
The following patterning property evaluation samples were prepared using the resin compositions obtained in the examples and comparative examples. First, a silicon nitride film was formed on glass to prepare a substrate. Next, the resin composition obtained in each of Examples and Comparative Examples was spin-coated on the substrate. The obtained substrate was heated on a hot plate heated to 100° C. for 2 minutes. Further, using an exposure device (high-pressure mercury lamp, manual exposure device, manufactured by Dainippon Kaken Co., Ltd.), each resin composition is exposed with an optimum integrated light amount through a mask having a line and space pattern of 5 μm engraved (software. Contact exposure) and left for 1 minute after exposure. After that, it was immersed in an alkaline developer (TMAH 2.38% aqueous solution) for 80 seconds, washed with water for 30 seconds, and water on the surface was removed with compressed air or compressed nitrogen to form a pattern.

Then, it heated for 30 minutes on the hot plate heated at 230 degreeC, and obtained the patterning property evaluation sample. Regarding the obtained patterning property evaluation sample, the pattern shape was observed using a 3D measurement laser microscope (LEXT OLS4000, manufactured by Olympus) and a stylus type surface shape measuring device (Dektak 150, manufactured by Veeco), and 5 μm line and space The state was evaluated according to the following criteria.

<Evaluation criteria>
◯: No residual film on 5 μm line and space.
X: There is a residual film on the line and space of 5 μm.

(Substrate adhesion evaluation)
A substrate adhesion evaluation sample was obtained in the same manner as the patterning evaluation sample, except that exposure was performed through a mask having 10 μm and 20 μm line and space patterns in place of the mask having 5 μm line and space patterns. It was

The obtained substrate adhesion evaluation sample was immersed in a resist stripping solution (TOK106, manufactured by Tokyo Ohka) for 120 minutes at 70° C., and then the pattern shape was observed using a 3D measurement laser microscope (LEXT OLS4000, manufactured by Olympus). The state of 10 μm and 20 μm line and space was evaluated according to the following criteria.

<Evaluation criteria>
⊚: No peeling in 10 μm line and space.
◯: No peeling in 20 μm line and space.
×: There was peeling in the line and space of 20 μm.

(Evaluation of residual film rate)
A residual film rate evaluation sample was obtained in the same manner as the patterning property evaluation sample, except that the exposure was performed through a mask having a 100 μm line and space pattern engraved in place of the mask having a 5 μm line and space pattern engraved.

The obtained residual film rate evaluation sample was dipped in a resist stripping solution (TOK106, manufactured by Tokyo Ohka) at 70° C. for 120 minutes, and a 100 μm line-and-contact was obtained using a stylus type surface profiler (Dektak 150, manufactured by Veeco). The residual film rate was calculated by measuring the film thickness of the space pattern and dividing the film thickness after immersion in the stripping solution by the film thickness before immersion.

(Production Example 1)
40 g of diallyl isocyanuric acid and 29 g of diallyl monomethyl isocyanuric acid are dissolved in 264 g of dioxane, and a xylene solution of a platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3% by weight of platinum, Yumicore Precious Metals Japan, Pt-VTSC-3X). 143 μL was added. The solution thus obtained was heated to 105° C. in a nitrogen atmosphere containing 3% oxygen to give 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane. 88 g was added dropwise to a solution obtained by dissolving 176 g in toluene over 3 hours.

After 30 minutes from the end of the dropping, it was confirmed by ¹ H-NMR that the reaction rate of the alkenyl group was 95% or more. Then, a solution prepared by dissolving 62 g of 1-vinyl-3,4-epoxycyclohexane in 62 g of toluene was added dropwise to the above solution over 1 hour. Thirty minutes after the end of dropping, the reaction rate of the alkenyl group was confirmed to be 95% or more by ¹ H-NMR, and then the reaction was terminated by cooling. After distilling off the solvent toluene and dioxane under reduced pressure, propylene glycol 1-monomethyl ether 2-acetate was substituted to obtain "solution A" which was a colorless and transparent 50% by weight polysiloxane compound solution.

The diallyl isocyanuric acid corresponds to the compound (α1). The diallyl monomethyl isocyanuric acid corresponds to the compound (α2). 1,3,5,7-Tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane corresponds to the compound (β). 1-Vinyl-3,4-epoxycyclohexane corresponds to the compound (γ1). That is, in Manufacturing Example 1, the above items <1-1. It corresponds to the second preferred embodiment described in the component (A)>.

(Example 1)
27 g of the “solution A” described in Production Example 1 as the component (A), 0.068 g of tris[3-(trimethoxysilylpropyl)]isocyanurate as the component (B), and BBI-103 as the photoacid generator. A 30% PGMEA solution containing 0.41 g and 0.68 g of 9,10-dibutoxyanthracene as a sensitizer was prepared.

(Example 2)
27 g of “solution A” described in Production Example 1 as component (A), 0.41 g of tris[3-(trimethoxysilylpropyl)]isocyanurate as component (B), and BBI-103 as a photoacid generator. A 30% PGMEA solution containing 0.41 g and 0.68 g of 9,10-dibutoxyanthracene as a sensitizer was prepared. That is, Example 2 differs from Example 1 in the amount of component (B) added.

(Comparative Example 1)
30% obtained by adding 27 g of "solution A" described in Production Example 1 as component (A), 0.41 g of BBI-103 as a photoacid generator, and 0.68 g of 9,10-dibutoxyanthracene as a sensitizer. A PGMEA solution was prepared. That is, Comparative Example 1 does not contain the component (B).

(Comparative example 2)
27 g of the “solution A” described in Production Example 1 as the component (A), 0.068 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane in place of the component (B), and BBI as the photoacid generator. A 30% PGMEA solution containing 0.41 g of -103 and 0.68 g of 9,10-dibutoxyanthracene as a sensitizer was prepared.

(Comparative example 3)
27 g of the “solution A” described in Production Example 1 as the component (A), 0.41 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane in place of the component (B), and BBI as the photoacid generator. A 30% PGMEA solution containing 0.41 g of -103 and 0.68 g of 9,10-dibutoxyanthracene as a sensitizer was prepared.

(Comparative example 4)
27 g of the “solution A” described in Production Example 1 as the component (A), 1.4 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane instead of the component (B), and BBI as the photoacid generator. A 30% PGMEA solution containing 0.41 g of -103 and 0.68 g of 9,10-dibutoxyanthracene as a sensitizer was prepared.

(result)
The above-mentioned evaluation was performed on the photosensitive resin compositions obtained in Examples 1 and 2 and Comparative Examples 1 to 4. The results are shown in Table 1.

In addition, "phr" in Table 1 is an abbreviation for "per hundred resin" and represents an addition amount.

As shown in Table 1, containing a polysiloxane compound having at least one photopolymerizable functional group and at least one alkali-soluble functional group in one molecule, and at least one compound having a specific structure By using the photosensitive resin composition of the present invention, it is possible to improve the patterning property and the substrate adhesion and obtain a cured film having a high residual film rate.

INDUSTRIAL APPLICATION This invention can be utilized in various fields, such as an insulating material, an adhesive agent, a coating agent, and a sealing agent, and can also be utilized especially in a permanent film, such as a liquid crystal display.

Claims (6)

(A) a polysiloxane compound having at least one photopolymerizable functional group and at least one alkali-soluble functional group in one molecule;
(B) The following formulas (Y1) to (Y3)

(In the formula, R ⁴³ represents a divalent organic group having 1 to 3 carbon atoms, R ⁴⁴ represents a monovalent organic group having 1 to 3 carbon atoms, and R ⁴⁵ represents a monovalent organic group having 1 to 3 carbon atoms. Represents an organic group or hydrogen atom)
And at least one compound represented by
Contain,
At least one of the photopolymerizable functional groups is an alicyclic epoxy group or a glycidyl group,
Said polysiloxane compound, silicon - negative photosensitive resin composition characterized compound der Rukoto that the photopolymerizable functional group and the alkali-soluble functional group is introduced by carbon bonds. The alkali-soluble functional group has the following formulas (X1) to (X3)

The negative photosensitive resin composition according to claim 1, which is at least one kind selected from the group consisting of each structure represented by, a phenolic hydroxyl group, and a carboxyl group. The negative photosensitive resin composition according to claim 1 or 2 , further comprising a photoacid generator. Cured negative-working photosensitive resin composition is cured according to any one of claims 1-3. A laminate comprising a substrate and a cured film obtained by curing the negative photosensitive resin composition according to any one of claims 1 to 5 . The laminate according to claim 5 , wherein the base material has a silicon nitride layer on the surface.