JP2018066818A - Negative photosensitive resin composition, cured product and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition showing excellent adhesiveness even after patterning, without impairing its patterning properties.SOLUTION: A negative photosensitive resin composition contains (A) a polysiloxane compound having, in one molecule, at least one photopolymerizable functional group and at least one alkali soluble functional group, and (B) at least one compound having a specific structure (a compound having a long-chain alkyl group and a specific reactive group).SELECTED DRAWING: None

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.

  Examples of the component of such a photosensitive resin composition include a polysiloxane compound. Polysiloxane compounds are known to have high transparency and heat resistance. As a technique using a polysiloxane compound, for example, a technique described in Patent Document 1 can be cited.

  Patent Document 1 has at least one photopolymerizable functional group in one molecule, and 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 a polysiloxane compound is described.

International Publication No. 2009/075233 (Released on June 18, 2009)

  When making a laminated structure of three or more layers by bonding the base material 1 and another base material 2 using the photosensitive resin composition as an adhesive layer, base material 1 / photosensitive resin composition / adhesive / base material 2 However, if it is possible to provide a photosensitive resin composition that exhibits excellent adhesive performance even after pattern formation, the substrate 1 / photosensitive resin composition / substrate 2 can be obtained. The present invention has been made based on the idea that can be greatly simplified. An object of the present invention is to realize a photosensitive resin composition that exhibits excellent adhesion performance even after pattern formation without impairing patterning properties.

  As a result of intensive studies in order to achieve the above object, the present inventor has obtained a compound having a specific structure that reduces the elastic modulus of the composition to a polysiloxane compound having a photopolymerizable functional group and an alkali-soluble functional group. It has been found that a photosensitive resin composition exhibiting excellent adhesion performance even after pattern formation can be realized without adding patterning, and the present invention has been completed. That is, this invention consists of the following structures.

  [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) at least represented by the following formula (Y1) A negative photosensitive resin composition comprising: one kind of compound.

(In the formula (Y1), R ¹ is a group represented by the following formulas (Y2) to (Y6), and R ² is an alkyl group having 1 to 20 carbon atoms.)

[2] The negative photosensitive resin composition as described in [1], wherein R ² in the formula (Y1) is an alkyl group having 4 to 20 carbon atoms.

  [3] The alkali-soluble functional group is represented by the following formula (X1) or (X2)

The negative photosensitive resin composition according to [1] or [2], wherein the negative photosensitive resin composition is at least one selected from the group consisting of each structure represented by:

  [4] The negative photosensitive resin composition according to any one of [1] to [3], wherein at least one of the photopolymerizable functional groups is an alicyclic epoxy group or a glycidyl group. object.

  [5] Any one of [1] to [4], 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 one.

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

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

  [8] A laminate comprising a cured film obtained by curing the negative photosensitive resin composition according to any one of [1] to [6] on a substrate.

  [9] The laminate according to [8], wherein the negative photosensitive resin composition of the laminate has a thickness of 10 μm or more.

  [10] The laminate according to [8], wherein at least one layer of the laminate has glass on the surface.

  [11] A hollow structure for a CMOS / CCD sensor, comprising a cured film obtained by curing the resin according to any one of [1] to [6].

  [12] A hollow structure for a MEMS device, comprising a cured film obtained by curing the resin according to any one of [1] to [6].

  [13] A step of coating and drying the resin according to any one of [1] to [6] on a base material (base material 1) to form a film, a pattern forming step of developing with an alkaline developer after exposure, The manufacturing method of the laminated body characterized by including the process of crimping | bonding to the pattern which formed the base material (base material 2).

  [14] The method for producing a laminate as described in [13], wherein the substrate 1 is made of glass.

  [15] The method for producing a laminate according to [13] or [14], wherein the substrate 2 is a silicon wafer.

  The present invention has an effect of providing a photosensitive resin composition that exhibits excellent adhesion performance even after pattern formation without impairing patterning properties. In addition, if the photosensitive resin composition of the present invention is used, it is possible to provide an optical sensor, an optical semiconductor, etc. by a simple process, and is particularly suitable for manufacturing a hollow structure for a CMOS / CCD sensor and a hollow structure for a MEMS device. ing.

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

[1. Negative photosensitive resin composition]
The negative photosensitive resin composition includes (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)”.

  Since the negative photosensitive resin composition contains the two components, it exhibits excellent adhesion and chemical resistance.

  In addition, when the said component (B) was added to the negative photosensitive resin composition, it was not known what kind of influence it had on patterning property. Further, depending on the type and / or addition amount of the conventional silane coupling agent, when added to the negative photosensitive resin composition, there are cases where the patterning property is unfavorably affected. On the other hand, the present inventors surprisingly found that when the component (B) having a specific structure described later together with the component (A) is used, the adhesion to the substrate is not impaired. It was also found that a negative photosensitive resin composition having excellent chemical resistance and excellent adhesion performance after pattern formation can be realized.

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

In this specification, the “polysiloxane compound” is not particularly limited as long as it is a compound having a siloxane unit Si—O—Si. Of the siloxane units in the polysiloxane compound, the higher the content of T units (XSiO _3/2 ) or Q units (SiO _4/2 ), the higher the hardness of the resulting cured product, and the better the heat resistance reliability. . 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 harder the resulting cured product is. It is stress.

  The polysiloxane compound has at least one photopolymerizable functional group in one molecule. In this specification, the photopolymerizable functional group means an acidic active substance generated by a photoacid generator or a radical species or a cation species generated by a photopolymerization initiator when an active energy ray is irradiated from the outside. It 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. There are no particular limitations on the type of reaction and the type of crosslinking with photopolymerizable functional groups.

  Among them, particularly from the viewpoint of reactivity and stability of the polysiloxane compound, at least one of the photopolymerizable functional groups is an epoxy group or a crosslinkable silicon group (sometimes referred to as a “hydrolyzable silyl group”). , A (meth) acryloyl group or a vinyloxy group. Among the 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 from the viewpoint of excellent cationic polymerization 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. In particular, from the viewpoints of availability and stability of the compound, the crosslinkable silicon group is preferably an alkoxysilyl group. Examples of the alkoxysilyl group include those in which the functional group bonded to silicon 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 standpoint that residual components after curing hardly remain, 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, more preferably three or more. If there are three or more photopolymerizable functional groups, a cured product having a high crosslinking density is 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.

  The polysiloxane compound has at least one alkali-soluble functional group in addition to at least one photopolymerizable functional group in the same molecule. In the present specification, the alkali-soluble functional group means a functional group that imparts alkali solubility to a compound. When 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 a resist material capable of alkali development.

  In particular, from the viewpoint of reactivity, the alkali-soluble functional group has the following formula (X1) or (X2)

A group consisting of a phenolic hydroxyl group and a carboxyl group (hereinafter each structure represented by the above formula (X1) or (X2), a phenolic hydroxyl group and a carboxyl group may be referred to as an “acidic group”). It is preferable that it is 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 the formula (X1) or (X2), may be a compound having a phenolic hydroxyl group, and has a carboxyl group. It may be a compound.

  From the viewpoint that the obtained cured product is less colored after heating, the alkali-soluble functional group is preferably any one of the structures represented by the above formula (X1) or (X2) or a carboxyl group. Further, from the viewpoint of obtaining a cured product having low thermal decomposability at high temperatures, the alkali-soluble functional group is particularly preferably any one of the structures represented by the above formula (X1) or (X2).

  Moreover, each structure represented by the said formula (X1) or (X2) is similar to the structure of the below-mentioned component (B) by the point that it has an isocyanuric ring. Therefore, when the polysiloxane compound has any one of the structures represented by the formula (X1) or (X2), the compatibility with the component (B) is good and preferable.

  The amount of component (A) added 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, More preferably, it is 70 to 99% by weight. If the amount of component (A) added is 30% by weight or more, it is preferable because excellent heat resistance and transparency can be obtained. If the addition amount of component (A) is 99.9% by weight or less, the effect of component (B) can be sufficiently exerted, 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. However, the photopolymerizable functional group is formed by a chemically stable silicon-carbon bond (Si-C bond). 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 embodiments of the polysiloxane compound include the following three embodiments. In the present specification, the “SiH group” may be referred to as a “hydrosilyl group”.

A first preferred embodiment includes a product obtained by a hydrosilylation reaction using the following compounds (α1), (β) and (γ1) as starting materials:
(Α1) In one molecule, one or more carbon-carbon double bonds having reactivity with SiH group, and each structure represented by the above formula (X1) or (X2), phenolic hydroxyl group and 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 reaction using the following compounds (α1), (α2), (β) and (γ1) as starting materials:
(Α1) In one molecule, at least one carbon-carbon double bond having reactivity with a SiH group, each structure represented by the above formula (X1) or (X2), 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 a product obtained by a hydrosilylation reaction using the following compounds (α3), (α4) and (γ2) as starting materials:
(Α3) a compound having at least two carbon-carbon double bonds having reactivity with a SiH group in one molecule;
(Α4) In one molecule, at least one SiH group and at least one acidic group selected from the group consisting of each structure represented by the above formula (X1) or (X2), 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 several compounds selected from the compounds (α1) to (α4), (β), (γ1) and (γ2).

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

(Compound (α1))
Compound (α1) has at least one carbon-carbon double bond having reactivity with SiH group in each molecule, each structure represented by the above formula (X1) or (X2), phenolic hydroxyl group And an organic compound having at least one acidic group selected from the group consisting of carboxyl groups.

  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 a constituent element selected from the group is preferred. When the compound (α1) does not contain a siloxane unit, gas permeability is good and repelling hardly occurs, which is preferable.

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

  The group containing the carbon-carbon double bond having reactivity with the SiH group is not particularly limited, but vinyl group, allyl group, methallyl group, acrylic 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, 2,2-bis (allyloxymethyl) butyl group, 3-allyloxy-2,2-bis (allyloxymethyl) propyl group, vinyl ether group and the like. In particular, 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) may have at least one carbon-carbon double bond having reactivity with the SiH group in one molecule, but has high heat resistance reliability because the resulting cured product has a high crosslinking density. In view of the above, it is preferable to have two or more carbon-carbon double bonds in one molecule, and more preferable to have three or more carbon-carbon double bonds.

  Although it does not specifically limit as a compound ((alpha) 1), From a viewpoint that there is little coloring at the time of high temperature, the following general formula (Ia) or (Ib) which has an isocyanuric ring

(Wherein 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 reactivity with the SiH group. It is preferable to use at least one compound represented by any one of (including a carbon-carbon double bond).

  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)

A compound represented by the formula: butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid or undecylenic acid is preferred. Among these, from the viewpoint of particularly high heat resistance, the compound (α1) is preferably diallyl isocyanuric acid, monoallyl isocyanuric acid, diallyl bisphenol A, diallyl bisphenol S, vinyl phenol or allyl phenol. Furthermore, from the viewpoint of transparency of the cured product, the compound (α1) is particularly preferably diallyl isocyanuric acid or monoallyl isocyanuric acid.

  As a compound ((alpha) 1), 1 type may be used and 2 or more types may be used together.

(Compound (α2))
The compound (α2) is a compound having at least one carbon-carbon double bond having reactivity with a SiH group in one molecule, which does not correspond to the compound (α1) and the compound (γ1) described later. There is no particular limitation.

  From the viewpoint that the resulting cured product has high heat resistance, 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 an alkenyl group-containing polysiloxane having a linear structure, a polysiloxane having an alkenyl group at the molecular end, and a cyclic siloxane compound containing an alkenyl group. The polysiloxane having at least one alkenyl group is not particularly limited by the structure, but is a polysiloxane having a polyhedral skeleton containing an alkenyl group in consideration of heat resistance, light resistance, chemical stability, and the like. It is preferable.

  Examples of the alkenyl group-containing polysiloxane having a linear structure include a copolymer of a dimethylsiloxane unit, a methylvinylsiloxane unit, and a terminal trimethylsiloxy unit, and a copolymer of a diphenylsiloxane unit, a methylvinylsiloxane unit, and a terminal trimethylsiloxy unit. Examples thereof include a copolymer, a copolymer of a methylphenylsiloxane unit, a methylvinylsiloxane unit and a terminal trimethylsiloxy unit, and a polysiloxane having a terminal blocked with a dimethylvinylsilyl group.

The polysiloxane having an alkenyl group at the molecular terminal is at least selected from the group consisting of polysiloxanes whose ends are blocked by dimethylalkenyl groups, and dimethylalkenylsiloxane units and SiO ₂ units, SiO _3/2 units and SiO units. Examples thereof include 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 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.

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

In the above formula, R ^{10 to} R ¹⁷ are an alkenyl group (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 hydrogen atoms bonded to carbon atoms of these groups Or it is the same or different monovalent hydrocarbon group selected from the group (chloromethyl group, trifluoropropyl group, cyanoethyl group, etc.) etc. which substituted all with the halogen atom or the cyano group, etc., or a hydrogen atom. The hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. The hydrocarbon group may be unsubstituted or substituted.

However, at least one of R ^{10 to} R ¹⁷ in the compound (α2) is an alkenyl group that is a reactive group for 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 R ^{10 to} R ¹⁷ described above, and X represents a hydrolyzable functional group such as a halogen atom or an alkoxy group). It is obtained by hydrolysis condensation reaction of a silane compound represented by

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

  Further preferred examples of the compound (α2) include silylated silicic acid having a polyhedral skeleton represented by the following general formula (IV) (here, the case where the number of Si atoms is 8 is shown as a representative example). In the silylated silicic acid having the polyhedral skeleton, the Si atoms forming the polyhedral skeleton and the reactive alkenyl group are bonded via a siloxane bond, so that the obtained cured product becomes rigid. Not too much. Therefore, if a silylated silicic acid having the polyhedral skeleton is used, a good cured product can be obtained.

In the above formula, R ^{18 to} R ⁴¹ are an alkenyl group (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 hydrogen atoms bonded to carbon atoms of these groups Or it is the same or different hydrocarbon group selected from the group (chloromethyl group, trifluoropropyl group, cyanoethyl group etc.) etc. which substituted all with the halogen atom or the cyano group, etc., or a hydrogen atom. However, at least one of R ^{18 to} R ⁴¹ in the compound (α2) is an alkenyl group that is a reactive group for the hydrosilylation reaction. The alkenyl group is preferably a vinyl group from the viewpoint of heat resistance.

  A method for synthesizing a 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 hydrolytically condensed in the presence of a base such as quaternary ammonium hydroxide. Examples of tetraalkoxysilane include tetraethoxysilane, tetramethoxysilane, and tetrabutoxysilane. Examples of the quaternary ammonium hydroxide include 2-hydroxyethyltrimethylammonium hydroxide and tetramethylammonium hydroxide. In the present invention, it is possible to obtain a silicate having the same polyhedral skeleton from a substance containing silica such as silica or rice husk instead of tetraalkoxylane.

  In this synthesis method, a silicate having a polyhedral skeleton is obtained by a hydrolytic condensation reaction of tetraalkoxysilane, and the obtained silicate is further reacted with a silylating agent such as an alkenyl group-containing silyl chloride. A polysiloxane in which a Si atom forming a polyhedral skeleton and an alkenyl group which is a reactive group are bonded via a siloxane bond can be obtained.

  The number of Si atoms contained in the polyhedral skeleton is preferably 6 to 24, and more preferably 6 to 10. In addition, polysiloxanes having polyhedral skeletons with different numbers of Si atoms may be used as a mixture. 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 present 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 substrate, an organic compound having at least one carbon-carbon double bond having reactivity with SiH group in one molecule is used for the compound (α2). You can also. The organic compound here can be classified into an organic polymer compound and an organic monomer compound.

  Examples of organic polymer compounds include polyether-based, polyester-based, polyarylate-based, polycarbonate-based, saturated hydrocarbon-based, unsaturated hydrocarbon-based, polyacrylate ester-based, polyamide-based, phenol-formaldehyde-based (phenolic resin). System) or polyimide compounds can be used.

  Examples of organic monomer compounds include aromatic hydrocarbons such as phenols, bisphenols, benzene and naphthalene; aliphatic hydrocarbons such as linear and alicyclics; heterocyclic compounds, and these 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, diarylidenepentaerythritol, diallylmonomethyl 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, Ethylene glycol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, diallyl ether of bisphenol 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 oligomers thereof, 1,2-polybutadiene All of glycidyl groups of conventional epoxy resins such as ene (one having a 1,2 ratio of 10 to 100%, preferably 1,2 ratio of 50 to 100%), allyl ether of novolak phenol, allylated polyphenylene oxide, etc. In which is substituted with an allyl group.

  As the compound (α2), a low molecular weight compound that is difficult to express by dividing into a skeleton portion and an alkenyl group (a carbon-carbon double bond having reactivity with a 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, fats such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene. And cyclic aliphatic polyolefin compound systems, and substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene.

  In particular, from the viewpoint of high heat resistance and light resistance, the compound (α2) is represented by 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 reactivity with a SiH group. (Including carbon-carbon double bond)
It is preferable that it is a compound represented by these.

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

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

  As a compound ((alpha) 2), 1 type may be used and 2 or more types may be used together.

(Compound (α3))
Among the compounds (α2), compounds having at least two carbon-carbon double bonds having reactivity with SiH groups 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 compound (α2). Moreover, as a compound ((alpha) 3), 1 type may be used and 2 or more types may be used together.

(Compound (α4))
Compound (α4) is at least one selected from the group consisting of at least one SiH group and each structure represented by the above formula (X1) or (X2), a phenolic hydroxyl group and a carboxyl group in one molecule. If it is a compound which has these acidic groups, it will not specifically limit.

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

  Examples of the polyfunctional hydrosilane compound include poly or oligosiloxanes whose ends are blocked with a dimethylhydrogensilyl group such as tetramethyldisiloxane or hexamethyltrisiloxane, 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-he Sa hydrogen -1,3,5,7,9,11- such hexamethylcyclotrisiloxane siloxanes, although cyclic siloxanes containing a hydrosilyl group and the like, but are not limited to.

(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. For example, the compound described in International Publication No. 96/15194 is at least in 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 are particularly limited by the structure. It is not a thing. Considering heat resistance, light resistance, chemical stability, etc., the compound (β) is preferably a polysiloxane having a polyhedral skeleton containing a hydrosilyl group.

  Examples of the hydrosilyl group-containing polysiloxane having the above 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 include copolymers, copolymers of methylphenylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units, and polysiloxanes whose ends are blocked by dimethylhydrogensilyl groups.

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

  Examples of the cyclic polysiloxane compound containing a hydrosilyl group include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trimethyl. 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 Examples include 7,9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclosiloxane and the like.

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

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

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, at least one of these R ^{18 to} R ⁴¹ is a hydrosilyl group that is a reactive group for the hydrosilylation reaction.

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

  In this synthesis method, a silicate having a polyhedral skeleton is obtained by hydrolytic condensation reaction of tetraalkoxysilane, and the obtained silicate is further reacted with a silylating agent such as hydrosilyl group-containing silyl chloride. In addition, it is possible to obtain a polysiloxane in which a Si atom forming a polyhedral structure and a hydrosilyl group that 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. In addition, polysiloxanes having polyhedral skeletons with different numbers of Si atoms may be used as a mixture.

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

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

(Wherein R ⁴ and R ⁵ represent an organic group having 1 to 6 carbon atoms, which may be the same or different, n is an integer of 1 to 10, and m is an integer of 0 to 10)
The cyclic organopolysiloxane having at least 3 SiH groups in one molecule represented by

  Examples of the organic group include hydrocarbon groups (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. 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 composed of an element selected from the group consisting of C, H and O, and are hydrocarbon groups. More preferably, it is 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 availability and reactivity. It is preferable.

  As said compound ((beta)), 1 type may be used and 2 or more types may be used together.

(Compound (γ1))
The compound (γ1) is particularly limited as long as it is 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. Not. In addition, the photopolymerizable functional group here is the same as the photopolymerizable functional group which the above-mentioned component (A) has, and a preferable aspect is 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 having reactivity with the SiH group in the aforementioned compounds (α1) and (α2). The same groups as those containing a bond are 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. Examples include nurate. 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 include but are not limited to ketoximate silanes such as vinyl silane and bis (cyclohexyl ketoximate) methyl vinyl silane.Of these, alkoxysilanes can be preferably used as the compound (γ1). In the compound (γ1), when the photopolymerizable functional group is a crosslinkable silicon group, there is an advantage that the obtained cured product is excellent in heat resistance.

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

(Wherein 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). Among them, from the viewpoint of easy removal of by-products after the reaction, the compound (γ1) is particularly trimethoxyvinylsilane, triethoxyvinylsilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, methoxydimethylvinylsilane or ethoxydimethylvinylsilane. Preferably there is.

  As the compound (γ1) having an acryloyl group or a methacryloyl group as a photopolymerizable functional group, 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), vinyl group or allyl group and the following general formula (VIII)

(Wherein R ⁴² represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 16)
And compounds having at least one organic group represented by the formula:

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 thereof include a compound that is a group having a carbon-carbon double bond that is reactive with a SiH group (such as a vinyl group or an allyl group). Furthermore, from the viewpoint of high selectivity in hydrosilylation, the compound (γ1) is preferably a compound having a methacryloyl group and an allyl group or vinyl group in the same molecule, and from the viewpoint of availability, (meth) More preferably, it is at least one of allyl acrylate and vinyl (meth) acrylate, and more preferably at least one of allyl methacrylate and vinyl methacrylate.

  In the hydrosilylation reaction, two or more compounds (γ1) can be used in combination regardless of the type of the photopolymerizable functional group.

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

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

  In particular, from the viewpoint of excellent heat resistance of the cured product, 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 (dimethylketoximate) methylsilane and Examples thereof include, but are not limited to, ketoximate silanes such as bis (cyclohexyl ketoximate) methyl silane. Among these, alkoxysilanes can be preferably used as the compound (γ2).

(Hydrosilylation catalyst)
A known hydrosilylation catalyst may be used as a catalyst when a compound selected from compounds (α1) to (α4), (β) and (γ1) to (γ2) is polymerized by a hydrosilylation reaction.

  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 smoothly proceeding the hydrosilylation reaction, the lower limit of the addition amount is a carbon-carbon double bond having reactivity with the SiH group charged during the reaction. Is preferably 10 ⁻⁸ mol, more preferably 10 ⁻⁶ mol, relative to 1 mol of a group containing 1 (hereinafter sometimes simply referred to as “alkenyl group”), and the upper limit of the amount added is 1 mol of the above alkenyl group Is preferably 10 ⁻¹ mol, more preferably 10 ⁻² mol.

A cocatalyst can be used in combination with the hydrosilylation catalyst. Examples of the cocatalyst include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, 2-hydroxy-2-methyl-1-butyne and 1-ethynyl-1-cyclohexanol. Acetylene alcohol compounds, and sulfur compounds such as simple sulfur. The addition amount of the cocatalyst is not particularly limited, but the lower limit of the addition amount relative 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. More preferably, it is 10 moles.

(Hydrosilylation reaction)
Various methods can be used as the order and method of the reaction. From the viewpoint that the synthesis process is simple, all compounds are charged in one pot, hydrosilylation reaction is performed, and unreacted compounds are finally removed. The method is preferred.

  From the viewpoint that it is difficult to contain a low molecular weight substance, an excess alkenyl group-containing compound (compound (α1), (α2) or (α3)) and a SiH group-containing compound (compound (β) or (α4)), or After 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 starting materials More preferably, a method of once removing an unreacted compound and performing a hydrosilylation reaction 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 the total amount of alkenyl groups of the compound to be reacted is A and the total amount of SiH groups of the compound to be reacted is B, it is preferable that 1 ≦ B / A ≦ 30. More preferably, 1 ≦ B / A ≦ 10. If 1 ≦ B / A, unreacted alkenyl groups are unlikely to remain in the composition, and coloration is unlikely to occur. Further, if B / A ≦ 30, unreacted SiH groups are unlikely to remain, and thus foaming and cracking are difficult to occur when the composition is cured.

  The reaction temperature can be appropriately set, 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 steps or continuously as required.

  The reaction time and the pressure during the reaction can also be set as appropriate. Oxygen can be used in the hydrosilylation reaction. The hydrosilylation reaction can be promoted by adding oxygen to the gas phase portion of the reaction vessel. In order to make the addition amount of oxygen below the lower limit of explosion limit, it is necessary to manage the oxygen volume concentration in the gas phase part to 3% or less. From the viewpoint that the effect of promoting the hydrosilylation reaction by addition of oxygen is observed, the oxygen volume concentration in the gas phase 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. Specifically, hydrocarbon solvents such as benzene, toluene, hexane and heptane, tetrahydrofuran, 1,4-dioxane, 1,3- And 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 can also be used as a mixed solvent of two or more types. More preferably, the solvent is toluene, tetrahydrofuran, 1,3-dioxolane or chloroform. The amount of solvent used can also be set as appropriate.

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

(Geling inhibitor)
The purpose of improving the storage stability of the resulting reaction product, or hydrosilylation reaction using compound (α1) (or compound (α2) depending on the embodiment), compound (β) and compound (γ1) or (γ2) After performing, a gelation inhibitor can be used for the purpose of suppressing alteration such as thickening due to heat treatment when the solvent and unreacted compound are removed by devolatilization under reduced pressure. 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. Can be used together.

  From the viewpoint of good delayed activity and good raw material availability, the gelation inhibitors are benzothiazole, thiazole, dimethylmalate, 3-hydroxy-3-methyl-1-butyne, 1-ethynyl-1-cyclohexanol. Or it is preferable that it is a triphenylphosphine. That is, a part of the promoter mentioned above can also be used as a gelation inhibitor.

Although the addition amount of the gelation inhibitor can be appropriately set, the lower limit of the addition amount with respect to 1 mol of the hydrosilylation catalyst to be 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. When the addition amount is small, the desired storage stability and the gelation suppressing effect at the time of vacuum devolatilization cannot be obtained. If the amount added is large, it can be a curing inhibitor during the curing reaction.

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

<1-2. Ingredient (B)>
The said negative photosensitive resin composition contains the compound shown below as a component (B). In the negative photosensitive resin composition, since the component (B) is contained, the elastic modulus of the composition in the exposed portion is reduced during photolithography, and as a result, the patternability is not impaired. Even after pattern formation, the adhesiveness of a laminate structure of three or more layers using the negative photosensitive resin composition as an adhesive layer is improved. On the other hand, since the component (B) is a low molecular compound in the unexposed area, the alkali solubility is not lowered, and the patterning property is not impaired. This is the first finding of the present inventors.

  Component (B) is at least one compound represented by the following formula (Y1).

(In the formula (Y1), R ¹ is a group represented by the following formulas (Y2) to (Y6), and R ² is an alkyl group having 4 to 16 carbon atoms.)

Preferable examples of R ² include butyl group, hexyl group, 2-ethylhexyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, and octadecyl group. From the viewpoint that the adhesiveness can be improved without degrading the patterning property, the formula (R ¹ ) in the component (B) is preferably a compound represented by the formula (Y2). R ² ) is preferably an alkyl group having 8 to 16 carbon atoms.

  The amount of component (B) added to 100% by weight of the negative photosensitive resin composition containing no solvent is preferably 0.1 to 40% by weight, more preferably 0.5 to 20% by weight. Preferably, it is 1 to 20% by weight. If the amount of component (B) added is 0.1% by weight or more, it is preferable because adhesion and chemical resistance can be sufficiently improved. If the addition amount of the component (B) is 40% by weight or less, it is preferable because sufficient patterning property can be secured.

<1-3. Photoacid generator>
The negative photosensitive resin composition may contain a photoacid generator. The photoacid generator is particularly a compound that can release an acidic active substance capable of crosslinking the photopolymerizable functional group of the component (A) when irradiated with active energy rays. It is not limited.

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

  A known photoacid generator can be used as the photoacid generator. Examples of the photoacid 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 photoacid generator is preferably a sulfonate ester, a carboxylic acid ester or an onium salt, 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 trifluoromethylsulfonate derivatives, Examples include benzoin sulfonates, sulfonates of 1-oxy-2-hydroxy-3-propyl alcohol, pyrogallol trisulfonates and benzyl sulfonates.

  Specific examples of the sulfonate esters include diphenyl disulfone, ditosyl disulfone, bis (phenylsulfonyl) diazomethane, bis (chlorophenylsulfonyl) diazomethane, bis (xylylsulfonyl) diazomethane, phenylsulfonylbenzoyldiazomethane, and bis (cyclohexylsulfonyl). ) Methane, 1,8-naphthalenedicarboxylic acid imidomethyl sulfonate, 1,8-naphthalenedicarboxylic acid imidotosyl sulfonate, 1,8-naphthalenedicarboxylic acid imide trifluoromethyl sulfonate, 1,8-naphthalenedicarboxylic acid imidocamphor sulfonate, amber Acid imide phenyl sulfonate, succinimide tosyl sulfonate, succinimide trifluoromethyl sulfonate, succinimide Sulfonate sulfonate, phthalimido trifluorosulfonate, cis-5-norbornene-endo-2,3-dicarboxylic 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 and para-nitrophenyl tosylate Etc.

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

  In general, sulfonic acid esters and carboxylic acid esters may require a heating step (50 ° C. to 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 hexafluoroacylate, 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, anisyldiphenyl Rufonium hexafluoroantimonate, 4-butoxyphenyldiphenylsulfonium tetrafluoroborate, 4-butoxyphenyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, tris (4-phenoxyphenyl) sulfonium Hexafluorophosphate, di (4-ethoxyphenyl) methylsulfonium hexafluoroarsenate, 4-acetylphenyldiphenylsulfonium tetrafluoroborate, 4-acetylphenyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, tris (4-thiomethoxyphenyl) Sulfonium hexafluorophosphate, di (methoxysulfonylpheny ) Methylsulfonium hexafluoroantimonate, di (methoxynaphthyl) methylsulfonium tetrafluoroborate, di (methoxynaphthyl) methylsulfonium tetrakis (pentafluorobenzyl) borate, di (carbomethoxyphenyl) methylsulfonium hexafluorophosphate, (4-octyl) Oxyphenyl) 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-oxo-Chi entrée tetrakis (pentafluorobenzyl) borate, and 5-methyl-10,10-dioxo-Chi entrée hexafluorophosphate, and the like. 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 hexaful Lophosphate, bis (4-t-butylphenyl) iodonium trifluorosulfonate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoro Borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium trifluoromethylsulfonate, di (dodecylphenyl) iodonium hexafluoroantimonate, di (dodecylphenyl) iodonium triflate, diphenyliodonium bissulfate, 4,4 '-Dichlorodiphenyliodonium bisulphate, 4,4'-Dibromodiphenyliodonium bisulphate 3,3′-dinitrodiphenyliodonium bisulphate, 4,4′-dimethyldiphenyliodonium bisulphate, 4,4′-bissuccinimide diphenyliodonium bisulphate, 3-nitrodiphenyliodonium bisulphate, 4,4′-dimethoxydiphenyl Iodonium bisulphate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, (4-octyloxyphenyl) phenyliodonium tetrakis (3,5-bis-trifluoromethylphenyl) borate, disclosed in US Pat. No. 5,554,664 and that (Torirukumiru) iodonium tetrakis (pentafluorophenyl) borate _{(CH 3 C 6 H 4)} 2 I- (SO 2 CF 3) 3, disclosed in U.S. Patent No. 5,514,728 (C ₆ H ₅ ) ₂ IB (C ₆ F ₅ ) ₄ , and those disclosed in US Pat. No. 5,340,898. These can be used alone or in combination of two or more.

  As other onium salts, aromatic diazonium salts can be used. For example, p-methoxybenzenediazonium / hexafluoroantimonate can be used.

  The commercially available onium salts include Sun Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI-L150, SI-L160, SI- L110 and SI-L147 (manufactured by Sanshin Chemical Industry Co., Ltd.), UVI-6950, UVI-6970, UVI-6974 and UVI-6990 (manufactured by Union Carbide), Adeka optomer SP-150, SP -151, SP-170, SP-171 and SP-172 (above, manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacure 261 (manufactured by Ciba Specialty Chemicals Co., Ltd.), CI-2481, CI-2624, CI-2623 and CI-2064 (Nippon Soda Co., Ltd.), CD-1010, CD-1011 And CD-1012 (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, manufactured by Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T and PCI -022T (Nippon Kayaku Co., Ltd.), IBPF and IBCF (Three Chemical Co., Ltd.), UVE1014 (manufactured by General Electronics Corp.), and the like RHODORSIL-PI2074 (Rhodia) and the like.

As anionic 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 ⁻ .

  Moreover, as said onium salt, J.I. Polymer Science: Part A: polymer Chemistry, Vol. 31, 1473-1482 (1993), J. MoI. Polymer Science: Part A: Polymer Chemistry, Vol. 31, 1483-1491 (1993) can also be used diaryl iodonium salts which can be prepared.

  The content of the photoacid generator in the negative photosensitive resin composition is not particularly limited, but is 0.01 to 10 parts by weight with respect to 100 parts by weight of the component (A) from the viewpoint of curability. Moreover, it is more preferable that it is 0.1-5.0 weight part from a viewpoint of the physical-property balance of hardened | cured material. If the amount of the photoacid generator is small, it may take a long time to cure, or a cured product that is sufficiently cured may not be obtained. Moreover, when there are many photo-acid generators, since a color remains in hardened | cured material or coloring or heat resistance or light resistance is impaired for rapid hardening, it may be unpreferable.

<1-4. Cationic polymerization initiator>
The negative photosensitive resin composition may contain a cationic polymerization initiator. The cationic polymerization initiator is particularly limited as long as it is an active energy ray cationic polymerization initiator that generates a cationic species or Lewis acid by active energy rays, or a thermal cationic polymerization initiator that generates a cationic species or Lewis acid by heat. It can be used without being. The photopolymerizable functional group of the component (A) can be crosslinked by the cationic species or 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 (perfluoride) as described in US Pat. No. 3,586,616. Alkylsulfonyl) methane metal salts; aryldiazonium 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; Aromatic onium salts of Group Va elements such as: dicarbonyl chelates of Group IIIa to Va elements as described in US Pat. No. 4068091; thiopyrylium salts as described in US Pat. No. 4,139,655; MF ₆ as described in JP 4161478 ^- Kagei Group VIa elements in the form of ON (where M is selected from phosphorus, antimony and arsenic); arylsulfonium complex salts as described in US Pat. No. 4,231,951; fragrances as described in US Pat. No. 4,256,828 Iodonium complex salts and aromatic sulfonium complex salts; 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 whose 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 (manufactured by 3M), UVR-6990 and UVR-6974 (manufactured by Union Carbide), UVE-1014 and UVE-1016 (manufactured by General Electric), KI-85. (Degussa), and SP-152 and SP-172 (Asahi Denka) are commercially available.

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

  Among the aromatic onium salts used as active energy ray cationic polymerization initiators, there are those that generate cationic species by heat, and these can also be used as thermal cationic polymerization initiators. Examples thereof include Sun-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 preferred in that 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 with respect to 100 parts by weight of the component (A). If the amount of the cationic polymerization initiator is small, it may take a long time for curing, or a cured product that is sufficiently cured may not be obtained. If the amount of the cationic polymerization initiator is large, the color of the initiator may remain in the cured product, or may be colored or raised due to rapid curing, or the heat and light resistance of the cured product may be impaired.

<1-5. Radical polymerization initiator>
The negative photosensitive resin composition may contain a radical polymerization initiator. The radical polymerization initiator is not particularly limited as long as it is an active energy ray radical polymerization initiator that generates radical species with active energy rays, or a thermal radical polymerization initiator that generates radical species with heat. The photopolymerizable functional group of component (A) can be cross-linked 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, polynuclear compounds. Quinone compounds, xanthone compounds, thioxanthone compounds, triazine compounds, ketal compounds, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, thiuram compounds, fluoroamine compounds, etc. Is mentioned.

  Specific examples of the acetophenone compounds include 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 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-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-hydroxycyclohexylphenylketo 2,2-dimethoxy-1,2-diphenylethane-1-one and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl -Propan-1-one etc. are mentioned.

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

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

  Specific examples of the oxime ester compounds 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 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, 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-et Sicarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl)- 1,2′-biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2, 4-dichlorophenyl) -4,4 ′, 5,5′-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′-biimidazole, 2, 2′-bis (2,4-dibromophenyl) -4,4 ′, , 5′-tetraphenyl-1,2′-biimidazole and 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 ′ -Biimidazole etc. are mentioned.

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

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

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

  Specific examples of the triazine compound include 1,3,5-tris (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 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-tri Gin, 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.

  In particular, 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). It is preferable.

  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- Propyl) ketone or 2,2-dimethoxyacetophenone is preferred.

  Specific examples of thermal radical polymerization initiators include diacyl peroxides (such as acetyl peroxide and benzoyl peroxide), ketone peroxides (such as methyl ethyl ketone peroxide and cyclohexanone peroxide), and hydroperoxides (hydrogen peroxide). , Tert-butyl hydroperoxide and cumene hydroperoxide), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyesters (tert-butyl peroxide) Acetate, tert-butyl peroxypivalate, etc.), azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.) and persulfates ( Ammonium sulfate, and a sodium persulfate and potassium persulfate, etc.) and the like.

  As these radical polymerization initiators, 1 type may be used and 2 or more types may be used together.

  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 with respect to 100 parts by weight of the component (A). If the amount of the cationic polymerization initiator is small, there is a tendency that the curing is insufficient and a contrast cannot be obtained during 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, adhesion and cured product strength. it can. The crosslinking agent is not particularly limited as long as it is selected depending on the curing reaction format, and examples thereof include epoxy compounds, oxetane compounds, alkoxysilane compounds, and (meth) acrylate compounds.

  Specific examples of the epoxy compound and the oxetane compound include novolak phenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, cyclohexyl epoxy 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-epoxycyclohexane carbo Xylate, ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene 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} benzene, bis {1-ethyl (3-oxetanyl)} methyl ether , 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, and the like.

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

  Specific examples of the (meth) acrylate compound include allyl (meth) acrylate, vinyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and (meth) acrylic. Acid-modified allyl glycidyl ether (manufactured by 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 Lumpur-based (meth) acrylate, bisphenol A di (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, and (meth) acrylate group-containing polyorganosiloxane.

  Although the addition amount of the crosslinking agent can be appropriately set, it is preferably 1 to 50 parts by weight, 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 crosslinking agent is small, the effect of addition does not appear, and if the addition amount of the crosslinking agent is large, the physical properties of the cured product may be adversely affected.

(Sensitizer)
The negative photosensitive resin composition may contain a sensitizer. According to the sensitizer, the sensitivity to visible light or the like can be improved in the negative photosensitive resin composition, and g-line (436 nm), h-line (405 nm), i-line (365 nm), etc. Sensitivity can be given to light having a high wavelength. 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 compounds 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. From the viewpoint of easy availability, anthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene and the like are preferable as the anthracene compound.

  As the 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.

  As these sensitizers, 1 type may be used and 2 or more types may be used together.

  The content of the sensitizer in the curable composition of the present invention is not particularly limited as long as it is an amount capable of exerting a sensitizing effect, but an added initiator (photo acid generator, cationic polymerization initiator or radical polymerization start). Agent) Preferably it is 0.01-300 mol with respect to 1 mol, More preferably, it is 0.1-100 mol. If the amount of the sensitizer is small, a 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, or may be colored 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 reactive modifier for adjusting the reactivity and suppressing the inhibition of curing by oxygen. Also 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 (manufactured by Shin-Etsu Chemical Co., Ltd., KF2001 and KF2004).

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

  Specific examples of the phosphine compound include triphenylphosphine and tributylphosphine.

(Adhesion improver)
The said negative photosensitive resin composition may contain the adhesive improvement agent. In addition to commonly used adhesives as adhesion improvers, for example, various coupling agents, epoxy compounds, oxetane compounds, phenol resins, coumarone-indene resins, rosin ester resins, terpene-phenol resins, α-methylstyrene -Vinyl toluene copolymer, polyethyl methyl styrene, aromatic polyisocyanate, etc. can be mentioned.

  An example of the coupling agent is a silane coupling agent. 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 one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably 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 from the viewpoint of handleability. From the viewpoints of adhesiveness and adhesiveness, an epoxy group, a methacryl 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 include 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 Methacrylic groups such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane and acryloxymethyltriethoxysilane Alkoxysilanes having a drill group can be exemplified.

  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, with respect to 100 parts by weight of the compound having a photopolymerizable functional group, More preferably, it is 0.5-5 weight part. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the curability and the physical properties of the cured product may be adversely affected.

  Moreover, 1 type may be used as these coupling agents, a silane coupling agent, an epoxy compound, etc., and 2 or more types may be used together.

  At least one of carboxylic acids and acid anhydrides can be used for at least one of improvement and stabilization of adhesion by the coupling agent or the epoxy compound. The carboxylic acids and acid anhydrides are not particularly limited, but 2-ethylhexanoic acid, cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, methylcyclohexanedicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylheimic acid, norbornene dicarboxylic 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, Naphthalenedicarboxylic acids and their single or complex acid anhydrides may be mentioned.

  Of these carboxylic acids and acid anhydrides, for example, tetrahydrophthalic acid, methyltetrahydrophthalic acid, and single or complex acid anhydrides are preferable from the viewpoint of hardly impairing the physical properties of the obtained cured product.

  The amount used in the case of using carboxylic acids and acid anhydrides can 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. It is. If the addition amount is small, the effect of improving adhesiveness does not appear.

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

(Phosphorus compound)
When the negative photosensitive resin composition is cured by light or heat, and particularly used in applications requiring transparency, the negative photosensitive resin composition is used in order to improve the hue after curing by light or heat. It is preferable to add a phosphorus compound to the type photosensitive resin composition.

  Specific examples of the phosphorus compound include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol diphosphite, tris (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl phosphite), cyclic neopentanetetrayl bis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetrayl bis (2 , 6-di-tert-butyl-4-methylphenyl) phosphite and bis [2-tert-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite Chosen from fights Antioxidants and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro- Coloring prevention selected from oxaphosphaphenanthrene oxides such as 9-oxa-10-phosphaphenanthrene-10-oxide and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Agents.

  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 with respect to 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. When the usage-amount of the said phosphorus compound becomes more than 10 weight part, it may have a bad influence on the sclerosis | hardenability and the physical property of hardened | cured material.

(Thermoplastic resin)
For the purpose of modifying the characteristics of the negative photosensitive resin composition, various thermoplastic resins can be added to the negative photosensitive resin composition. Examples of the thermoplastic resin include, for example, a methyl methacrylate homopolymer or a polymethyl methacrylate resin such as a random, block, or graft polymer of methyl methacrylate and another monomer (for example, Optretz manufactured by Hitachi Chemical Co., Ltd.) Acrylic resins represented by polybutyl acrylate resins such as homopolymers of butyl acrylate or random, block, or graft polymers of butyl acrylate and other monomers, bisphenol A, 3,3,5-trimethylcyclohexyl Polycarbonate resins such as polycarbonate resins containing silidene bisphenol or the like as a monomer structure (for example, APEC made by Teijin Limited), norbornene derivatives, resins obtained by homopolymerizing or copolymerizing vinyl monomers, norbornene derivatives Cycloolefin resins such as ring-opening metathesis polymerized resins or hydrogenated products thereof (for example, APEL manufactured by Mitsui Chemicals, ZEONOR, ZEONEX manufactured by Nippon Zeon Co., Ltd., ARTON manufactured by JSR Co., Ltd.), ethylene and maleimide Olefin-maleimide resins such as coalescence (eg, TI-PAS manufactured by Tosoh Corporation), bisphenols (such as bisphenol A and bis (4- (2-hydroxyethoxy) phenyl) fluorene) or diols (such as diethylene glycol), and phthalates Polyester resins such as polyester (for example, O-PET manufactured by Kanebo Co., Ltd.) obtained by polycondensation of acids (such as terephthalic acid and isophthalic acid) or aliphatic dicarboxylic acids, polyethersulfone resins, polyarylate resins, polyvinyl acetal resins, Polyethylene tree , Polypropylene resins, polystyrene resins, polyamide resins, silicone resins, other like fluorine resin, natural rubber, but the rubber-like resins such as EPDM, but is not limited thereto.

  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 tends 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 5000 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 tends to be tough. The molecular weight distribution is not particularly limited, but from the viewpoint that the viscosity of the mixture tends to be low and the moldability tends to be good, the molecular weight distribution is preferably 3 or less, more preferably 2 or less, and 1.5 More preferably, it is as follows.

  Although there is no limitation in particular as a compounding quantity of the said thermoplastic resin, Preferably it is 5 to 50 weight% with respect to the whole negative photosensitive resin composition, More preferably, it is 10 to 30 weight%. If the amount of the thermoplastic resin added is small, the resulting cured product may become brittle. If 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 dispersed by dissolving in a solvent and mixing. . In the point that the obtained hardened | cured material tends to become more transparent, it is preferable to melt | dissolve in a polysiloxane type compound and to mix as a uniform state. Also in this case, the thermoplastic resin may be directly dissolved in the polysiloxane compound, or may be uniformly mixed using a solvent or the like, and then the solvent may be removed to obtain a uniform dispersed state or mixed state. .

  When the thermoplastic resin is used in a dispersed state, the average particle diameter of the thermoplastic resin can be set as appropriate, 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. There may be a distribution of the particle system, which may be monodispersed or have 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 diameter variation coefficient is preferably 10% or less.

(Filler)
You may add a filler to the said negative photosensitive resin composition as needed.

  Various fillers are used, for example, silica-based fillers (quartz, fume silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine powder 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, white clay, clay, talc, calcium carbonate, magnesium carbonate, barium sulfate and inorganic balloon First, examples include fillers generally used or proposed as fillers for conventional sealing materials, such as epoxy-based fillers.

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

  As the hindered phenol-based anti-aging agent, various types such as Irganox 1010 available from Ciba Specialty Chemicals may be used.

  Examples of the sulfur-based antioxidant include mercaptans, mercaptan salts, sulfides (sulfide carboxylic acid esters and hindered phenol sulfides, etc.), polysulfides, dithiocarboxylates, thioureas, thiophosphates, Examples include sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.

  Moreover, as these anti-aging agents, 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 radical inhibitors include 2,6-di-t-butyl-3-methylphenol (BHT), 2,2′-methylene-bis (4-methyl-6-t-butylphenol) and tetrakis (methylene- 3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate) phenolic radical inhibitors such as methane, and phenyl-β-naphthylamine, α-naphthylamine, N, N′-secondarybutyl-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)
You may add a ultraviolet absorber to the said 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 (A) polysiloxane compound has a high viscosity, it can be dissolved in a solvent. The solvent is not particularly limited, and specifically, hydrocarbon solvents such as benzene, toluene, hexane and heptane; ether solvents 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.

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

  Although the usage-amount of a solvent can be set suitably, the minimum of the preferable usage-amount with respect to 1 g of negative photosensitive resin compositions to be used is 0.1 mL, and the upper limit of a preferable usage-amount is 10 mL. 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, if the amount of the solvent used is large, the solvent remains in the material, which is likely to cause problems such as thermal cracks, which is disadvantageous in terms of cost and may reduce the industrial utility value.

  As these solvents, one kind may be used and two or more kinds of mixed solvents may be used.

(Other)
The negative photosensitive resin composition includes a colorant, a release agent, a flame retardant, a flame retardant aid, a surfactant, an antifoaming agent, an emulsifier, a leveling agent, a repellent agent, an ion trap agent (antimony-bismuth). Etc.), thixotropic agent, tackifier, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, thermal 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 peroxide decomposing agent, a lubricant, a pigment, a metal deactivator, a thermal conductivity imparting agent and a physical property modifier. Can be added within a range that does not impair.

[2. Method for preparing negative photosensitive resin composition]
The preparation method of the said negative photosensitive resin composition is not specifically limited, It can prepare by various methods. Various components may be mixed and prepared immediately before curing, or may be stored at a low temperature in a one-component state in which all components are mixed and prepared in advance.

[3. Laminated body 1 (base material 1 / photosensitive resin composition): a step of applying a negative photosensitive resin composition onto a base material and drying to form a film]
The negative photosensitive resin composition can be handled in liquid form, and a film can be easily formed by solution coating. Therefore, a laminated body (base material 1 / photosensitive resin composition) can be easily formed by applying the negative photosensitive resin composition in a layered manner on a base material (base material 1) and drying it.

  Specifically, for example, the laminate may be produced by the following method. First, the said negative photosensitive resin composition is apply | coated on a base material. Examples of the base material (base material 1) include glasses, polycarbonates, films, silicon wafers on which an image sensor is formed, patterned colored resin films for LCD or CCD color filters, printing paper, and printing. Examples thereof include fibers, ceramic substrates, and metal plates. Examples of the coating method include spin coating, roll coating, printing, and bar coating. The film thickness to apply | coat is 0.05-500 micrometers normally, Preferably it is 0.1-100 micrometers, More preferably, it is 1-100 micrometers. Next, a laminated body can be obtained by performing exposure with active energy rays.

  The laminated body thus obtained can then be developed with an alkaline developer as described later.

[4. Alkali development method (pattern formation process)]
A layered product (base material 1 / photosensitive resin composition) obtained by laminating the negative photosensitive resin composition on a base material (base material 1) and drying it is exposed to an alkaline developer after exposure. By developing, a pattern can be formed.

  As a light source for photocuring (exposure) the negative photosensitive resin composition, a light source that emits an absorption wavelength of a polymerization initiator and a sensitizer to be used may be used, and usually in the range of 200 to 450 nm. A light source including a wavelength (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.

Although the exposure amount for photocuring the negative photosensitive resin composition is not particularly limited, it is preferably 1 to 10,000 mJ / cm ² , more preferably 1 to 3000 mJ / cm ² . If the exposure amount is small, the negative photosensitive resin composition may not be cured. If the exposure amount is large, the color may change due to rapid curing. The range of curing time is preferably 1 to 600 seconds, more preferably 1 to 150 seconds. When the curing time is long, the fast curing characteristic of photocuring is not utilized.

  Further, for the purpose of removing the solvent and improving the physical properties of the cured product, pre-baking and after-baking may be performed by applying heat before and after photocuring. The curing temperature can be appropriately set, but is preferably 40 to 400 ° C, more preferably 60 to 350 ° C.

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

  There is no particular limitation on patterning with an alkaline developer, and a desired pattern can be formed by dissolving and removing unexposed portions by a commonly used development method such as an immersion method or a spray method.

  In addition, the developer used in alkali development can be used without particular limitation as long as it is generally used. Specific examples of the developer include tetramethylammonium hydroxide (TMAH) aqueous solution and organic alkaline aqueous solution such as choline aqueous solution, potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium carbonate aqueous solution, sodium carbonate aqueous solution and lithium carbonate aqueous solution. Inorganic alkaline aqueous solution etc. are mentioned. The aqueous solution may contain an alcohol and a surfactant for adjusting 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 still more preferably 5% by weight or less, from the viewpoint that the contrast between the exposed part and the unexposed part is easily obtained. .

[5. Laminate 2 (Substrate 1 / Photosensitive Resin Composition / Substrate 2): Step of Crimping to Pattern Formed on Substrate]
In the pattern forming step, the base material (base material 2) is pressure-bonded to the pattern of the obtained laminate (base material 1 / photosensitive resin composition). The crimping temperature is usually 25 ° C to 350 ° C, preferably 60 ° C to 300 ° C, more preferably 80 ° C to 250 ° C. As a load at the time of crimping | compression-bond, it is 0-10000 gram weight normally, Preferably it is 0-5000 gram weight, More preferably, it is 0-2500 gram weight.

  From the viewpoint of improving the adhesive force, it is preferable to heat cure at 25 ° C. to 350 ° C. after the pressure bonding.

The base material (base material 2) may be the same material as the base material 1, or may be different.
Examples of the base material (base material 2) include glasses, polycarbonates, films, silicon wafers on which an imaging element is formed, colored resin films patterned with color filters for LCD or CCD, printing paper, and printing. Examples thereof include fibers, ceramic substrates, and metal plates.

[6. (Use)
The said negative photosensitive resin composition and its hardened | cured material can be used for various uses. It can be applied to various uses where conventional acrylic resin and epoxy resin adhesives are used.

  Examples of the applications include transparent materials, optical materials, optical lenses, optical films, optical sheets, optical component adhesives, optical waveguide coupling optical adhesives, optical waveguide peripheral member fixing adhesives, and DVD bonding adhesives. 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 material, adhesive, high heat-resistant adhesive, high heat dissipation adhesive, optical adhesive, LED element adhesive, adhesive for various substrates, heat sink adhesive , Paint, UV powder paint, ink, colored ink, UV inkjet ink, coating material (hard coat, sheet, film, release paper coat, optical disc Coatings and optical fiber coatings), molding materials (including sheets, films and FRPs), sealing materials, potting materials, sealing materials, light-emitting diode sealing materials, optical semiconductor sealing materials, CMOS Hollow structure for CCD sensor, hollow structure for MEMS device, liquid crystal sealant, sealant for display device, sealing material for electrical material, sealing material for various solar cells, high heat resistant sealing material, resist material, liquid resist material , Colored resist, Dry film resist material, Solder resist material, Color filter binder resin, Color filter transparent planarizing material, Black matrix binder resin, Liquid crystal cell photo spacer material, OLED element transparent sealing material, Stereolithography , Solar cell materials, fuel cell materials, display materials, recording materials Anti-vibration materials, waterproof materials, moisture-proof materials, heat-shrinkable rubber tubes, O-rings, photocopier drums for copying machines, solid electrolytes for batteries, gas separation membranes, concrete protective materials, linings, soil injectants, cold storage materials, sterilization equipment Sealing materials, contact lenses, oxygen permeable membranes and the like. Moreover, the said negative photosensitive resin composition may be used as an additive to other resin etc.

  If the negative photosensitive resin composition of the present invention is applied to the hollow structure for a CMOS / CCD sensor and the hollow structure for a MEMS device, the thickness of the wall can be reduced and the structure can be downsized. Therefore, it is preferable. Moreover, since the photosensitive resin composition can be utilized as an adhesive layer, it is also preferable from the viewpoint of simplifying the manufacturing process.

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

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to a following example.

(Patternability evaluation)
The following patternability evaluation samples were produced using the resin compositions obtained in the examples and comparative examples. First, the resin composition obtained by the Example and the comparative example was spin-coated on the glass substrate. The obtained substrate was heated on a hot plate heated to 100 ° C. for 10 minutes. Furthermore, using an exposure device (high-pressure mercury lamp, manual exposure machine, manufactured by Dainippon Kaken Co., Ltd.), each resin composition is exposed with an optimal integrated light amount through a mask engraved with a 50 μm line and space pattern (soft Contact exposure) and left for 1 minute after exposure. Thereafter, the substrate was immersed in an alkaline developer (TMAH 2.38% aqueous solution) for 300 seconds, washed with water for 30 seconds, and moisture on the surface was removed with compressed air or compressed nitrogen to form a pattern.

  Then, it heated for 30 minutes on the hotplate heated at 230 degreeC, and obtained the patternability evaluation sample. About the obtained patternability evaluation sample, a pattern shape was observed using a 3D measurement laser microscope (LEXT OLS4000, Olympus) and a stylus type surface shape measuring instrument (Dektak 150, Veeco), and a 50 μm line and space. The state of was evaluated according to the following criteria.

<Evaluation criteria>
○: Practical level (no residual film in 50 μm line and space)
×: Unsuitable for practical use (with residual film in 50 μm line and space)
(Adhesion evaluation)
A substrate adhesion evaluation sample was obtained in the same manner as the patterning evaluation sample, except that the entire surface was exposed without using a mask instead of the mask with a 50 μm line and space pattern. A silicon wafer cut into 2 mm squares is placed on an evaluation sample heated to 150 ° C. on a hot plate, and a resin film and a silicon wafer are bonded together while applying a load for 10 minutes using a 2000 g weight. Thus, a three-layer laminate of glass, resin film, and silicon wafer was produced. Using a die shear tester (SERIES 4000, manufactured by DAGE) under the following conditions, the adhesion was evaluated from the weight (kgf) at which the resin and the silicon wafer were peeled off.
Share height: 50 μm
Share speed: 80μm / s
<Evaluation criteria>
A: Very good level (die shear strength of 15 kgf or more)
○: Good level (die shear strength 10 kgf to 15 kgf)
Δ: Practical level (die shear strength 1 kgf to 10 kgf)
X: Level not suitable for practical use (die shear strength 1 kgf or less)
(Compatibility evaluation)
The resin compositions obtained in Examples and Comparative Examples were allowed to stand at room temperature for 24 hours in a transparent sample tube bottle, and the compatibility state was evaluated according to the following criteria.

<Evaluation criteria>
○: Practical level (composition is uniform)
X: Level not suitable for practical use (the composition is cloudy)
(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 vinylsiloxane complex (platinum vinylsiloxane complex containing 3 wt% platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) 143 μL was added. 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane was heated to 105 ° C. in a nitrogen atmosphere containing 3% oxygen. 88 g was dropped into a solution prepared by dissolving 176 g of toluene over 3 hours.

30 minutes after the completion of dropping, the reaction rate of the alkenyl group was confirmed to be 95% or more by ¹ H-NMR. Thereafter, a solution prepared by dissolving 62 g of 1-vinyl-3,4-epoxycyclohexane in 62 g of toluene was dropped into the above solution over 1 hour. 30 minutes after the completion of the dropping, ¹ H-NMR confirmed that the reaction rate of the alkenyl group was 95% or more, and then the reaction was terminated by cooling. Solvents toluene and dioxane were distilled off under reduced pressure, and then substituted with PGMEA (propylene glycol 1-monomethyl ether 2-acetate) to obtain “solution A” which was a colorless and transparent 75 wt% polysiloxane compound solution.

  In addition, diallyl isocyanuric acid corresponds to the compound (α1). 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 Production Example 1, the above item <1-1. This corresponds to the second preferred embodiment described in the component (A)>.

Example 1
18 g of “Solution A” described in Production Example 1 as component (A), 0.68 g of lauryl glycidyl ether as component (B), 0.41 g of BBI-103 (manufactured by Midori Chemical Co., Ltd.) as a photoacid generator, A 60% PGMEA (propylene glycol monomethyl ether acetate) solution to which 0.68 g of 9,10-dibutoxyanthracene was added as a sensitizer was prepared.

(Example 2)
27 g of “Solution A” described in Production Example 1 as component (A), 1.35 g of lauryl glycidyl ether as component (B), 0.41 g of BBI-103 as a photoacid generator, 9, A 60% PGMEA solution to which 0.68 g of 10-dibutoxyanthracene was added was prepared. That is, Example 2 differs from Example 1 in the amount of component (B) added.

(Example 3)
27 g of “Solution A” described in Preparation Example 1 as component (A), 1.35 g of octyl glycidyl ether as component (B), 0.41 g of BBI-103 as photoacid generator, 9, A 60% PGMEA solution to which 0.68 g of 10-dibutoxyanthracene was added was prepared. That is, Example 3 differs from Example 1 in the type of component (B).

Example 4
27 g of “Solution A” described in Production Example 1 as component (A), 1.35 g of butyl glycidyl ether as component (B), 0.41 g of BBI-103 as photoacid generator, 9, A 60% PGMEA solution to which 0.68 g of 10-dibutoxyanthracene was added was prepared. That is, Example 4 differs from Example 1 in the type of component (B).

(Comparative Example 1)
60% of 27% 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).

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

  Note that “phr” in Table 1 is an abbreviation for “per hundred resin” and represents the amount of component (B) added when the solid content other than component (B) is 100.

  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, a cured film having patterning properties and high substrate adhesion can be obtained.

  Although the comparative example 1 is an example which does not contain a component (B), adhesiveness was inadequate.

  INDUSTRIAL APPLICABILITY The present invention can be used in various fields such as insulating materials, adhesives, coating agents and sealants, and in particular, it can also be used for hollow structures for CMOS / CCD sensors and hollow structures for MEMS devices. Can do.

Claims (15)

(A) In one molecule, a polysiloxane compound having at least one photopolymerizable functional group and at least one alkali-soluble functional group, and (B) at least one kind represented by the following formula (Y1) A negative photosensitive resin composition comprising: a compound;

(In the formula (Y1), R ¹ is a group represented by the following formulas (Y2) to (Y6), and R ² is an alkyl group having 1 to 20 carbon atoms.)

The negative photosensitive resin composition according to claim 1, wherein R ² in the formula (Y1) is an alkyl group having 4 to 20 carbon atoms.
The alkali-soluble functional group is represented by the following formula (X1) or (X2)

3. The negative photosensitive resin composition according to claim 1, wherein the negative photosensitive resin composition is at least one selected from the group consisting of a structure represented by: phenolic hydroxyl group and carboxyl group.   The negative photosensitive resin composition according to any one of claims 1 to 3, wherein at least one of the photopolymerizable functional groups is an alicyclic epoxy group or a glycidyl group.   The said polysiloxane type compound is a compound in which the said photopolymerizable functional group and the said alkali-soluble functional group were introduce | transduced by the silicon-carbon bond, The any one of Claims 1-4 characterized by the above-mentioned. Negative photosensitive resin composition.   The negative photosensitive resin composition according to any one of claims 1 to 5, further comprising a photoacid generator.   Hardened | cured material which the negative photosensitive resin composition of any one of Claims 1-6 hardened | cured.   The laminated body provided with the cured film which the negative photosensitive resin composition of any one of Claims 1-6 hardened | cured on a base material.   The layered product according to claim 8, wherein the film thickness of the negative photosensitive resin composition of the layered product is 10 µm or more.   The laminate according to claim 8, wherein at least one layer of the laminate has glass on the surface.   A hollow structure for a CMOS / CCD sensor, comprising a cured film obtained by curing the resin according to claim 1.   A hollow structure for a MEMS device, comprising a cured film obtained by curing the resin according to claim 1. Applying and drying the resin according to any one of claims 1 to 6 on a substrate (substrate 1) to form a film;
A method for producing a laminate comprising a pattern forming step of developing with an alkaline developer after exposure, and a step of pressure-bonding to a pattern on which a base material (base material 2) is formed.   The method for producing a laminate according to claim 13, wherein the substrate 1 is made of glass.   The method for manufacturing a laminate according to claim 13 or 14, wherein the substrate 2 is a silicon wafer.