JP2010235862A - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new photosensitive curable composition which gives a coating film excellent in transparency, heat resistance and light resistance and is suitable for a resist material. <P>SOLUTION: The curable composition comprises (A) a basic compound, (B) a photo acid generator, and (C) a modified polyorganosiloxane having at least two SiH groups in one molecule. Its cured product is also provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a curable composition, and more specifically, relates to a curable material that provides a coating having excellent transparency and heat and light resistance, having photosensitivity composed mainly of a modified polyorganosiloxane compound.

  In general, many resist materials having alkali developability are widely used, especially in the field of electronic materials, as patterning materials using resins having acidic groups such as novolak resins, acrylic acid copolymers, and polyamic acids. It is shown in documents 1-3.

  However, these representative materials also have excellent alkali developability, heat resistance and transparency due to lack of reliability (thermal decomposition, cracks, peeling, etc.) and transparency at high temperatures exceeding 200 ° C. However, no satisfactory material has been obtained in terms of achieving both high temperature reliability and the like.

Japanese Patent No. 3203843 JP 2005-266673 A JP-A-4-218051

  An object of the present invention is to provide a photosensitive curable composition suitable for a resist material and capable of providing a coating film excellent in transparency and heat and light resistance.

  As a result of intensive studies by the present inventors, a modified polyorganosiloxane compound having at least two SiH groups in one molecule was cured with a basic compound in the presence of a photoacid generator. It succeeded in forming a coating film in an unexposed part, and discovered that the formed coating film was excellent in transparency and a heat-resistant weather resistance, and came to complete this invention.

That is, the present invention
[1] Curability characterized by containing (A) a basic compound, (B) a photoacid generator, and (C) a modified polyorganosiloxane compound having at least two SiH groups in one molecule. A composition,
[2] The (C) modified polyorganosiloxane compound is — (— RHSiO—) n—
Curing as described in [1], having a siloxane unit represented by (R represents a monovalent organic group having 1 to 50 carbon atoms, which may be the same or different, n = 1 to 10). Sex composition,
[3] The (C) modified polyorganosiloxane compound is
R ₂ HSiO-
The curable composition according to [1] or [2], having a siloxane unit represented by (R represents a monovalent organic group having 1 to 50 carbon atoms, which may be the same or different). Is a thing,
[4] The (C) modified polyorganosiloxane compound has the same molecule as at least one selected from the group consisting of the following structures (Y1) to (Y3), a phenolic hydroxyl group, and a carboxyl group: The curable composition according to any one of [1] to [3]

And
[5] The (C) modified polyorganosiloxane compound has the following general formula (I):

It is a curable composition as described in any one of [1]-[4] which has a structure represented by these,
[6] The curable composition according to any one of [1] to [5], wherein the (C) modified polyorganosiloxane compound has an alicyclic hydrocarbon structure and / or an aromatic ring.
[7] The (C) modified polyorganosiloxane compound includes a compound having at least two SiH groups in one molecule and a compound having one or more alkenyl groups having reactivity with SiH groups in one molecule; The curable composition according to any one of [1] to [6], which is obtained by hydrosilylating
[8] The curable composition according to any one of [1] to [7], further comprising (D) a compound having two or more alkenyl groups having reactivity with SiH groups in one molecule. Is a thing,
[9] The curable composition according to any one of [1] to [8], wherein the component (A) is a quaternary amine.
[10] The curable composition according to any one of [1] to [9], wherein the photoacid generator is an aromatic iodonium salt,
[11] A positive resist using the curable composition according to any one of [1] to [10] above,
[12] A technique relating to an interlayer insulating film for electronic equipment formed using the curable composition according to any one of [1] to [11].

  According to the curable composition of this invention, the coating film excellent in transparency and heat-and-light resistance can be given.

(Ingredient (A))
The component (A) of the present invention will be described.

  The component (A) is not particularly limited as long as it is a basic compound, but is preferably one that promotes the condensation reaction of the SiH group, and examples thereof include amine compounds, amide compounds, or triazine compounds that are nitrogen-containing compounds. .

  Specifically, alkylamines represented by the following general formula (II):

(Wherein R represents a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms, and each R may be different or the same).

  From the viewpoint of volatility, a compound having a boiling point of 150 ° C. or higher is preferable, and pyridine, polyvinylpyridine, aniline, N-methylaniline, N, N-dimethylaniline, o-toluidine, m-toluidine, p-toluidine, and 2,4-lutidine. Quinoline, isoquinoline, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone, imidazole, α-picoline, β- Picoline, γ-picoline, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2-quinolinecarboxylic acid 2-amino-4-nitrophenol, 2- (p Chlorophenyl) -4,6-trichloromethyl -s- triazine, and the like.

  From the viewpoint of good curability, quaternary amines such as diazabicycloundecene (DBU) or diazabicyclononene (DBN) or tetramethylammonium hydroxide, choline, which are said to be strongly basic and reactive super strong bases, or Inorganic salts such as sodium hydroxide and potassium hydroxide are preferred, particularly diazabicycloundecene (DBU), diazabicyclononene (DBN), tetramethylammonium hydroxide, choline and the like which do not generate impurity ions. Quaternary amines are preferred.

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

  The addition amount of the basic compound is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the main component (C), from the viewpoint of storage stability and transparency of the cured product. Preferably, the amount is 0.01 to 3 parts by weight, and more preferably 0.01 to 1 part by weight.

(Ingredient (B))
The component (B) of the present invention will be described.

  The component (B) is not particularly limited as long as it is a photoacid generator that generates Bronsted acid or Lewis acid by active energy rays.

Photoacid generators include metal fluoroboron complex salts and boron trifluoride complex compounds as described in US Pat. No. 3,379,653; bis (perfluoroalkylsulfonyl) methane as described in US Pat. No. 3,586,616. 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; Va as described in US Pat. Aromatic onium salts of group elements; thiopyrylium salts as described in US Pat. No. 4,139,655; MF6 ^- anions as described in US Pat. No. 4,161,478 where M is selected from phosphorus, antimony and arsenic Element VIa; aryl as described in US Pat. No. 4,231,951 Sulfonium complex salts; U.S. Patent aromatic iodonium complex salts and aromatic sulfonium complex salts as described in No. 4256828; W. R. Bis [4- (diphenylsulfonio) phenyl] sulfide-bis-hexa as described by Watt et al in "Journal of Polymer Science, Polymer Chemistry Edition", Vol. 22, p. 1789 (1984). Fluorometal salts (for example, phosphates, arsenates, antimonates, etc.); one or more aromatic iodonium complex salts and aromatic sulfonium complex salts whose anion is B (C ₆ F ₅ ) ₄ ^— are included.

  Preferred photoacid generators 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.

  Specifically, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethaneantimonate, triphenylsulfonium benzosulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexyl (2-oxocyclohexyl) sulfonium Sulfonium salt compounds such as trifluoromethanesulfonate, dicyclohexylsulfonylcyclohexanone, dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, iodonium salts such as diphenyliodonium trifluoromethanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, FX-512 (3M Company), UVR-69 0 and UVR-6974 (Union Carbide), UVE-1014 and UVE-1016 (General Electric), KI-85 (Degussa), SP-152 and SP-172 (Asahi Denka) and Sun-Aid SI- 60L, SI-80L and SI-100L (Sanshin Chemical Industry Co., Ltd.), WPI113 and WPI116 (Wako Pure Chemical Industries, Ltd.), RHODORSIL PI2074 (Rhodia Co., Ltd.) and the like.

  From the viewpoint of compatibility with the component (C), an aromatic iodonium salt is preferable, and a boron aromatic iodonium salt is particularly preferable.

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

  The addition amount of the photoacid generator is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the main component (C). From the viewpoint of storage stability and transparency of the cured product More preferably, the content is 0.01 to 3 parts by weight, and still more preferably 0.01 to 1 part by weight.

(Ingredient (C))
The (C) modified polyorganosiloxane compound having at least two SiH groups in one molecule of the present invention (hereinafter sometimes simply referred to as “(C) modified polyorganopolysiloxane compound”) will be described.

  The modified polyorganosiloxane compound of the present invention refers to a compound obtained by partially reacting an organic compound having no siloxane bond with a compound having a siloxane bond (polyorganosiloxane compound) as a main skeleton. What is obtained by hydrosilylation reaction from the point from which the compound which is excellent in stability since it couple | bonds by Si-C bond after reaction is obtained is preferable.

  The compound having a siloxane bond (polyorganosiloxane compound) is not particularly limited as long as it is a compound having a siloxane bond, and is described in a known linear or cyclic polyorganosiloxane structure, for example, International Publication WO96 / 15194. The compound in which the structure to be contained in a compound corresponds. The polyorganosiloxane having an alkenyl group having reactivity with the SiH group described later is also included in the category.

  Specific examples of linear polyorganosiloxanes include poly or oligosiloxanes whose ends are blocked with dimethylhydrogensilyl groups or dimethylalkoxysilyl groups, and poly or oligosiloxanes having SiH groups and / or alkoxysilyl groups in the side chains. Examples include siloxane, tetramethyldisiloxane, hexamethyltrisiloxane and the like.

  Specific examples of the cyclic polyorganosiloxane include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trimethyl. Hydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5 -Trihydrogen-trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11- Examples include hexahydrogen-1,3,5,7,9,11-hexamethylcyclosiloxane and those having these SiH groups as alkoxysilyl groups.

  Although the (C) modified polyorganosiloxane compound of the present invention has at least two SiH groups in one molecule, it is preferably 3 or more and more preferably 4 or more from the viewpoint of curability.

The siloxane structure containing a SiH group in the (C) modified polyorganopolysiloxane compound of the present invention is not particularly limited, but from the viewpoint of increasing the hardness of the resulting cured product, the following formula — (— RHSiO—) n -
It is preferable to have a siloxane unit represented by (R represents a monovalent organic group having 1 to 50 carbon atoms, which may be the same or different, n = 1 to 10), and obtainable curability. From the viewpoint of high reactivity of the composition, the following formula R ₂ HSiO—
Those having a siloxane unit represented by (R represents a monovalent organic group having 1 to 50 carbon atoms, which may be the same or different) are preferable.

  The R represented by the monovalent organic group having 1 to 50 carbon atoms is not particularly limited, but from the viewpoint of availability, a methyl group, an ethyl group, a propyl group, an octyl group, a phenyl group. A cyclohexyl group and the like are preferable. Furthermore, a methyl group and an ethyl group are preferable from the viewpoint of excellent heat resistance and light resistance.

  The (C) modified polyorganosiloxane compound of the present invention may have an organic structure introduced to impart functionality to the cured product.

  The organic structure is not particularly limited as long as it has no reactivity with the SiH group, but from the point that the hygroscopicity of the resulting cured product can be lowered, a norbornyl structure, a cycloalkyl structure, an adamantyl structure, etc. An alicyclic hydrocarbon structure is preferable, and aromatic rings such as a phenyl structure, a biphenyl structure, a bisphenol structure, a naphthalene structure, and an anthracene structure are preferable from the viewpoint that the strength of the cured product can be improved.

  In addition, the following general formula (I)

It is preferable that a structure represented by the formula is introduced because a cured product having excellent transparency and heat and light resistance can be obtained.

  The (C) modified polyorganosiloxane compound of the present invention can be obtained by various methods, and a hydrosilane compound / alkoxysilane compound having a hydrolyzable silyl group is hydrolyzed and condensed in the presence of an acid or base catalyst, hydrosilane compound And the like.

  In the method of obtaining a compound by condensing a hydrolyzable silyl group, the precursor used is not particularly limited as long as it contains a hydrolyzable silyl group and a hydrosilyl group in the molecule, and specifically, trichlorosilane. , Halogenated silanes such as methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane.

  As a method of obtaining the compound by the latter hydrosilylation, it is possible to control the number and position of introduction of SiH groups, and in particular, in the case of thick film, from the viewpoint that the cured film obtained for the obtained thin film tends to be tough. preferable.

  Examples of the compound that can be used in the reaction include a compound having two or more SiH groups (SiH group-containing compound) and a compound having one or more alkenyl groups (alkenyl group-containing compound).

  As the compound having two or more SiH groups, the same compounds as the linear or cyclic polyorganosiloxane can be used without particular limitation.

  The compound having one or more alkenyl groups can be used without any particular limitation, and the bonding position of the carbon-carbon double bond is not particularly limited and may be present anywhere in the molecule.

  Specific examples include alkenyl group-containing polysiloxanes, alkenyl group-containing organic polymer compounds and organic monomer compounds that do not contain siloxane units (Si—O—Si), and the like.

  Examples of alkenyl group-containing polyorganosiloxanes include straight-chain polysiloxanes having alkenyl groups, polysiloxanes having alkenyl groups at the molecular terminals, and cyclic siloxanes containing alkenyl groups, and the cured product obtained in the present invention. From the viewpoint of the strength, it is preferably a polysiloxane having an alkenyl group at the molecular end, and more preferably a linear polysiloxane having an alkenyl group at both ends.

  Specific examples of the linear siloxane having an alkenyl group include copolymers of dimethylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units. Examples 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-trimethylcyclosiloxane, , 3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexavinyl-1,3,5,7,9, Examples thereof include 11-hexamethylcyclosiloxane. In the present invention, from the viewpoint of heat resistance and light resistance, the Si atom is preferably composed of a hydrogen atom, a vinyl group and a methyl group.

  Examples of the organic polymer in the alkenyl group-containing organic polymer compound include, for example, polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, polyacrylate, polyamide, Phenol-formaldehyde (phenolic resin) and polyimide compounds can be used.

  Examples of the organic monomer in the alkenyl group-containing organic monomer compound include aromatic hydrocarbons such as phenol, bisphenol, benzene, and naphthalene: aliphatic hydrocarbons such as linear and alicyclic: Heterocyclic compounds and mixtures thereof.

  Specific examples of these compounds 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 monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate, 1,2,4-trivinylcyclohexane 1,4-butanediol divinyl ether, nonanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, triethylene glycol Cole divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, diallyl ether of bisphenol S, divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-bis (Allyloxy) adamantane, 1,3-bis (vinyloxy) adamantane, 1,3,5-tris (allyloxy) adamantane, 1,3,5-tris (vinyloxy) adamantane, dicyclopentadiene, vinylcyclohexene, 1,5 Hexadiene, 1,9-decadiene, diallyl ether, bisphenol A diallyl ether, tetraallyl bisphenol A, 2,5-diallylphenol allyl ether, and oligomers thereof 1,2-polybutadiene (that of 1,2 Ratio 10-100%, preferably 1,2 ratio 50-100% of those), allyl ether of novolak phenol, allylated polyphenylene oxide,

In addition, there may be mentioned those in which part or all of the glycidyl group of a conventionally known epoxy resin is replaced with an allyl group.

  As described above, low molecular weight compounds that are difficult to express separately 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.

  The average number of alkenyl groups may be one or more per molecule, but when it is desired to further improve the mechanical strength of the cured product, it is preferably more than 2 and more preferably 3 or more.

  From the viewpoint that the resulting cured product is less colored and has high light resistance, vinylcyclohexene, dicyclopentadiene, triallyl isocyanurate, diallyl ether of 2,2-bis (4-hydroxycyclohexyl) propane, 1,2, 4-trivinylcyclohexane is preferred, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl ether of 2,2-bis (4-hydroxycyclohexyl) propane, 1,2,4-trivinyl Cyclohexane is particularly preferred.

  You may have reactive groups other than an alkenyl group. Examples of the reactive group in this case include an epoxy group, an oxetanyl group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. When it has these functional groups, the adhesiveness of the resulting curable composition tends to be high, and the strength of the resulting cured product tends to be high. Of these functional groups, an epoxy group is preferable from the viewpoint that the adhesiveness can be further increased. Moreover, it is preferable to have 1 or more reactive groups in one molecule on average from the point that the heat resistance of the obtained cured product tends to be high.

  In addition, when an acidic group is introduced into the modified polyorganopolysiloxane compound, it can be obtained by using a compound having an alkenyl group and a phenol group, a carboxyl group or an isocyanuric acid group in one molecule. From the viewpoint of availability, examples of the compound having a phenol group include diallyl bisphenol A, diallyl bisphenol S, vinyl phenol, and allyl phenol. Examples of the compound having a carboxyl group include butenoic acid, pentenoic acid, hexenoic acid, and heptene. Examples of the compound having an isocyanuric acid group include monoallyl isocyanuric acid, diallyl isocyanuric acid, triallyl cyanurate, and the like.

  In particular, an isocyanuric acid derivative represented by the following general formula (V) is particularly preferable from the viewpoint of high heat resistance and light resistance.

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

  As R of the said general formula (V), it is preferable that it is a hydrocarbon group from a viewpoint that the heat resistance of the hardened | cured material obtained can become higher, and it is preferable that carbon number is 1-20. More preferably, it has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. Examples of these preferable R include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,

Etc.

  As R in the general formula (V), from the viewpoint that the adhesion of the obtained cured product with various materials can be improved, at least one of the three Rs has 1 or more carbon atoms containing one or more epoxy groups. Preferably a monovalent organic group of ~ 50,

It is more preferable that it is a C1-C50 monovalent organic group containing 1 or more of epoxy groups represented by these. Examples of these preferable R include a glycidyl group,

Etc.

  The various compounds described above can be used alone or in admixture of two or more.

(About hydrosilylation reaction)
In the hydrosilyl reaction for obtaining the modified polyorganosiloxane (C) of the present invention, all alkenyl groups may be reacted as long as the resulting reaction product has two or more SiH groups per molecule. However, some of them may remain. From the viewpoint of avoiding degradation of the handling property of the modified product due to gelation or viscosity increase during the reaction, the reaction is carried out under the condition that either one of the compounds to be reacted is charged in excess, and the unreacted product is distilled off to obtain the reaction product. The method is preferred.

  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.

  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. Specific examples include 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 catalyst for the hydrosilylation reaction, a known hydrosilylation catalyst can be used, and chloroplatinic acid, a platinum-olefin complex, a platinum-vinylsiloxane complex, and the like are preferable from the viewpoint of catalytic activity. Moreover, these catalysts may be used independently and may be used together 2 or more types.

  A gelation inhibitor can be used for the purpose of improving the storage stability of the resulting reaction product. Examples of the gelation inhibitor include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, an organic peroxide, and the like, and these can be used in combination.

  The ratio of modification of each compound is not particularly limited, but when the total alkenyl group amount of the alkenyl group-containing compound is A and the total SiH group amount of the SiH group-containing compound is B, 1 ≦ B / A ≦ 30. More preferably, 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 addition amount of the catalyst is not particularly limited, and in order to keep the cost of the curable composition relatively low, the preferable lower limit of the addition amount is 10 ⁻⁸ mol, more preferably, 1 mol of the alkenyl group of the alkenyl group-containing compound. is 10 ^-6 moles, the upper limit of the preferable amount is 10 ^-1 mol per alkenyl group 1 mole of the compound, more preferably 10 ^-2 moles.

(About acidic groups)
In the component (C), each structure represented by the following (Y1) to (Y3):

  A group consisting of a phenolic hydroxyl group and a carboxyl group (hereinafter, “each structure represented by the above formulas (Y1) to (Y3), phenolic hydroxyl group and carboxyl group” may be referred to as “acidic group”). In the same molecule, at least one selected from the above can be dissolved in an alkaline aqueous solution and can be applied as a resist material capable of alkali development.

  Among these organic structures, the structure represented by the carboxyl group and the above (Y1) to (Y3) is preferable from the viewpoint that the obtained cured product is less colored at high temperature. In particular, those having a structure represented by the above (Y1) to (Y3) are preferable from the viewpoint of obtaining a low cured product.

  In the curable composition of the present invention, the polyorganosiloxane compound having at least two SiH groups in one molecule may be used alone, or two or more kinds may be used in combination.

(Component (D))
To the curable composition of the present invention, (D) a compound having two or more alkenyl groups having reactivity with SiH groups in one molecule may be added.

  In the curable composition of the present invention, as the component (D), any compound having two or more alkenyl groups may be used, and the compound that can be used in the hydrosilylation reaction is not particularly limited. Of the described alkenyl group-containing compounds, any compound having two alkenyl groups can be used without particular limitation.

  Component (D) may be used alone or in combination of two or more.

  The amount of component (D) added is preferably such that the total amount of alkenyl groups in component (D) is 0.3 mol or more and 1 mol or less with respect to 1 mol of total SiH groups in component (C). From the viewpoint that it is difficult to bleed out later, it is preferably 0.5 mol or more and 0.8 mol or less.

  When component (D) is added, it is preferable to add a hydrosilylation catalyst, and any known hydrosilylation catalyst can be used without particular limitation. What is necessary is just to set the addition amount suitably in the range which does not impair the effect of this invention. When the modified polyorganosiloxane obtained by the above hydrosilylation reaction is used as the component (C), the hydrosilylation catalyst mixed in the modified polyorganosiloxane can be allowed to act as it is.

(Method for preparing curable composition and film forming method)
The preparation method of the curable composition of this invention is not specifically limited, It can prepare by various methods. Various components may be mixed and prepared immediately before curing, or may be stored at a low temperature in a one-component state in which all components are mixed and prepared in advance.

  The coating method of the curable composition of the present invention on various substrates is not particularly limited as long as it can be uniformly applied, and is generally applied by spin coating or slit coating. Can do.

As a light source for sensitization, a light source that emits light having an absorption wavelength of a photoacid generator or a sensitizer to be used may be used. A light source usually having 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 .

  For the purpose of removing the solvent, a pre-bake or vacuum devolatilization process can be performed before exposure. However, the prebaking temperature is preferably 80 ° C. or lower, more preferably 60 ° C. or lower, from the problem that developability is lowered by applying heat. Vacuum devolatilization and heating can be performed simultaneously.

  The curable composition of the present invention exhibits positive performance because the unexposed portion is cured and contrasted by heating after exposure. The heating temperature is preferably 50 ° C. or higher and 200 ° C. or lower, and preferably 80 ° C. or higher and 150 ° C. or lower because the contrast is good.

  There is no particular limitation on the patterning formation by development, and a desired pattern can be formed by dissolving and removing the exposed portion by a general developing method such as dipping or spraying. The developer can be used without particular limitation as long as it is generally used. Specific examples thereof include organic alkali aqueous solutions such as tetramethylammonium hydroxide aqueous solution and choline aqueous solution, potassium hydroxide aqueous solution, sodium hydroxide. Inorganic aqueous alkali solutions such as aqueous solution, aqueous potassium carbonate solution, aqueous sodium carbonate solution, and aqueous lithium carbonate solution, those obtained by adding an alcohol or a surfactant to the aqueous solution for adjusting the dissolution rate, and various organic solvents. .

  Further, after development, post-baking may be performed in order to improve the strength and reliability of the resist film. Although various baking temperatures can be set, a preferable temperature range is 60 to 400 ° C, more preferably 90 to 350 ° C.

(Additive)
(Sensitizer)
In order to give the curable composition of the present invention sensitivity to light and sensitivity to light having a high wavelength such as g-line (436 nm), h-line (405 nm), and i-line (365 nm), A sensitizer can be added as appropriate. These sensitizers can be used in combination with the photoacid generator and the like to adjust the curability.

  Examples of sensitizers that can 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 compound include thioxanthone, 2-chlorothioxanthone, 2,5-diethyldioxanthone and the like.

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

(Adhesion improver)
An adhesion improver can also be added to the curable composition of the present invention. 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 which 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 (C) modified polyorganosiloxane compound. More preferably, it is 0.5 to 5 parts by weight. If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the physical properties of the resist film may be adversely affected.

(Thermoplastic resin)
Various thermoplastic resins can be added to the curable composition of the present invention 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 such as terephthalic acid and isophthalic acid and aliphatic dicarboxylic acids (for example, 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.

  As a thermoplastic resin, you may have the carbon-carbon double bond and / or SiH group which have a reactivity with SiH group in a molecule | numerator. In the point that the obtained cured product tends to be tougher, the molecule has one or more carbon-carbon double bonds and / or SiH groups having reactivity with SiH groups in the molecule on average. It is preferable.

  The thermoplastic resin may have other crosslinkable groups. 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, in terms of easy compatibility with the (C) modified polyorganosiloxane compound. It is more preferable that 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 (C) modified polyorganosiloxane compound and mixed in a uniform state, or may be pulverized and mixed in a particle state, or dissolved and mixed in a solvent. It is good also as a state. In the point that the hardened | cured material obtained becomes easy to become more transparent, it is preferable to melt | dissolve in (C) modified polyorganosiloxane compound and to mix in a uniform state. Also in this case, the thermoplastic resin may be directly dissolved in the (C) modified polyorganosiloxane compound, or may be uniformly mixed using a solvent or the like. And it is good also as a mixed state.

  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 the curable composition of this invention 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 aging inhibitor may be added to the curable composition of the present invention. 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 carboxylates, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.

  These anti-aging agents may be used alone or in combination of two or more.

(Radical inhibitor)
You may add a radical inhibitor to the curable composition obtained by this invention. 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.

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

(solvent)
(C) When the modified polyorganosiloxane compound has a high viscosity, it can be dissolved 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.

  As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane, propylene glycol-1-monomethyl ether-2-acetate, and chloroform are preferable.

(Other additives)
The curable composition of the present invention 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, an anti-fogging agent, 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 add in the range which does not impair.

(Use)
The curable composition or cured product of the present invention can be used for various applications. It can be applied to various uses in which a conventional epoxy resin adhesive is 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, insulating packings, insulating coating materials, adhesives, high heat resistant adhesives, high heat dissipation adhesives , Optical adhesives, LED element adhesives, various substrate adhesives, heat sink adhesives, paints, UV powder paints, inks, colored inks, UV inkjet inks, coating materials (hard coats, sheets, films, peeling Paper coating, optical disk coating, optical fiber coating, etc.), molding materials (including sheets, films, FRP, etc.), sealing materials, pottes Encapsulating material, encapsulating material, encapsulating material for light emitting diode, optical semiconductor encapsulating material, liquid crystal sealing agent, sealing agent for display device, encapsulating material for electric material, encapsulating material for various solar cells, high heat resistant encapsulating material, Resist materials, liquid resist materials, colored resists, dry film resist materials, solder resist materials, color filter materials, stereolithography, solar cell materials, fuel cell materials, display materials, recording materials, anti-vibration materials, waterproof materials, It can be applied to moisture-proof materials, heat-shrinkable rubber tubes, O-rings, photosensitive drums for copying machines, solid electrolytes for batteries, and gas separation membranes. In addition, concrete protective materials, linings, soil injection agents, cold storage heat materials, sealing materials for sterilization treatment devices, contact lenses, oxygen-enriched films, additives to other resins, and the like can be mentioned.

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

  The reaction rate of the allyl group in the synthesis example was confirmed by the following measuring method.

(NMR)
A 300 MHz NMR apparatus manufactured by Varian Technologies Japan Limited was used. The reaction rate of the allyl group in the synthesis was measured by adding a reaction solution diluted to about 1% with deuterated chloroform to an NMR tube and confirming the presence or absence of a peak derived from an unreacted allyl group or vinyl group.

(Synthesis Example 1)
A 2 L autoclave was charged with 602 g of toluene and 626 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase was replaced with nitrogen, and then heated and stirred at an internal temperature of 105 ° C. A mixed liquid of 90.0 g of triallyl isocyanurate, 90.0 g of toluene, and 0.05570 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise. After completion of the dropwise addition, it was confirmed by ¹ H-NMR that the peak due to the allyl group had disappeared, and the reaction solution was cooled and devolatilized to obtain a colorless and transparent liquid “Reaction 1”.

(Synthesis Example 2)
A 500 mL four-necked flask was charged with 150 g of toluene and 50 g of “Reactant 1” of Synthesis Example 1, and the gas phase was purged with nitrogen, and then heated and stirred at an internal temperature of 105 ° C. A mixed solution of 18.8 g of methoxydimethylvinylsilane and 17.8 g of toluene was added dropwise. After completion of the dropwise addition, it was confirmed by ¹ H-NMR that the vinyl group-derived peak had disappeared, and the reaction solution was cooled and devolatilized to obtain a colorless and transparent liquid “Reaction product 2”.

(Synthesis Example 3)
To a 2 L autoclave, 600 g of toluene and 600 g of 1,1,3,3-tetramethyldisiloxane were added, and the gas phase portion was purged with nitrogen, and then heated and stirred at an internal temperature of 105 ° C. A mixed liquid of 90.0 g of triallyl isocyanurate, 90.0 g of toluene, and 0.05570 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise. After completion of the dropwise addition, it was confirmed by ¹ H-NMR that the peak due to the allyl group had disappeared, and the reaction solution was cooled and devolatilized to obtain a colorless transparent liquid “Reaction product 3”.

(Synthesis Example 4)
A 500 mL four-necked flask was charged with 100 g of toluene and 57.49 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase was purged with nitrogen, and then heated and stirred at an internal temperature of 105 ° C. A mixed liquid of 10.0 g of diallyl isocyanuric acid, 70.0 g of 1,4-dioxane, and 0.01186 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise. After completion of the dropwise addition, it was confirmed by ¹ H-NMR that the peak due to the allyl group had disappeared, and the reaction solution was cooled and devolatilized to obtain a colorless transparent liquid “Reaction product 4”.

(Synthesis Example 5)
A 500 mL four-necked flask was charged with 100 g of toluene and 57.49 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase was purged with nitrogen, and then heated and stirred at an internal temperature of 105 ° C. A mixture of 7.5 g of 1,3,5,7-tetramethylvinylcyclotetrasiloxane, 70.0 g of toluene, and 0.01186 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise. After completion of the dropwise addition, it was confirmed by ¹ H-NMR that the peak due to the allyl group had disappeared, and the reaction solution was cooled and devolatilized to obtain a colorless transparent liquid “Reaction product 5”.

(Synthesis Example 6)
A 500 mL four-necked flask was charged with 100 g of toluene and 60 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase portion was purged with nitrogen, and then heated and stirred at an internal temperature of 105 ° C. A mixed solution of 10 g of vinylnorbornene, 70.0 g of toluene, and 0.0186 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise. After completion of the dropwise addition, it was confirmed by ¹ H-NMR that the peak due to the allyl group had disappeared, and the reaction solution was cooled and devolatilized to obtain a colorless and transparent liquid “Reaction product 6”.

(Synthesis Example 7)
A 500 mL four-necked flask was charged with 100 g of toluene and 60 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase was purged with nitrogen, and then heated and stirred at an internal temperature of 70 ° C. A mixed solution of 10 g of divinylbenzene, 70.0 g of toluene, and 0.0090 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise. After completion of the dropwise addition, it was confirmed by ¹ H-NMR that the peak due to the allyl group had disappeared, and the reaction solution was cooled and devolatilized to obtain a colorless transparent liquid “Reaction product 7”.

(Examples 1-8)
50 parts by weight of a solvent (methyl isobutyl ketone, MIBK), a 1 wt% toluene solution of a basic compound (bicyclodiazaoundecene), a photoacid generator (reaction products 1 to 7 obtained in Synthesis Examples 1 to 7) A 25 wt% propylene glycol methyl ether acetate (PGMEA) solution of Tridia, trade name RHODORSIL PI2074) and triallyl isocyanurate were added in the ratios shown in Table 1 to obtain a curable composition.

The obtained curable composition was applied to a glass plate (50 × 100 × 0.7 mm) by spin coating, and a part of the coated surface of the glass plate was covered with a light-shielding plate of an aluminum plate, and exposed portions and unexposed portions And an integrated light amount of 250 mJ / cm ^{2 was} exposed using a conveyor type exposure apparatus (high pressure mercury lamp, LH6 manufactured by Fusion). After the sample exposure, the sample was heated on a hot plate at 80 ° C. for 1 hour, and the glass plate on which the coating film was formed was immersed in acetone for 30 seconds for development. Thereafter, the sample was further post-baked on a hot plate at 200 ° C. for 1 hour.

(Comparative Examples 1-3)
In the curable composition obtained in Example 1 above, a formulation in which a basic compound and a photoacid generator were not added was prepared, and a sample was prepared in the same manner as described above. In Comparative Example 3, a sample was prepared in the same manner as in Example 1 by using a commercially available photocurable epoxy compound (Celoxide 2021P, manufactured by Daicel Chemical Industries) instead of the reactant 1.

(Coating film evaluation)
The samples obtained in Examples 1 to 8 and Comparative Examples 1 to 3 were stored in a circulating hot air oven at 200 ° C. for 24 hours, and a heat resistance test was performed. Table 1 shows the results of measuring the coating film appearance and light transmittance before and after the heat test.

  Here, the appearance of the coating film was visually evaluated.

  The light transmittance was measured under the condition of a scan speed of 300 nm / min using U-3300 manufactured by Hitachi, Ltd.

  The thin film obtained from the curable composition containing the basic compound, the photoacid generator, and the modified polyorganosiloxane compound as essential components according to the present invention has a performance as a positive resist, and has an unexposed portion. The remaining film gives a resist film excellent in heat resistance and transparency.

Example 9
A cured product thin film of about 1 μm was formed on a SUS plate (30 × 30 × 1 mm thickness, # 400 surface polishing) in the same manner as in Example 1. A conductive tape was applied on this thin film, and when the conductivity of the SUS plate and the conductive tape was measured with a tester (manufactured by Sanwa Denki Keiki Co., Ltd., PC510), current did not flow and insulation was maintained. It was confirmed that it functions as a membrane.

Claims (13)

As an ingredient
(A) a basic compound,
(B) a photoacid generator, and
(C) A curable composition containing a modified polyorganosiloxane compound having at least two SiH groups in one molecule. The (C) modified polyorganosiloxane compound is
-(-RHSiO-) n-
The hardening of Claim 1 which has a siloxane unit represented by (R represents a C1-C50 monovalent organic group and may be the same or different, n = 1-10). Sex composition. The (C) modified polyorganosiloxane compound is
R ₂ HSiO-
The curable composition of Claim 1 or 2 which has a siloxane unit represented by (R represents a C1-C50 monovalent organic group and may be the same or different.). The (C) modified polyorganosiloxane compound has in the same molecule at least one selected from the group consisting of each structure represented by the following formulas (Y1) to (Y3), a phenolic hydroxyl group, and a carboxyl group, The curable composition as described in any one of Claims 1 thru | or 3.

The (C) modified polyorganosiloxane compound has the following general formula (I)

The curable composition as described in any one of Claims 1 thru | or 4 which has a structure represented by these.   The curable composition according to any one of claims 1 to 5, wherein the (C) modified polyorganosiloxane compound has an alicyclic hydrocarbon structure and / or an aromatic ring.   The (C) modified polyorganosiloxane compound is a hydrosilylation of a compound having at least two SiH groups in one molecule and a compound having one or more alkenyl groups having reactivity with SiH groups in one molecule. The curable composition as described in any one of Claims 1 thru | or 6 which is obtained by making it.   The curable composition according to any one of claims 1 to 7, further comprising (D) a compound having two or more alkenyl groups having reactivity with SiH groups in one molecule.   The curable composition according to any one of claims 1 to 8, wherein the basic compound (A) is a quaternary amine.   The curable composition according to claim 1, wherein the (B) photoacid generator is an aromatic iodonium salt.   Hardened | cured material formed by hardening | curing the curable composition as described in any one of Claims 1 thru | or 10.   A positive resist using the curable composition according to claim 1.   The interlayer insulation film for electronic devices formed using the curable composition as described in any one of Claims 1 thru | or 10.