JP2017090515A - Negative type curable composition, cured article and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition excellent in heat resistant transparency and capable of manufacturing a cured article excellent in tack and patterning.SOLUTION: The above described problem is solved by providing a negative type curable composition containing (A) an ester compound having a specific structure and (B) a specific modified polyorganosiloxane compound.SELECTED DRAWING: None

Description

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

  In electronic parts and semiconductor parts, polysiloxanes containing polyhedral structures having various functional groups, since the cured products obtained are highly transparent and have high reliability such as good heat resistance and light resistance. Application of compounds is under consideration.

  The applicant of the present application has previously made an invention relating to a polysiloxane compound having a developability in an alkaline aqueous solution and capable of giving a cured product excellent in heat-resistant transparency, and a curable composition thereof. A patent application was filed (Patent Document 1).

  One application of the polysiloxane material is a resist material. As the resist material, for example, an interlayer insulating film for display is cited, and the insulating film is desired to have high heat resistance and low dielectric constant. The interlayer insulating film can be obtained by making the photosensitive resin uniform with a thickness of several μm, exposing through a pattern mask, and developing with alkali. In the case of a negative photosensitive resin, the exposed portion is cured, and the unexposed portion is uncured, so that it is dissolved in the developer to obtain a patterning film. Control of the process of removing the uncured portion by dissolving it in an alkaline developer is important for producing a cured product having excellent tack and patterning properties.

  As a method for adjusting the dissolution rate of the uncured portion in the developing solution, for example, molecular design of a matrix resin, addition of a quencher, and the like are known (Patent Documents 2 and 3).

International Publication No. 2009/075233 (released on June 18, 2009) International Publication No. 2014/199967 (released on December 18, 2014) JP 2001-330957 A (published November 30, 2001)

  However, in the prior art, it is difficult to adjust the dissolution rate of the uncured portion generated when the curable composition is cured with respect to the developer, and the uncured portion is appropriately removed to achieve tack and patternability. There was room for improvement in producing an excellent cured product.

  This invention is made | formed in view of the said problem, The objective is providing the curable composition which can manufacture the hardened | cured material which was excellent in heat-resistant transparency, and excellent in tack and patterning property. is there.

  As a result of intensive studies to achieve the above object, the present inventor can adjust the dissolution rate of the uncured portion in the developer by adding a small amount of a specific ester compound to the negative curable composition. I found. Furthermore, as a result of adjusting the dissolution rate of the uncured part by the addition of the ester compound, it was found that a cured product having excellent tack and patterning properties was obtained, and the present invention was completed.

  That is, the present invention includes the following configurations.

[1] (A) The boiling point at 5 mmHg is 200 ° C. or more, and 0.01 to 5 parts by weight of the ester compound represented by the following formula (1) with respect to the component (B);
R ^1- (COO-R ² ) _m (1)
(Wherein R ¹ and R ² are each independently an aliphatic chain hydrocarbon, an aliphatic cyclic hydrocarbon, or an aromatic hydrocarbon, and m is an integer of 2 to 4);
(B) having at least two photopolymerizable functional groups in one molecule, and
Structures represented by the following formulas (2) and (3);

A modified polyorganosiloxane compound having in the same molecule at least one selected from the group consisting of phenolic hydroxyl groups and carboxyl groups;
A negative curable composition comprising:

[2] The negative curable composition according to [1], wherein R ¹ and R ² of the ester compound (A) are aliphatic chain hydrocarbons.

  [3] The ester compound of (A) is dioctyl adipate, di (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, dioctyl azelate, di (2-ethylhexyl) azelate, diisononyl azelate, The negative curable composition according to [1], which is diisodecyl azelate, dioctyl sebacate, di (2-ethylhexyl) sebacate, diisononyl sebacate or diisodecyl sebacate.

  [4] The negative curable composition according to any one of [1] to [3], further comprising a photoacid generator as the component (C).

  [5] A cured product obtained by curing the negative curable composition according to any one of [1] to [4].

  [6] A laminate comprising a cured film obtained by curing the negative curable composition according to any one of [1] to [4] on a substrate.

  The present invention has the effect of enabling the production of a cured product having excellent heat-resistant transparency and excellent tack and patterning properties.

  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 curable composition]
The negative curable composition according to an embodiment of the present invention includes (A) an ester compound having a specific structure, (B) at least two photopolymerizable functional groups in one molecule, and at least And a modified polyorganosiloxane compound having one specific acidic group in the same molecule. Hereinafter, the ester compound (A) having a specific structure is simply referred to as “component (A)”, and (B) the molecule has at least two photopolymerizable functional groups, and at least one A modified polyorganosiloxane compound having a specific acidic group in the same molecule may be simply referred to as “component (B)”. Further, the “curable composition” may be referred to as “resin composition”, “photosensitive resin composition”, or “photosensitive resin”.

  Since this negative curable composition contains the above-mentioned two components, it makes it possible to produce a cured product having excellent heat-resistant transparency and excellent tack and patterning properties. By including the component (B), the present curable composition can produce a cured product having alkali developability and excellent heat-resistant transparency. On the other hand, by containing the component (A), it is possible to adjust the dissolution rate of the uncured portion with respect to the developer at the time of curing, and as a result, it is possible to produce a cured product having excellent tack and patterning properties.

<1-1. (A) component>
This negative curable composition contains the compound shown below as (A) component. Since this negative curable composition contains the component (A), it becomes possible to produce a cured product having excellent tack and patterning properties. This is a finding found by the present inventors for the first time.

The component (A) is represented by the following formula (1):
R ^1- (COO-R ² ) _m (1)
(Wherein, R ¹ and R ² are each independently an aliphatic chain hydrocarbon, an aliphatic cyclic hydrocarbon or an aromatic hydrocarbon, and m is an integer of 2 to 4)
It is an ester compound represented by these.

  An aliphatic chain hydrocarbon, an aliphatic cyclic hydrocarbon, or an aromatic hydrocarbon is technical common sense in the technical field, and is not particularly limited as long as it is commonly used by those skilled in the art.

  Examples of the aliphatic chain hydrocarbon include normal ethyl, normal propyl, normal butyl, normal pentyl, normal hexyl, normal heptyl, normal octyl, normal nonyl, normal decyl, stearyl, 2-ethylhexyl, isononyl, isodecyl, isostearyl. Etc. Examples of the aliphatic cyclic hydrocarbon include cyclohexanyl, dicyclopentanyl, dicyclopentenyl, isobornyl and the like. Furthermore, examples of the aromatic hydrocarbon include phenyl, benzyl, nonylphenyl, bisphenol, bisphenol A, and bisphenol F.

As R ¹ and R ² , an aliphatic chain hydrocarbon is preferably used from the viewpoint of compatibility with the component (B).

  Examples of the component (A) include, for example, dioctyl adipate, di (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, dioctyl azelate, di (2-ethylhexyl) azelate, diisononyl azelate, azelain Examples include diisodecyl acid, dioctyl sebacate, di (2-ethylhexyl) sebacate, diisononyl sebacate, diisodecyl sebacate and the like. As the component (A), dioctyl adipate, di (2-ethylhexyl) adipate, diisononyl adipate and diisodecyl adipate are preferably used from the viewpoint of improving tack and patterning properties.

  The component (A) is also characterized by having a specific boiling point. The boiling point is preferably 200 ° C. or higher at 5 mmHg, more preferably 210 ° C. or higher, further preferably 230 ° C. or higher, and particularly preferably 240 ° C. or higher. If the boiling point at 5 mmHg is at least 200 ° C., a cured product having excellent tack and patterning properties can be produced. The upper limit of the boiling point of the ester compound is not particularly limited, but if the ester compound remains in the cured film after post-baking, the heat resistance of the interlayer insulating film is lowered, and 400 ° C. is preferable at 5 mmHg.

  The component (A) is used in a specific amount so that the dissolution rate of the uncured portion generated when the curable composition is cured can be adjusted with respect to the developer. The amount of component (A) used is preferably 0.01 to 5 parts by weight with respect to component (B) and more preferably 0.1 to 4 parts by weight with respect to component (B). When the amount of component (A) used is in the above range, it is preferable because sufficient functions can be obtained for both tack and patterning.

<1-2. (B) component>
The present negative curable composition contains a modified polyorganosiloxane compound (hereinafter sometimes simply referred to as “polysiloxane compound”) as the component (B). By containing (B) component, while having alkali developability, the hardened | cured material excellent in heat-resistant transparency can be manufactured.

  Hereinafter, the polysiloxane compound as the component (B) will be described in detail.

(Polysiloxane compounds)
The polysiloxane compound has a structure represented by the following formulas (2) and (3);

And a group consisting of a phenolic hydroxyl group and a carboxyl group (hereinafter, “the structures represented by the above formulas (2) to (3), the phenolic hydroxyl group and the carboxyl group” may be referred to as “acidic group”). A modified polyorganosiloxane compound having at least one selected from the above in the same molecule is preferably used. By having the acidic group in the same molecule, it can be dissolved in an alkaline aqueous solution, and can be applied as a resist material capable of alkali development.

  Among these organic structures, a carboxyl group and each structure represented by the above formulas (2) to (3) are preferable from the viewpoint that the obtained cured product is less colored after heating, and further, thermal decomposition at high temperatures. In particular, those having structures represented by the above formulas (2) to (3) are preferable from the viewpoint of obtaining a cured product having low properties. The polysiloxane compound further has at least one photopolymerizable functional group in one molecule. The photopolymerizable functional group as used herein refers to a functional group that is polymerized and cross-linked by radicals or cationic species generated from a photopolymerization initiator when light energy is applied from the outside, and the reaction / crosslinking mode is particularly limited. It is not a thing.

  Among them, particularly from the viewpoint of reactivity and stability of the compound, at least one of the photopolymerizable functional groups is an epoxy group, a crosslinkable silicon group (sometimes referred to as a “hydrolyzable silyl group”), (meta ) An acryloyl group and a vinyloxy group are preferable. Among the epoxy groups, an alicyclic epoxy group and a glycidyl group are 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. From the viewpoint, an alkoxysilyl group is particularly preferable. 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, A methoxy group and an ethoxy group are particularly preferable from the viewpoint that residual components after curing hardly remain.

  From the viewpoint of reactivity, an alkoxysilylethyl group or an alkoxysilylpropyl group is preferable, and specifically, (alkoxysilylethyl) dimethylsilyl group, (alkoxysilylethyl) diphenylsilyl group, (alkoxysilylpropyl) dimethyl group. Silyl groups and (alkoxysilylpropyl) diphenyl groups are preferred.

  The polysiloxane compound may have at least one photopolymerizable functional group in one molecule, but is preferably 2 or more, more preferably 3 or more. If it is three or more, there exists an advantage that the hardened | cured material with a high crosslinking density is obtained and it is excellent in heat resistance. Each photopolymerizable functional group may be the same or may have two or more different functional groups.

The polysiloxane compound is not particularly limited as long as it has a siloxane unit Si—O—Si. Among the siloxane units in these compounds, the cured product obtained with a higher content of T unit (XSiO _3/2 ) or Q unit (SiO _4/2 ) in the constituent component has higher hardness and more heat resistance reliability. The cured product is more flexible and has lower stress as it is more excellent and has a higher content of M units (X3SiO _1/2 ) or D units (X2SiO _2/2 ).

  By introducing the acidic group structure and the photocrosslinking functional group into the polysiloxane, it can be applied as a resist material capable of alkali development. The method for introducing the acidic group structure and the photocrosslinking functional group into the polysiloxane is not particularly limited, but it is preferable to use a hydrosilylation reaction that can be introduced with a chemically stable Si—C bond.

  The polysiloxane compound is preferably a hydrosilylation reaction product. As a preferable aspect of a hydrosilylation reaction product, the following aspects can be mentioned, for example.

As a first preferred embodiment, hydrosilylation reaction products of the following compounds (α1), (β) and (γ):
(Α1) one molecule having at least one carbon-carbon double bond having reactivity with a SiH group, and a structure represented by the above formulas (2) to (3), a phenolic hydroxyl group, An organic compound having at least one selected from the group consisting of a carboxyl group in the same molecule,
(Β) a polysiloxane compound having at least two SiH groups in one molecule, and (γ) a carbon-carbon having reactivity with at least one photopolymerizable functional group and SiH groups in one molecule. A compound having one or more double bonds.

As a second preferred embodiment, hydrosilylation reaction products of the following compounds (α1), (α2), (β) and (γ):
(Α1) one molecule having at least one carbon-carbon double bond having reactivity with a SiH group, and a structure represented by the above formulas (2) to (3), a phenolic hydroxyl group, An organic compound having at least one selected from the group consisting of a carboxyl group in the same molecule,
(Α2) a compound having one or more carbon-carbon double bonds having reactivity with SiH groups in one molecule;
(Β) a polysiloxane compound having at least two SiH groups in one molecule, and (γ) a carbon-carbon having reactivity with at least one photopolymerizable functional group and SiH groups in one molecule. A compound having one or more double bonds.

  Hereinafter, the preferable embodiment of the polysiloxane compound will be described.

(Compound (α1))
The compound (α1) has a structure of any one of the group consisting of each structure represented by the above formulas (2) to (3), a phenolic hydroxyl group, and a carboxyl group in the molecule, and an SiH group. The organic compound is not particularly limited as long as it is an organic compound having one or more carbon-carbon double bonds having reactivity with the same in the same molecule.

  The organic compound does not contain a siloxane unit (Si-O-Si) like polysiloxane-organic block copolymer or polysiloxane-organic graft copolymer, and is composed of C, H, N, O, S and halogen as constituent elements. It is preferable that only those selected from the group are included. Those containing siloxane units have gas permeability and repelling problems.

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

  The carbon-carbon double bond having reactivity with the SiH group of the compound (α1) is not particularly limited and can be used. Vinyl, allyl, methallyl, acryl, methacryl, 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 Examples include-(allyloxy) ethyl group, 2,2-bis (allyloxymethyl) butyl group, 3-allyloxy-2, 2-bis (allyloxymethyl) propyl group, and vinyl ether group. In particular, a vinyl group and an allyl group are preferable from the viewpoint of reactivity.

  The compound (α1) may have at least one carbon-carbon double bond having reactivity with the SiH group in one molecule. However, since the resulting cured product has a high crosslinking density, it has high heat reliability. Two or more are preferable, and three or more are more preferable.

  Although it does not necessarily limit as a compound ((alpha) 1), From a viewpoint with few coloring at high temperature, the structure shown by following formula (4) and (5) which has an isocyanuric ring;

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

  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, a phenyl group, a methyl group, an ethyl group, a propyl group, a benzyl group, and a glycidyl group. Group, and the organic group having 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, diallyl isocyanuric acid, monoallyl isocyanuric acid, vinylphenol, allylphenol, a structure represented by the following formula (9);

Butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid and undecylenic acid are preferred. Among these, diallyl isocyanuric acid, monoallyl isocyanuric acid, diallyl bisphenol A, diallyl bisphenol S, vinyl phenol, and allyl phenol are preferable from the viewpoint of particularly high heat resistance, and diallyl isocyanuric acid from the viewpoint of transparency of the cured product, Monoallyl isocyanuric acid is particularly preferred.

  The compound (α1) can be used alone or in combination of two or more.

(Compound (α2))
If the compound (α2) is a compound that does not correspond to the compound (α1) and the compound (γ) described later, and has one or more carbon-carbon double bonds having reactivity with SiH groups in one molecule, It is not limited.

  From the viewpoint of high heat resistance of the resulting cured product, it is preferably a polysiloxane having at least one alkenyl group, specifically, an alkenyl group-containing polysiloxane having a linear structure, an alkenyl group at the molecular end. It is possible to use a polysiloxane having an alkenyl group, a cyclic siloxane compound containing an alkenyl group, and the like. Although not particularly limited by the structure, in view of heat resistance, light resistance, chemical stability, etc., alkenyl A polysiloxane having a polyhedral skeleton containing a group is preferred.

  Specific examples of the alkenyl group-containing polysiloxane having a linear structure include copolymers of dimethylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units. Examples thereof include copolymers, copolymers of methylphenylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units, and polysiloxanes whose ends are blocked with dimethylvinylsilyl groups.

Specific examples of the polysiloxane having an alkenyl group at the molecular end include the polysiloxane whose end is blocked by the dimethylalkenyl group exemplified above, a dimethylalkenylsiloxane unit and a SiO ₂ unit, a SiO _3/2 unit, and a SiO unit. Examples thereof include polysiloxane composed of at least one siloxane unit selected from the group.

  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, 1,3,5,7,9,11-hexavinyl-1,3 Examples include 5,7,9,11-hexamethylcyclosiloxane.

  The polyhedral polysiloxane having an alkenyl group preferably has 6 to 24 Si atoms contained in the polyhedral skeleton. Specifically, for example, a silsesquiski having a polyhedral structure represented by the following structure is used. Oxan (formula (10)) is exemplified (here, the number of Si atoms = 8 is exemplified as a representative example).

In the above formula, R ^{10 to} R ¹⁷ are alkenyl groups such as vinyl group, allyl group, butenyl group, hexenyl group, (meth) acryloyl group, epoxy group, mercapto group, amino group-containing organic group, hydrogen atom, methyl group Group, ethyl group, propyl group, alkyl group such as butyl group, cycloalkyl group such as cyclohexyl group, aryl group such as phenyl group and tolyl group, or part or all of hydrogen atoms bonded to carbon atoms of these groups Is the same or different, preferably an unsubstituted group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, selected from a chloromethyl group, a trifluoropropyl group, a cyanoethyl group, etc. Or it is a substituted monovalent hydrocarbon group.

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

The silsesquioxane having the polyhedral structure is, for example, RSiX ₃ (wherein R represents R ^{10 to} R ¹⁷ described above, and X represents a hydrolyzable functional group such as a halogen atom or an alkoxy group). ) Of the silane compound.

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

  As a more preferable example of the compound (α2), a silylated silicic acid (formula (11)) having a polyhedral structure represented by the following structure is exemplified (here, the number of Si atoms = 8 is a representative example) As an example). In this compound, since the Si atom forming the polyhedral skeleton and the alkenyl group which is a reactive group are bonded via a siloxane bond, the resulting cured product is not too rigid, and a good molded product Can be obtained.

In the above structure, R ^{18 to} R ⁴¹ are an alkenyl group such as vinyl group, allyl group, butenyl group, hexenyl group, (meth) acryloyl group, epoxy group, mercapto group, amino group-containing organic group, hydrogen atom A methyl group, an ethyl group, a propyl group, an alkyl group such as a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group or a tolyl group, or a part of hydrogen atoms bonded to carbon atoms of these groups Alternatively, they are the same or different organic groups selected from a chloromethyl group, a trifluoropropyl group, a cyanoethyl group and the like, all of which are substituted with a halogen atom, a cyano group or the like. However, at least one of these R ^{18 to} R ⁴¹ 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.

  It does not specifically limit as a synthesis method of the silicate which has a polyhedral structure, It can synthesize | combine using a well-known method. 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, a silicate having a similar polyhedral structure can be obtained from a silica-containing substance such as silica or rice husk instead of tetraalkoxylane.

  In this synthesis method, a silicate having a polyhedral structure 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. It is possible to obtain a polysiloxane in which Si atoms forming a polyhedral structure and an alkenyl group which is a reactive group are bonded via a siloxane bond.

  In the present invention, the number of Si atoms contained in the polyhedral skeleton is preferably 6 to 24, more preferably 6 to 10. Further, it may be a mixture of polysiloxanes having polyhedral skeletons having different numbers of Si atoms. Further, it is desirable that the number of alkenyl groups contained in one molecule is at least 1, more preferably at least 2, and further preferably at least 3. From the viewpoint of heat resistance and light resistance, the Si atom is preferably composed of vinyl and methyl groups.

  Further, from the viewpoint of high adhesion to the substrate, an organic compound having one or more carbon-carbon double bonds having reactivity with SiH groups in one molecule can also be used.

  As the compound (α2), an organic compound having one or more carbon-carbon double bonds having reactivity with SiH groups in one molecule may be used. The organic compound here can be classified into an organic polymer compound and an organic monomer compound.

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

  Examples of organic monomer compounds include aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene: aliphatic hydrocarbons such as straight-chain and alicyclics: heterocyclic compounds, and these A mixture etc. are mentioned.

  Specific examples of the compound (α2) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether. 1,1,2,2-tetraallyloxyethane, diarylidenepentaerythritol, triallyl cyanurate, triallyl isocyanurate, diallyl monobenzyl isocyanurate, 1,2,4-trivinylcyclohexane, 1,4 -Butanediol divinyl ether, nonanediol divinyl ether, 1,4-cyclohexane dimethanol divinyl ether, triethylene glycol divinyl ether, trimethylo Propane 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 (1,2 ratio of 10 to 100% by weight, preferably 1 and 2 in a proportion of 50 to 100% by weight), allyl ether of novolak phenol, allylated polyphenylene oxide, and those in which all glycidyl groups of conventionally known epoxy resins are substituted with allyl groups.

  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. Examples thereof include aromatic cyclic polyene compound systems and substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene.

  In particular, a compound represented by the following formula (6) is particularly preferable from the viewpoint of high heat resistance and light resistance.

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

  Examples of the organic group include a hydrocarbon group (which may be partially substituted with oxygen), and the number of carbon atoms is 1 to 20 from the viewpoint that the obtained cured product can have higher heat resistance. It is preferable that it is C1-C10, and it is more preferable that it is C1-C4. Examples of these preferable R3 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 organic compound include triallyl isocyanurate.

  The compound (α2) can be used alone or in combination of two or more.

(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 WO96 / 15194 is at least two in one molecule. Those having SiH groups can be used.

  Specifically, it is possible to use a hydrosilyl group-containing polysiloxane having a linear structure, a polysiloxane having a hydrosilyl group at the molecular end, and a cyclic polysiloxane compound containing a hydrosilyl group, and the structure is particularly limited. It is not a thing. In view of heat resistance, light resistance, chemical stability, and the like, polysiloxane having a polyhedral skeleton containing a hydrosilyl group is preferable. A compound ((beta)) may be used independently and may use 2 or more types together.

  Specific examples of hydrosilyl group-containing polysiloxanes having a linear structure include copolymers of dimethylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units. And a copolymer of a methylphenylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, a polysiloxane having a terminal blocked with a dimethylhydrogensilyl group, and the like.

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

  Cyclic polysiloxane compounds containing hydrosilyl groups include 1,3,5,7-hydrogen-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-tri Hydrogen-1,3,5-trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7, Examples include 9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclosiloxane.

  The polyhedral polysiloxane containing a hydrosilyl group preferably has 6 to 24 Si atoms contained in the polyhedral skeleton. Specifically, for example, a polysiloxane having a polyhedral structure represented by the following structure is used. Sesquioxane (formula (10)) is exemplified (here, Si atom number = 8 is exemplified as a representative example).

In the above formula, R ^{10 to} R ¹⁷ are an alkenyl group such as vinyl group, allyl group, butenyl group, hexenyl group, (meth) acryloyl group, epoxy group, mercapto group, amino group-containing organic group, hydrogen atom, Alkyl group such as methyl group, ethyl group, propyl group and butyl group, cycloalkyl group such as cyclohexyl group, aryl group such as phenyl group and tolyl group, or a part of hydrogen atoms bonded to carbon atoms of these groups or The same or different, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, all selected from a chloromethyl group, a trifluoropropyl group, a cyanoethyl group, etc., all substituted with halogen atoms, cyano groups, etc. A substituted or substituted monovalent hydrocarbon group. However, at least one of R ^{10 to} R ¹⁷ is a hydrosilyl group that is a reactive group of the hydrosilylation reaction.

The silsesquioxane having the polyhedral structure is, for example, RSiX ³ (wherein R represents R ^{10 to} R ¹⁷ described above, and X represents a hydrolyzable functional group such as a halogen atom or an alkoxy group). ) Of the silane compound. Alternatively, after synthesizing a trisilanol compound having three silanol groups in the molecule by the hydrolysis condensation reaction of RSiX ₃ , the ring is closed by reacting the same or different trifunctional silane compounds to form a polyhedral skeleton. A method for synthesizing silsesquioxane is also known.

  As a more preferred example of the compound (β), a silylated silicic acid (formula (11)) having a polyhedral structure as shown by the following structure is exemplified (here, the number of Si atoms = 8 is a representative example) As an example). In this compound, since the Si atom forming the polyhedral skeleton and the reactive group are bonded via a siloxane bond, the obtained cured product is not too rigid, and an excellent cured product can be obtained. it can.

In the above structure, R ^{18 to} R ⁴¹ are an alkenyl group such as vinyl group, allyl group, butenyl group, hexenyl group, (meth) acryloyl group, epoxy group, mercapto group, amino group-containing organic group, hydrogen atom A methyl group, an ethyl group, a propyl group, an alkyl group such as a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group or a tolyl group, or a part of hydrogen atoms bonded to carbon atoms of these groups Alternatively, they are the same or different organic groups selected from a chloromethyl group, a trifluoropropyl group, a cyanoethyl group and the like, all of which are substituted with a halogen atom, a cyano group or the like. However, at least one of these R ^{18 to} R ⁴¹ is a hydrosilyl group that is a reactive group for the hydrosilylation reaction.

  It does not specifically limit as a synthesis method of the silicate which has a polyhedral structure, It can synthesize | combine using a well-known method. 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, a silicate having a similar polyhedral structure can be obtained from a silica-containing substance such as silica or rice husk instead of tetraalkoxylane.

  In this synthesis method, a silicate having a polyhedral structure 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.

  In the present invention, the number of Si atoms contained in the polyhedral skeleton is preferably 6 to 24, more preferably 6 to 10. Further, it may be a mixture of polysiloxanes having polyhedral skeletons having different numbers of Si atoms.

  In the present invention, the number of hydrosilyl groups contained in one molecule is desirably at least 2, more preferably at least 3. In the present invention, from the viewpoint of heat resistance and light resistance, the Si atom is preferably composed of a hydrogen atom and a methyl group.

  The compound (β) is a structure represented by the following formula (7) from the viewpoint of availability and reactivity with the compounds (α1), (α2) and (γ);

(In the formula, R ⁴ and R ⁵ each represent an organic group having 1 to 6 carbon atoms, and the carbon number may be the same or different, n is 1 to 10, and m is 0 to 10. A cyclic organopolysiloxane having at least 3 SiH groups in one molecule is preferred.

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

The substituents R ⁴ and R ⁵ in the compound represented by the formula (7) are preferably selected from the group consisting of C, H and O, more preferably a hydrocarbon group. Preferably, it is a methyl group.

  The compound represented by the formula (7) is preferably 1,3,5,7-tetramethylcyclotetrasiloxane from the viewpoint of availability and reactivity.

  The various compounds (β) described above can be used alone or in combination of two or more.

(Compound (γ))
The compound (γ) is not particularly limited as long as it is a compound having at least one photopolymerizable functional group and one or more carbon-carbon double bonds having reactivity with SiH groups in one molecule. In addition, the photopolymerizable functional group here is the same as the photopolymerizable functional group which the above-mentioned polysiloxane compound has, and its preferable aspect is also preferable.

  The carbon-carbon double bond having reactivity with the SiH group is preferably the same as the carbon-carbon double bond having reactivity with the SiH group of the aforementioned compounds (α1) and (α2).

  Specific examples of the compound having an epoxy group as a photopolymerizable functional group include vinylcyclohexene oxide, allyl glycidyl ether, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate and the like, and has excellent photopolymerization reactivity. From the viewpoint, vinylcyclohexene oxide, which is a compound having an alicyclic epoxy group, is particularly preferable.

  Specific examples of the compound 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, phenyldimethoxyvinylsilane; acyloxysilanes such as methyldiacetoxyvinylsilane, phenyldiacetoxyvinylsilane; bis (dimethylketoximate ) Examples include, but are not limited to, ketoximate silanes such as methyl vinyl silane and bis (cyclohexyl ketoximate) methyl vinyl silane. Not to. Among these, alkoxysilanes can be preferably used. When the photopolymerizable functional group is a crosslinkable silicon group, there is an advantage of excellent heat resistance.

  From the viewpoint of easy availability, the structure represented by the following formula (8);

(Wherein R ⁶ and R ⁷ each represents an organic group having 1 to 6 carbon atoms, n represents 1 to 3, and m represents a number of 0 to 10). Trimethoxyvinyl silane, triethoxyvinyl silane, dimethoxymethyl vinyl silane, diethoxymethyl vinyl silane, methoxy dimethyl vinyl silane, and ethoxy dimethyl vinyl silane are particularly preferable from the viewpoint of easy removal of by-products after the reaction.

  Examples of the compound having an acryloyl group or a methacryloyl group as a photopolymerizable functional group include allyl (meth) acrylate, vinyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ( (Meth) acrylic acid-modified allyl glycidyl ether (manufactured by Nagase ChemteX, trade name: Denacol acrylate DA111), and vinyl group or allyl group and the following formula (12);

(In the formula, R ⁴² represents a hydrogen atom or a methyl group.) A compound having one or more organic groups each in the same molecule, for example, in the above formula (6), R ³ in the formula At least one of the groups represented by the above formula (13) and at least one of R3 is a group having a carbon-carbon double bond having reactivity with a SiH group such as a vinyl group or an allyl group. There are certain compounds. Further, from the viewpoint of high selectivity for hydrosilylation, a compound in which a methacryloyl group coexists with an allyl or vinyl group in the same molecule is preferable, and allyl (meth) acrylate and / or (meta ) Vinyl acrylate is preferred, and allyl methacrylate and vinyl methacrylate are preferred.

  Moreover, in the case of hydrosilylation reaction, 2 or more types of compounds ((gamma)) can also be used together regardless of the kind of photopolymerizable functional group.

(Hydrosilylation catalyst)
A known hydrosilylation catalyst may be used as a catalyst for the hydrosilylation reaction of the compounds (α1), (α2), (β) and (γ).

  From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable. Moreover, these catalysts may be used independently and may be used together 2 or more types.

The addition amount of the catalyst is not particularly limited, but the lower limit of the preferred addition amount is a carbon-carbon double bond having reactivity with the SiH group charged at the time of the reaction (hereinafter simply referred to as “additional amount”). It may be referred to as an “alkenyl group.”) 10 ⁻⁸ mol, more preferably 10 ⁻⁶ mol per 1 mol, and the upper limit of the preferable addition amount is 10 ⁻¹ per mol of the alkenyl group of the above compound. Mol, more preferably ^10-2 mol.

In addition, a cocatalyst can be used in combination with the above catalyst. Examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, 2-hydroxy-2-methyl-1 Examples include acetylene alcohol compounds such as butyne and 1-ethynyl-1-cyclohexanol, and sulfur compounds such as simple sulfur. The addition amount of the cocatalyst is not particularly limited, but the lower limit of the preferable addition amount relative to 1 mol of the hydrosilylation catalyst is 10 ⁻² mol, more preferably 10 ⁻¹ mol, and the upper limit of the preferable addition amount is 10 ^2. Mol, more preferably 10 mol.

(Reaction method of hydrosilylation)
There are various reaction orders and methods, but from the viewpoint that the synthesis step is simple, a method in which all compounds are hydrosilylated in one pot and finally unreacted compounds are removed is preferred.

  From the viewpoint that it is difficult to contain a low molecular weight substance, an excess alkenyl group-containing compound (compound (α1) and / or (α2)) and a SiH group-containing compound (compound (β)) or an excess of SiH groups Hydrosilylation reaction of the compound containing compound (compound (β)) and the alkenyl group-containing compound (compound (α1) and / or (α2)), once removing the unreacted compound, the obtained reactant and compound A method in which (γ) is hydrosilylated is more preferable.

  The proportion of each compound to be reacted is not particularly limited, but when the total alkenyl group amount of the compound to be reacted is A and the total SiH group amount of the compound to be reacted is B, it is preferable that 1 ≦ B / A ≦ 30, Furthermore, it is preferable that 1 ≦ B / A ≦ 10. When 1> B / A, unreacted alkenyl groups remain in the composition, which causes coloring. When 30 <B / A, many unreacted SiH groups remain, so that the composition is cured. It may cause foaming and cracking.

  The reaction temperature can be variously set. In this case, the lower limit of the preferable temperature range is 30 ° C., more preferably 50 ° C., and the upper limit of the preferable temperature range is 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.

  Various reaction times and pressures during the reaction can be set as required. Oxygen can be used during the hydrosilylation reaction. The hydrosilylation reaction can be promoted by adding oxygen to the gas phase portion of the reaction vessel. From the point of setting the amount of oxygen to be below the lower limit of explosion limit, the oxygen volume concentration in the gas phase must be controlled to 3% or less. The oxygen volume concentration in the gas phase is preferably 0.1% or more, more preferably 1% or more, from the viewpoint that the effect of promoting the hydrosilylation reaction by addition of oxygen is observed.

  A solvent may be used during the hydrosilylation reaction. Solvents that can be used are not particularly limited as long as they do not inhibit the hydrosilylation reaction. Specifically, hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1, Ether solvents such as 3-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 can be preferably used. The solvent can also be used as a mixed solvent of two or more types. As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable. The amount of solvent to be used can also be set as appropriate.

In the above-described method for producing a polysiloxane compound, various additives can be used depending on the purpose.
(Geling inhibitor)
For the purpose of improving the storage stability of the resulting reaction product, or after subjecting compound (α1) (or compound (α2) in some embodiments, compound (α2)), compound (β) and compound (γ) to a hydrosilylation reaction, Alternatively, a gelation inhibitor can be used for the purpose of suppressing alteration such as thickening due to heat treatment when removing unreacted compounds 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, benzothiazole, thiazole, dimethyl malate, 3-hydroxy-3-methyl-1-butyne, 1-ethynyl-1-cyclohexanol, and triphenylphosphine are preferable.

  Although the addition amount of the gelation inhibitor can be variously set, the lower limit of the preferable addition amount with respect to 1 mol of the hydrosilylation catalyst to be used is 10-1 mol, more preferably 1 mol, and the upper limit of the preferable addition amount is 103 mol. Preferably it is 102 mol. When there is little addition amount, the desired storage stability and the gelatinization inhibitory effect at the time of vacuum devolatilization will not be acquired. If the amount added is large, it can be a curing inhibitor during the curing reaction.

  Moreover, these gelation inhibitors may be used alone or in combination of two or more.

<1-3. Photoacid generator>
The present negative curable composition may contain a photoacid generator. The photoacid generator is formed by irradiating active energy rays such as visible light, ultraviolet rays, infrared rays, X rays, α rays, β rays, γ rays, i rays, and the like to form a crosslinkable silyl group in the component (B). The compound is not particularly limited as long as it is a compound capable of releasing an acidic active substance capable of crosslinking.

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

  As a photoacid generator that can be used in the present negative curable composition, a known photoacid generator can be used. For example, various compounds which are considered suitable in JP-A No. 2000-1648, JP-T 2001-515533, and International Publication No. 2002-83964 can be mentioned, but the present invention is particularly limited to these. Do not mean. Examples of the photoacid generator that can be preferably used in the present invention include sulfonate esters, carboxylic acid esters, and onium salts, and onium salts are preferably used.

  As a photoacid generator for sulfonate esters, various sulfonic acid derivatives can be used. For example, disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imide sulfonates such as trifluoromethylsulfonate derivatives, benzoin sulfonates, sulfonates of 1-oxy-2-hydroxy-3-propyl alcohol , Pyrogallol trisulfonates, and benzyl sulfonates.

  Specifically, diphenyldisulfone, ditosyldisulfone, bis (phenylsulfonyl) diazomethane, bis (chlorophenylsulfonyl) diazomethane, bis (xylylsulfonyl) diazomethane, phenylsulfonylbenzoyldiazomethane, 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 imide camphor sulfonate, succinimide phenyl sulfonate, succinate Acid imidotosyl sulfonate, succinimide trifluoromethyl sulfonate, succinimide camphor sulfonate, phthalic acid Midtrifluorosulfonate, cis-5-norbornene-endo-2,3-dicarboxylic acid imide trifluoromethylsulfonate, benzoin tosylate, 1,2-diphenyl-2-hydroxypropyl tosylate, 1,2-di (4- Methylmercaptophenyl) -2-hydroxypropyl tosylate, pyrogallol methyl sulfonate, pyrogallol ethyl sulfonate, 2,6-dinitrophenyl methyl tosylate, ortho-nitrophenyl methyl tosylate, para-nitrophenyl tosylate, etc. .

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

  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 onium salts that can be used in the present invention include tetrafluoroborate (BF4-), hexafluorophosphate (PF6-), hexafluoroantimonate (SbF6-), hexafluoroarsenate (AsF6-), hexachloroantimonate (SbCl6). -), Tetraphenylborate, tetrakis (trifluoromethylphenyl) borate, tetrakis (pentafluoromethylphenyl) borate, perchlorate ion (ClO4-), trifluoromethanesulfonate ion (CF3SO3-), fluorosulfonate ion (FSO3) -), Sulfonium salts or iodonium salts having anions such as toluenesulfonate ion, trinitrobenzenesulfonate anion, and trinitrotoluenesulfonate anion are used. It is possible.

  Examples of sulfonium salts include triphenylsulfonium hexafluoroacylate, triphenylsulfonium hexahexafluoroborate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorobenzyl) borate, methyldiphenylsulfonium tetrafluoroborate, methyldiphenyl. Sulfonium tetrakis (pentafluorobenzyl) borate, dimethylphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, diphenylnaphthylsulfonium hexafluoroarsenate, tritoylsulfonium hexafluorophosphate, anisyldipheny Sulfonium hexahexafluoroantimonate, 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 (methoxysulfoni Phenyl) methylsulfonium hexafluoroantimonate, di (methoxynaphthyl) methylsulfonium tetrafluoroborate, di (methoxynaphthyl) methylsulfonium tetrakis (pentafluorobenzyl) borate, di (carbomethoxyphenyl) methylsulfonium hexafluorophosphate, (4- Octyloxyphenyl) diphenylsulfonium tetrakis (3,5-bis-trifluoromethylphenyl) borate, tris (dodecylphenyl) sulfonium tetrakis (3,5-bis-trifluoromethylphenyl) borate, 4-acetamidophenyldiphenylsulfonium tetrafluoro Borate, 4-acetamidophenyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, dimethyl Tyrnaphthylsulfonium hexafluorophosphate, trifluoromethyldiphenylsulfonium tetrafluoroborate, trifluoromethyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, phenylmethylbenzylsulfonium hexafluorophosphate, 10-methylphenoxathinium hexafluorophosphate, 5- Methylthiantrenium hexafluorophosphate, 10-phenyl-9,9-dimethylthioxanthenium hexafluorophosphate, 10-phenyl-9-oxothioxanthenium xanthenium tetrafluoroborate, 10-phenyl-9-oxothio Xanthenium tetrakis (pentafluorobenzyl) borate, 5-methyl-10-oxothiatrenium Tiger fluoroborate, 5-methyl-10-oxo-thia Torre tetrakis (pentafluorobenzyl) borate, and 5-methyl-10,10-and di-oxo-thia tray hexafluorophosphate and the like. These can be used alone or in combination of two or more.

  Examples of the iodonium salt that can be used in the present invention 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-tetradecyloxy) phenyl] phenyliodonium tetrakis (pentafluorophenyl) borate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) io Donium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium trifluorosulfonate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) ) Iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium trifluoromethylsulfonate, di (dodecylphenyl) iodonium hexafluoroantimonate, di (dodecylphenyl) iodonium triflate, diphenyl Iodonium bisulphate, 4,4'-dichlorodiphenyl iodonium bisulphate, 4,4'-dibromodiphe Ruiodonium bisulphate, 3,3′-dinitrodiphenyliodonium bisulphate, 4,4′-dimethyldiphenyliodonium bisulphate, 4,4′-bissuccinimide diphenyliodonium bisulphate, 3-nitrodiphenyliodonium bisulphate, 4,4 '-Dimethoxydiphenyliodonium bisulphate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, (4-octyloxyphenyl) phenyliodonium tetrakis (3,5-bis-trifluoromethylphenyl) borate, US Pat. No. 5 , 554, 664, (Torcumyl) iodonium tetrakis (pentafluorophenyl) borate (CH3C6H4) 2I- (SO2CF3) ) 3, (C6H5) 2I-B (C6F5) 4 disclosed in US Pat. No. 5,514,728, 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.

  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. SI-L147 (manufactured by Sanshin Chemical Industry Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990 (manufactured by Union Carbide), Adekaoptomer SP-150, SP- 151, SP-170, SP-171, 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, CI -2064 (above, Nippon Soda Co., Ltd.), CD-1010, CD-1011, CD-1012 (above 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, BBI-109 (above, manufactured by Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI-022T (above, Nipponization) Yakuhin Co., Ltd.), IBPF, IBCF (Sanwa Chemical Co., Ltd.) CD1012 Tomer), IBPF, IBCF (above, Sanwa Chemical Co., Ltd.), BBI-101, BBI-102, BBI-103, BBI-109 (above, Midori Chemical Co., Ltd.), UVE1014 (General Electronics) And RHODORSIL-PI2074 (manufactured by Rhodia).

  In addition, J.H. 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.

  Although there is no restriction | limiting in particular in content of the photo-acid generator in this negative type curable composition, it is 0.01-10 weight part with respect to 100 weight part of (B) component from a sclerosing | hardenable point. Moreover, it is more preferable that it is 0.1-5.0 weight part from the point of the physical-property balance of hardened | cured material. If the amount of the photoacid generator is small, it takes a long time to cure or a cured product that is sufficiently cured cannot be obtained. Moreover, when there are many photo-acid generators, since a color remains in hardened | cured material or coloring for rapid hardening, heat resistance and light resistance are impaired, it is unpreferable.

<1-4. Cationic polymerization initiator>
The present negative curable composition may contain a cationic polymerization initiator. The cationic polymerization initiator 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, in particular. Can be used without limitation. The photopolymerizable functional group of the component (B) can be crosslinked with the cationic species or Lewis acid.

Examples of active energy ray cationic polymerization initiators include metal fluoroboron complex salts and boron trifluoride complex compounds as described in US Pat. No. 3,379,653; bis (perfluoroalkyls) as described in US Pat. No. 3,586,616. Sulfonyl) 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; described in US Pat. Aromatic onium salts of group Va elements such as: dicarbonyl chelates of group IIIa to Va elements as described in US Pat. No. 4068091; US Pat.
A thiopyrylium salt as described in US Pat. No. 55; a VIa element in the form of an MF6-anion (where M is selected from phosphorus, antimony and arsenic) as described in US Pat. No. 4,161,478; Arylsulfonium complex salts as described in US Pat. No. 4,231,951; aromatic iodonium complex salts and aromatic sulfonium complex salts as described in US Pat. No. 4,256,828; R. Bis [4- (diphenylsulfonio) phenyl] sulfide-bishexafluoro as described by Watt et al. In “Journal of Polymer Science, Polymer Chemistry Edition”, Volume 22, page 1789 (1984). Metal salts (for example, phosphates, arsenates, antimonates, etc.); one or more of aromatic iodonium complex salts and aromatic sulfonium complex salts whose anions are B (C6F5) 4- are included.

Preferred cationic active energy ray cationic polymerization initiators include arylsulfonium complex salts, aromatic sulfonium or iodonium salts of halogen-containing complex ions, and aromatic onium salts of Group II, Group V and Group VI elements. Some of these salts are FX-512 (3M), UVR-6990 and UVR-6974 (Union Carbide), UVE-1014 and UVE-1016 (General Electric), KI-85 (Degussa) ), SP-152 and SP-172 (Asahi Denka Co.) and Sun-Aid SI-60L, SI-80L and SI-100L (Sanshin Chemical Industry Co., Ltd.), WPI113 and WPI1
16 (Wako Pure Chemical Industries) and RHODORSIL PI2074 (Rhodia) are available as commercial products.

  Cationic or protonic acid catalysts such as sulfonium salts, ammonium salts, pyridinium salts, phosphonium salts, iodonium salts, trifluoro acid salts, boron trifluoride etherate compounds, boron trifluoride, etc. Can be used. It can be said to be a latent curing catalyst because it has high stability until it generates cationic species by heating. The polymerization activity varies depending on the type of substituent and the type of anion of the onium salt. Particularly, the anion has a polymerization activity in the order of BF- <AsF6- <PF6- <SbF6- <B (C6F5) 4-. It is known to be higher. In addition, it is known that specific phenol compounds such as an aluminum complex and a silanol compound, and an aluminum complex and bisphenol S serve as a cationic polymerization catalyst.

  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 include Sun Aid SI-60L, SI-80L and SI-100L (Sanshin Chemical Co., Ltd.), RHODORSIL PI2074 (Rhodia). Among these cationic polymerization initiators, aromatic onium salts are preferable 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 component (B). When the amount of the cationic polymerization initiator is small, it takes a long time for curing or a cured product that is sufficiently cured cannot be obtained. When the amount of the initiator is large, the color of the initiator remains in the cured product, coloring or bulging due to rapid curing, or the heat and light resistance of the cured product is impaired.

<1-5. Radical polymerization initiator>
The present negative curable 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 the component (B) can be cross-linked by the radical species.

Active energy ray radical polymerization initiators 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. Specific examples of acetophenone compounds include 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 2- Hydroxy -Methyl-1-phenylpropan-1-one, 1- (4'-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2'-hydroxyethoxy) phenyl (2- Hydroxy-2-propyl) ketone, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- (4′-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl 2-dimethylamino-1- (4′-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-1 -[4- [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one Specific examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. Specific examples of the oxime ester compounds include 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone 1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like. Specific examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl. Ether, methyl 2-benzoylbenzoate Etc.
Specific examples of the benzophenone compounds include benzyldimethylketone, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and specific examples of α-diketone compounds. And diacetyl, dibenzoyl, methylbenzoyl formate and the like. 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- Toxicarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'- Biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′- Bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetrakis (4-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 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and the like, and specific examples of the polynuclear quinone compound include anthraquinone, Examples include 2-ethylanthraquinone, 2-t-butylanthraquinone, 1,4-naphthoquinone, and specific examples of xanthone compounds include xanthone, thioxanthone, 2-chlorothioxanthone, 2,5-diethyldixanthone, and the like. Specific examples of the triazine compounds 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-triazine, 2 (4′-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2′-bromo-4′-methylphenyl) -4,6-bis (trichloromethyl) -s-triazine 2- (2′-thiophenylethylidene) -4,6-bis (trichloromethyl) -s-triazine and the like.

  In particular, from the viewpoint of excellent thin film curability, 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) )], Ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred.

  In particular, from the viewpoint that the cured product is excellent in transparency, 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, 2,2-dimethoxyacetophenone preferable.

  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, hydrogen peroxide, and tert-butyl hydroperoxide. , Hydroperoxides such as cumene hydroperoxide, dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxypivalate Peroxyesters, azo compounds such as azobisisobutyronitrile, azobisisovaleronitrile, ammonium persulfate, sodium persulfate, potassium persulfate It is possible to persulfate salts, etc. of listed.

  These radical polymerization initiators may be used alone or in combination of two or more.

  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 compound having a photopolymerizable functional group. When 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. A large amount of initiator is not preferable because the cured film itself is colored.

<1-6. Other additives>
(Crosslinking agent)
A cross-linking agent having two or more photopolymerizable functional groups in one molecule can be added to the present negative curable composition in order to adjust workability, reactivity, adhesion, and cured product strength. . 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, vinylcyclohexylene 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 and 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane Etc.

  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 (B). If the addition amount of the crosslinking agent is small, the addition effect 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 present negative curable composition, when cured with light energy, has an improved light sensitivity and has a high wavelength such as g-line (436 nm), h-line (405 nm), i-line (365 nm). In order to give sensitivity to light, a sensitizer can be appropriately added. These sensitizers can be used in combination with the above cationic polymerization initiator, radical polymerization initiator, photoacid generator and the like to adjust the curability.

  Examples of the compound to be added include anthracene compounds and thioxanthone compounds.

  Specific examples of the anthracene compound include anthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-di. Ethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 2-tert-butylanthracene, 2,6-di-tert-butylanthracene, 9,10-diphenyl-2,6-di- tert-butylanthracene and the like can be mentioned, and from the viewpoint of easy availability, anthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene and the like preferable.

  Anthracene is preferable from the viewpoint of excellent transparency of the cured product, and 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-diethoxyanthracene from the viewpoint of excellent compatibility with the curable composition. Etc. are preferred.

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

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

  The content of the sensitizer in the present negative curable composition is not particularly limited as long as it can exert a sensitizing effect, but the added initiator (cationic polymerization initiator / radical polymerization initiator / photoacid generation). Agent) It is preferable to add 0.01 to 300 mol of the sensitizer with respect to 1 mol, and more preferably 0.1 to 100 mol. If the amount of the sensitizer is small, the sensitization effect cannot be obtained, and it may take a long time for curing or may adversely affect the developability, while if it is large, the color may remain in the cured product. , Coloring for rapid curing, heat resistance and light resistance may be impaired.

(Reactivity modifier)
When this negative curable composition is used as a radical curing system, a thiol compound, an amine compound, a phosphine compound, or the like can be added to adjust the reactivity and suppress the inhibition of curing by oxygen.

  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, mercapto group-containing polyorganosiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KF2001, KF2004, etc.) and the like.

  From the viewpoint of excellent heat resistance, in particular, 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, KF2004, etc.) are preferred.

  Specific examples of the phosphine compound include triphenylphosphine and tributylphosphine.

(Adhesion improver)
An adhesion improver can also be added to the present negative curable composition. 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 handling. From the viewpoints of adhesion and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methacrylic or acrylic groups such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Alkoxysilanes having can be exemplified.

  The addition amount of the silane coupling agent can be variously 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 physical properties of the cured product may be adversely affected.

  These coupling agents, silane coupling agents, epoxy compounds, etc. may be used alone or in combination of two or more.

  In the present invention, carboxylic acids and / or acid anhydrides can be used in order to enhance the effect of the coupling agent or the epoxy compound, and adhesion can be improved and / or stabilized. Such carboxylic acids and acid anhydrides are not particularly limited, but 2-ethylhexanoic acid, cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, methylcyclohexanedicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylhymic acid, Norbornene dicarboxylic acid, hydrogenated methyl nadic acid, maleic acid, acetylenedicarboxylic acid, lactic acid, malic acid, citric acid, tartaric acid, benzoic acid, hydroxybenzoic acid, cinnamic acid, phthalic acid, trimellitic acid, pyromellitic acid, naphthalenecarboxylic acid Examples include acids, naphthalenedicarboxylic acids, and single or complex acid anhydrides thereof.

  Among these carboxylic acids and / or acid anhydrides, preferred carboxylic acids and / or acid anhydrides include, for example, tetrahydrophthalic acid, methyltetrahydrophthalic acid, and the like in that the properties of the resulting cured product are not easily impaired. Examples thereof include acids and their single or complex acid anhydrides.

  The amount of carboxylic acids and / or acid anhydrides to be used can be variously set, but the preferred range of addition amount with respect to 100 parts by weight of the coupling agent and / or epoxy compound is 0.1 to 50 parts by weight, More preferably, it is 1-10 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 physical properties of the cured product may be adversely affected.

  Further, these carboxylic acids and / or acid anhydrides may be used alone or in combination of two or more.

(Phosphorus compound)
When the present negative curable composition is cured by light or heat, particularly when used in applications requiring transparency, a phosphorus compound may be used to improve the hue after curing by light or heat. preferable. Specific examples of phosphorus compounds include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol diphosphite, tris (2,4-di-t-butyl). Phenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl phosphite), cyclic neopentane tetrayl bis (2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bis (2, 6-di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, etc. Antioxidant chosen from Stopper or 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, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Agents are preferably used.

  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 component (B). When the amount of the phosphorus compound used is less than 0.01 parts by weight, the effect of improving the hue is reduced. If the amount used exceeds 10 parts by weight, the curability and the physical properties of the cured product may be adversely affected.

(Thermoplastic resin)
Various thermoplastic resins may be added to the curable composition for the purpose of modifying the properties. Various thermoplastic resins can be used. For example, a homopolymer of methyl methacrylate or a polymethyl methacrylate resin such as a random, block or graft polymer of methyl methacrylate and other monomers (for example, Hitachi Chemical) Optretz, etc.), acrylic resins represented by polybutyl acrylate resins such as butyl acrylate homopolymers or random, block or graft polymers of butyl acrylate and other monomers, bisphenol A, 3, A polycarbonate resin such as a polycarbonate resin containing 3,5-trimethylcyclohexylidenebisphenol or the like as a monomer structure (for example, APEC manufactured by Teijin Limited), a norbornene derivative, a vinyl monomer, or the like is copolymerized alone or copolymerized. Cycloolefin resins such as fat, norbornene derivative ring-opening metathesis polymer, or hydrogenated products thereof (for example, APEL manufactured by Mitsui Chemicals, ZEONOR, ZEONEX manufactured by Nippon Zeon, ARTON manufactured by JSR, etc.), ethylene and Olefin-maleimide resins such as maleimide copolymers (eg TI-PAS manufactured by Tosoh Corporation), bisphenols such as bisphenol A and bis (4- (2-hydroxyethoxy) phenyl) fluorene, and diols such as diethylene glycol Polyester resins such as polyester obtained by polycondensation of phthalic acids and aliphatic dicarboxylic acids such as terephthalic acid and isophthalic acid (eg O-PET manufactured by Kanebo Co., Ltd.), polyethersulfone resins, polyarylate resins, polyvinyl acetal resins, Polyethylene resin Polypropylene resins, polystyrene resins, polyamide resins, silicone resins, other like fluorine resin, not natural rubber, but the rubber-like resin is exemplified such EPDM is not limited thereto.

  The thermoplastic resin may have a crosslinkable group. Examples of the crosslinkable group in this case 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, it is preferable to have 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 in that the compatibility with the polysiloxane compound is likely to be good. More preferred. On the contrary, the number average molecular weight is preferably 10,000 or more, and more preferably 100,000 or more in that the obtained cured product tends to be tough. The molecular weight distribution is not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less, in that the viscosity of the mixture tends to be low and the moldability tends to be good. More preferably, it is as follows.

  Although there is no limitation in particular as a compounding quantity of a thermoplastic resin, the range of the preferable usage-amount is 5 to 50 weight% of the whole curable composition, More preferably, it is 10 to 30 weight%. If the amount added is small, the resulting cured product tends to be brittle. If the amount 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 is removed to obtain a uniform dispersed state and / or mixed state. It is good.

  When the thermoplastic resin is dispersed and used, the average particle diameter can be variously set, but the lower limit of the preferable average particle diameter is 10 nm, and the upper limit of the preferable average particle diameter is 10 μm. 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 this negative curable composition as needed.

  Various fillers are used. For example, silica-based fillers such as quartz, fume silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine powder amorphous silica, silicon nitride, silver powder, etc. Inorganic fillers such as alumina, aluminum hydroxide, titanium oxide, glass fiber, carbon fiber, mica, carbon black, graphite, diatomaceous earth, clay, clay, talc, calcium carbonate, magnesium carbonate, barium sulfate, inorganic balloon As a filler for a conventional sealing material such as an epoxy type, a filler that is generally used or / and proposed can be used.

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

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

  Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylic acid esters, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.

  Moreover, these anti-aging agents may be used independently and may be used together 2 or more types.

(Radical inhibitor)
A radical inhibitor may be added to the present negative curable composition. Examples of the radical inhibitor include 2,6-di-t-butyl-3-methylphenol (BHT), 2,2′-methylene-bis (4-methyl-6-t-butylphenol), tetrakis (methylene- Phenol radical inhibitors such as 3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane, phenyl-β-naphthylamine, α-naphthylamine, N, N′-secondary butyl-p- Examples include amine radical inhibitors such as phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine, and the like.

  Moreover, these radical inhibitors may be used alone or in combination of two or more.

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

  Moreover, these ultraviolet absorbers may be used independently and may be used together 2 or more types.

(solvent)
When the polysiloxane compound used in the present negative curable composition has a high viscosity, it can be used by dissolving in a solvent. Solvents that can be used are not particularly limited, and specific examples include hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether, and the like. Ether solvents, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, glycol solvents such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA), ethylene glycol diethyl ether, chloroform, methylene chloride, A halogen-based solvent such as 1,2-dichloroethane can be preferably used.

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

  Although the amount of solvent to be used can be set as appropriate, the lower limit of the preferred amount of use for 1 g of the curable composition to be used is 0.1 mL, and the upper limit of the preferred amount of use is 10 mL. If the amount used is small, it is difficult to obtain the effect of using a solvent such as a low viscosity, and if the amount used is large, the solvent tends to remain in the material, causing problems such as thermal cracks, and also from a cost standpoint. It is disadvantageous and the industrial utility value decreases.

  These solvents may be used alone or as a mixed solvent of two or more.

(Other)
This negative curable composition includes other ions such as a colorant, a release agent, a flame retardant, a flame retardant aid, a surfactant, an antifoaming agent, an emulsifier, a leveling agent, a repellent, and antimony-bismuth. Trapping agent, thixotropic agent, tackifier, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, heat stabilizer, conductivity The purpose and effect of the present invention include an imparting agent, an antistatic agent, a radiation shielding 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. It can be added as long as it is not impaired.

[2. Method for adjusting curable composition and curing method]
The preparation method of this negative type curable 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 low temperature in a one-component state in which all components are mixed and prepared in advance.

  As a light source for photocuring, a light source that emits an absorption wavelength of a polymerization initiator or a sensitizer to be used may be used, and a light source usually containing a wavelength in the range of 200 to 450 nm, such as a high-pressure mercury lamp, High pressure mercury lamp, metal halide lamp, high power metal halide lamp, xenon lamp, carbon arc lamp, light emitting diode, etc. can be used.

The exposure amount is not particularly limited, but a preferable exposure amount range is 1 to 5000 mJ / cm ² , more preferably 1 to 1000 mJ / cm ² . If the exposure is small, it will not cure. If the exposure amount is large, the color may change due to rapid curing. A preferred curing time range is 30 to 120 seconds, more preferably 1 to 60 seconds. When the curing time is long, the characteristics of rapid curing of photocuring are 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. Various curing temperatures can be set, but a preferable temperature range is 60 to 400 ° C, more preferably 90 to 350 ° C.

  The cured product thus obtained (that is, a cured product obtained by curing the curable composition) is also encompassed in the present invention.

[3. (Laminated body)
Since this negative curable composition is liquid and can be easily formed into a thin film by handling and solution coating, a laminate can be easily formed by layer-curing on a substrate.

  Specifically, for example, the laminate can be produced by the following method. The polysiloxane composition is formed on a base material by a spin coating method, a roll coating method, a printing method, a bar coating method or the like, and the film thickness is usually 0.05 to 100 μm, preferably 0.1 to 50 μm. More preferably, it is applied so as to be 0.5 to 20 μm. Examples of the base material include glass, polycarbonates, films, silicon wafers on which an image sensor is formed, patterned colored resin films for LCD or CCD color filters, printing paper, printing fibers, metal plates, etc. Is mentioned. Next, a laminate can be obtained by performing exposure with the active energy rays.

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

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

  In addition, the developer at this time can be used without particular limitation as long as it is generally used. Specific examples thereof include an aqueous organic alkali solution such as an aqueous tetramethylammonium hydroxide solution and an aqueous choline solution, and an aqueous potassium hydroxide solution. Inorganic alkali aqueous solutions such as sodium hydroxide aqueous solution, potassium carbonate aqueous solution, sodium carbonate aqueous solution and lithium carbonate aqueous solution, and those obtained by adding alcohol or surfactant to these aqueous solutions for adjusting the dissolution rate, etc. . Since the curable composition of the present invention can adjust the dissolution rate of the uncured portion in the developer, the uncured portion can be dissolved and removed with high accuracy, and has excellent tack and patterning properties. Can be manufactured.

  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. (Use)
The present negative curable composition and the cured product thereof can be used for various applications. It can be applied to various uses where conventional acrylic resin and epoxy resin adhesives are used.

  For example, transparent materials, optical materials, optical lenses, optical films, optical sheets, optical component adhesives, optical waveguide coupling optical adhesives, optical waveguide peripheral member fixing adhesives, DVD bonding adhesives, adhesives, Dicing tape, 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, TFT transparent flattening Membrane, insulating packing, insulation coating material, adhesive, high heat resistant adhesive, high heat dissipation adhesive, optical adhesive, LED element adhesive, various substrate adhesive, heat sink adhesive, paint, UV powder Body paint, ink, colored ink, UV inkjet ink, coating material (hard coat, sheet, film, release paper coat, optical disc coat, optical fabric ), Molding materials (including sheets, films, FRP, etc.), sealing materials, potting materials, sealing materials, light-emitting diode sealing materials, optical semiconductor sealing materials, liquid crystal sealing agents, display devices Sealing material, sealing material for electrical materials, 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, binder resin for color filter, color Transparent flattening material for filter, binder resin for black matrix, photo spacer material for liquid crystal cell, transparent sealing material for OLED element, stereolithography, solar cell material, fuel cell material, display material, recording material, vibration proof material , Waterproof materials, moisture-proof materials, heat-shrinkable rubber tubes, O-rings, photoconductor drums for copying machines, battery fixing The electrolyte can be applied to a gas separation membrane. Further, concrete protective materials, linings, soil injection agents, cold storage heat materials, sealing materials for sterilization treatment devices, contact lenses, oxygen permeable membranes, additives to other resins, and the like can be mentioned.

  Among them, the curable composition of the present invention is a material that can be used as an alkali-developable transparent resist, and is particularly suitable as an FPD material. More specifically, a passivation film for TFT, a gate insulating film for TFT, an interlayer insulating film for TFT, a transparent planarizing film for TFT, a binder resin for color filter, a transparent planarizing material for color filter, a binder resin for black matrix, Examples thereof include a photospacer material for liquid crystal cells and a transparent sealing material for OLED elements.

[6. Others]
In addition to the above, the present invention can include the following aspects.

<1> (A) The boiling point at 5 mmHg is 200 ° C. or more, and 0.01 to 5 parts by weight of the ester compound represented by the above formula (1) with respect to the component (B);
(B) At least one selected from the group consisting of a structure represented by the above formulas (2) and (3), a phenolic hydroxyl group and a carboxyl group, having at least two photopolymerizable functional groups in one molecule And a modified polyorganosiloxane compound having one in the same molecule.

  <2> The photopolymerizable functional group (B) is at least one selected from the group consisting of an epoxy group, a crosslinkable silicon group, and a (meth) acryloyl group. <1> The negative curable composition as described.

  <3> The negative curable composition according to <1>, wherein at least one of the photopolymerizable functional groups (B) is an alicyclic epoxy group or a glycidyl group.

<4> The modified polyorganosiloxane compound (B) is a hydrosilylation reaction product of the following compounds (α1), (β), and (γ): <1> to <3> Negative curable composition according to any one of the following:
(Α1) one molecule having at least one carbon-carbon double bond having reactivity with a SiH group, the structure represented by the above formulas (2) and (3), a phenolic hydroxyl group, An organic compound having at least one selected from the group consisting of a carboxyl group in the same molecule,
(Β) a polysiloxane compound having at least two SiH groups in one molecule, and (γ) a carbon-carbon having reactivity with at least one photopolymerizable functional group and SiH groups in one molecule. A compound having one or more double bonds.

<5> The modified polyorganosiloxane compound (B) is a hydrosilylation reaction product of the compounds (α1), (β) and (γ), and the following compound (α2), 4> negative curable composition according to
(Α2) A compound having one or more carbon-carbon double bonds having reactivity with SiH groups in one molecule.

  <6> The group in which (α1) is composed of diallyl isocyanuric acid, monoallyl isocyanuric acid, diallyl bisphenol A, diallyl bisphenol S, vinyl phenol, allyl phenol, butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid and undecylenic acid The negative curable composition according to <4> or <5>, wherein the negative curable composition is at least one selected from the above.

  <7> The negative curable composition according to <5>, wherein the (α2) is a compound represented by the structure represented by the formula (6).

  <8> Any one of <4> to <7>, wherein (β) is a cyclic polyorganosiloxane compound having a SiH group represented by the structure represented by the formula (7). Negative curable composition as described in 2.

  <9> Said (γ) is at least one selected from the group consisting of vinylcyclohexene oxide, allyl glycidyl ether, diallyl monoglycidyl isocyanurate and monoallyl diglycidyl isocyanurate, <4> The negative curable composition in any one of-<8>.

  <10> The negative curable composition according to any one of <4> to <9>, wherein (γ) is a compound represented by the structure represented by the formula (8). .

  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 and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following.

(Tack evaluation)
A tack evaluation sample was prepared using the resin compositions shown in the examples and comparative examples. Specifically, a glass substrate spin-coated with a photosensitive resin composition is heated on a hot plate heated to 100 ° C. for 2 minutes, and an exposure apparatus (high pressure mercury lamp, manual exposure machine, manufactured by Dainippon Kaken Co., Ltd.) ) Was used to expose each with an optimal integrated light quantity through a mask engraved with a 5 μm line and space pattern (soft contact exposure), and the mask was peeled off immediately after exposure.

  The method of peeling the mask was evaluated according to the following criteria.

<Evaluation criteria>
○: When the mask is lifted vertically, the mask peels off from the resin film without resistance. ×: When the mask is lifted vertically, the mask does not peel from the resin film (patterning evaluation)
A patterning evaluation sample was prepared using the resin compositions shown in Examples and Comparative Examples. Specifically, a glass substrate spin-coated with a resin composition is heated on a hot plate heated to 100 ° C. for 2 minutes, and an exposure apparatus (high pressure mercury lamp, manual exposure machine, manufactured by Dainippon Kaken Co., Ltd.) is used. Using a mask engraved with a 5 μm line and space pattern, each was exposed with an optimal integrated light quantity (soft contact exposure), left for 1 minute after exposure, and then placed in an alkaline developer (TMAH 2.38% aqueous solution). After dipping for 2 seconds, it was 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 evaluation sample. A pattern shape of the obtained evaluation sample was observed using a 3D measurement laser microscope (LEXT OLS4000, manufactured by Olympus) and a stylus type surface shape measuring device (Dektak 150, manufactured by Veeco), and a state of 5 μm line and space. Were evaluated according to the following criteria.

<Evaluation criteria>
○: No residual film in 5 μm line and space ×: Residual film in 5 μm line and space ×: Film reduction in pattern shape (Synthesis Example)
40 g of diallyl isocyanuric acid and 29 g of diallyl monomethyl isocyanuric acid are dissolved in 264 g of dioxane, and a platinum vinylsiloxane complex xylene solution (platinum vinylsiloxane complex containing 3 wt% as platinum, Pt-VTSC-3X, manufactured by Umicore Precious Metals Japan) 143 μL Was added. 88 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane heated to 105 ° C. in a nitrogen atmosphere containing 3% oxygen was obtained from the solution thus obtained. The solution was added dropwise to a solution of 176 g of toluene over 3 hours. 30 minutes after the completion of dropping, 1H-NMR confirmed that the reaction rate of the alkenyl group was 95% or more, and then a solution of 1-vinyl-3,4-epoxycyclohexane 62 g and toluene 62 g was added dropwise over 1 hour. . 30 minutes after the completion of the dropping, 1H-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 propylene glycol-1-monomethyl ether-2-acetate to obtain a colorless and transparent 50 wt% polysiloxane compound solution “Reactant A”.

Example 1
For the reactant A obtained in the synthesis example, a curable composition was prepared with the composition shown in Table 1 and evaluated as described below. The results are shown in Table 1. A specific method for preparing the curable composition is as follows. First, PGMEA, BBI-103 and 9,10-dibutoxyanthracene are uniformly dissolved, and then the reactant A and the ester compound (DOA) are uniformly mixed. Produced.

(Example 2)
A resin composition was produced in the same manner as in Example 1 except that the composition ratio of DOA was changed.

(Example 3)
A resin composition was produced in the same manner as in Example 1 except that the composition ratio of DOA was changed.

Example 4
A resin composition was produced in the same manner as in Example 1 except that the composition ratio of DOA was changed.

(Example 5)
A resin composition was produced in the same manner as in Example 1 except that DIDA was used instead of DOA and the composition ratio was changed.

(Comparative Example 1)
A resin composition was produced in the same manner as in Example 1 except that DOA was not used (that is, the component (A) was not included).

(Comparative Example 2)
A resin composition was produced in the same manner as in Example 1 except that the composition ratio of DOA was changed.

(Comparative Example 3)
A resin composition was produced in the same manner as in Example 1 except that DIBA was used instead of DOA and the composition ratio was changed.

(result)
Table 1 shows the results of tack evaluation and patterning evaluation for the resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 3.

  As shown in Table 1, it was confirmed that the resin composition containing an ester compound having a boiling point at 5 mmHg of 200 ° C. or higher in the range of 0.01 to 5 parts by weight is highly evaluated for both tack and patterning properties. It was. Therefore, it has been found that by adding an ester compound having a boiling point of 200 ° C. or higher at 5 mmHg in the range of 0.01 to 5 parts by weight, a resin composition excellent in both tack and patterning properties upon curing can be obtained. It was.

  In addition, it is as follows regarding evaluation of Comparative Examples 1-3.

  In Comparative Example 1, since no ester compound is added, a remaining film is generated in the patterning evaluation.

  Further, in Comparative Example 2, since the amount of DOA added is large, there is a tack, and the film shape is reduced in the pattern shape.

  In Comparative Example 3, since the boiling point of the ester compound at 5 mmHg is less than 200 ° C., a remaining film is generated in the patterning evaluation.

  The present invention can be used in various fields such as an insulating material, an adhesive, a coating agent, and a sealant, and in particular, can also be used for an interlayer insulating film such as a liquid crystal display.

Claims (6)

(A) The boiling point at 5 mmHg is 200 ° C. or higher, and the ester compound represented by the following formula (1) is 0.01 to 5 parts by weight with respect to the component (B);
R ^1- (COO-R ² ) _m (1)
(Wherein R ¹ and R ² are each independently an aliphatic chain hydrocarbon, an aliphatic cyclic hydrocarbon or an aromatic hydrocarbon, and m is an integer of 2 to 4);
(B) having at least two photopolymerizable functional groups in one molecule, and
Structures represented by the following formulas (2) and (3);

A modified polyorganosiloxane compound having in the same molecule at least one selected from the group consisting of phenolic hydroxyl groups and carboxyl groups;
A negative curable composition comprising: ^2. The negative curable composition according to claim 1, wherein R ¹ and R ² of the ester compound (A) are aliphatic chain hydrocarbons.   The ester compound (A) is dioctyl adipate, di (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, dioctyl azelate, di (2-ethylhexyl) azelate, diisononyl azelate, diisodecyl azelate The negative curable composition according to claim 1, which is dioctyl sebacate, di (2-ethylhexyl) sebacate, diisononyl sebacate or diisodecyl sebacate.   Furthermore, a negative acid curable composition as described in any one of Claims 1-3 characterized by containing a photo-acid generator as (C) component.   Hardened | cured material formed by hardening | curing the negative curable composition as described in any one of Claims 1-4.   The laminated body characterized by providing the cured film which the negative curable composition of any one of Claims 1-4 hardened | cured on the base material.