JP2005042050A - Curable silicone composition and method for forming pattern by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable silicone composition curable by hydrosilylation. <P>SOLUTION: This curable silicone composition consists of the following: (i) an organopolysiloxane having at least 2 alkenyl groups bonded with silicon atom in one molecule, (ii) an organohydrogenpolysiloxane or hydrosilane compound having at least 2 hydrogen atoms bonded with a silicon atom in one molecule, (iii) an organopolysiloxane having an alkenyl group and hydrogen atom bonded with silicon atom and (iv) a hydrosilylation catalyst component of (1) a substance containing an onium salt as a hydrosilylation catalyst and an inhibitor, or (2) a selected substance from the reaction products of the hydrosilylation catalyst with the onium salt. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a curable silicone composition that can be cured by hydrosilylation. More specifically, the present invention is useful for pattern formation in the production of optical waveguides, printed wiring boards, and semiconductor chips. The present invention relates to a curable curable silicone composition having photosensitivity excellent in properties, applicability and stability. The present invention also relates to a method for forming an arbitrary positive or negative pattern by using a catalyst component obtained by blending or reacting an onium salt as an inhibitor with a hydrosilylation catalyst in a photoreaction. is there.

  In recent years, research on resists using organopolysiloxane has been actively conducted for the purpose of developing photoresists that form fine patterns with high precision. For example, an alkali-soluble organopolysiloxane having a methyl group and a silanol group directly bonded to silicone has been proposed (see Patent Document 1), and an organopolysiloxane having a phenol derivative that becomes alkali-soluble by addition of exposure or an acid catalyst is disclosed. It is disclosed (see Patent Document 2). However, in order for these organopolysiloxanes to have photosensitivity, photosensitive organic functional groups must be introduced, or organic functional groups that are easily decomposed into acids and bases must be introduced, and the synthesis is also complicated. Until the pattern is further formed, processes such as pattern formation of a general resist layer on the substrate, oxygen or fluorine reactive ion etching, and removal of the resist layer are necessary. Many known cured organopolysiloxanes have poor heat resistance and mechanical properties and are unsuitable as substrate materials. In particular, the loss of light transmission due to containing many organic functional groups is large, and it has been difficult to use as an optical material.

Japanese Patent Laid-Open No. 10-246960 JP 2001-154366 A

  The present invention relates to a curable silicone composition that is cured by a cross-linking reaction by hydrosilylation, in which hydrosilylation by light irradiation distinguishes between curing of an exposed part and an unexposed part at a certain temperature and develops a pattern. It is intended to be formed. This method does not require a long and complicated process to form a pattern on the substrate while using a conventional polysiloxane, and allows direct pattern formation, and is excellent in heat resistance, mechanical properties, and optical properties. Pattern formation is possible. In particular, there is little loss of light transmission, and it can be applied to optical materials such as optical waveguides.

That is, the present invention provides a curable silicone composition containing the following components (i), (ii) and (iv), or containing the following components (iii) and (iv). is there.
(I) an organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule;
(Ii) an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to a silicon atom in one molecule, or a hydrosilane compound;
(Iii) an organopolysiloxane having an alkenyl group bonded to a silicon atom and a hydrogen atom;
(Iv) Hydrosilylation catalyst component comprising (1) a hydrosilylation catalyst and an onium salt as an inhibitor, or (2) a reaction product of the hydrosilylation catalyst and the onium salt. What is chosen from things.

  Furthermore, the present invention forms a layer comprising a curable silicone composition containing a catalyst component (1) containing the hydrosilylation catalyst and an onium salt as an inhibitor on a substrate, and a pattern mask is formed on the layer. Or directly irradiate only the pattern forming portion with light, and then heat to form a latent image of pattern formation, and then remove the uncured portion irradiated with light with a solvent, The present invention provides a pattern forming method for producing a positive-type uneven pattern on a substrate.

  Alternatively, a layer made of a curable silicone composition containing the catalyst component (2) consisting of the reaction product of (2) the hydrosilylation catalyst and the onium salt is formed on the substrate, and light is emitted in the same manner as described above. An uncured portion that is irradiated and unirradiated with light is removed with a solvent, and a pattern forming method for producing a negative-type uneven pattern on the substrate is provided.

  Without being bound by theory, in the case of the curable silicone composition containing the hydrosilylation catalyst component (1), the onium salt is decomposed by irradiation with light, which inhibits the hydrosilylation. Thus, in the case of the curable silicone composition containing the hydrosilylation catalyst component (2), the light irradiation portion becomes an uncured portion of the silicone, and the coordinate bond between the hydrosilylation catalyst and the onium salt is This is probably because it decomposes when irradiated with light, the catalytic activity is restored, and the silicone in the light-irradiated portion is cured.

  In the present invention, light may be exemplified by ultraviolet light or visible light, but is not limited thereto, and energy that excites a chemical reaction, such as infrared light, X-rays, α-rays, β-rays, and γ-rays. Includes what you have.

The present invention is described in further detail below.
((I) component: organopolysiloxane having an alkenyl group bonded to a silicon atom)
The organopolysiloxane of component (i) of the present invention must have at least two alkenyl groups bonded to one silicon atom in one molecule.

  The organopolysiloxane may contain a small amount of hydroxyl groups or alkoxy groups. The chemical structure of this organopolysiloxane is a linear or branched polymer. These polymers may be single polymers or copolymers or a mixture of two or more polymers. The molecular weight of this organopolysiloxane is not particularly limited, and includes those from liquid to raw rubber or solid having a very high viscosity, and is not particularly limited. Usually, those having a viscosity at 25 ° C. of 10 to 100000 cp are used. The

Examples of such an organopolysiloxane include the following: a trimethylsiloxy group-blocked methylalkenylsiloxane / dimethylsiloxane copolymer, a dimethylvinylsiloxy group-blocked dimethylpolysiloxane, and a dimethylvinylsiloxy at both ends. Blocked dimethylsiloxane / methylphenylsiloxane copolymer, both ends dimethylvinylsiloxy group-blocked dimethylsiloxane / diphenylsiloxane / methylvinylsiloxane copolymer, both ends trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, both ends Dimethylvinylsiloxy-capped methyl (3,3,3-trifluoropropyl) polysiloxane, dimethylvinylsiloxy-capped dimethylsiloxane methyl (3,3,3-trifluoro) Ropuropiru) _{copolymer, CH 2 = CH (CH 3} ) 2 SiO 1/2 units and (CH _{3) 3} made of SiO _1/2 units and SiO _4/2 units polysiloxane; R ₁ SiO _3/2 units And R ₂ SiO _2/2 units; R ₃ SiO _1/2 and RSiO _3/2 units; polysiloxanes containing R ₃ SiO _1/2 units, R ₁ SiO _3/2 units and R ₂ SiO _2/2 units Or R ₃ SiO _1/2 unit, R ₁ SiO _3/2 unit, R ₂ SiO _2/2 unit and SiO _4/2 unit; RSiO _3/2 unit and SiO _4/2 unit; R ₃ SiO _1/2 unit And SiO _4/2 units (wherein R is alkyl, aryl, fluoroalkyl or alkenyl, having at least two alkenyl groups bonded to silicon in one molecule), and alkenyl bonded to a silicon atom Organopolysiloxane having at least two groups per molecule.

((Ii) component: organohydrogenpolysiloxane)
The organohydrogenpolysiloxane of component (ii) of the present invention is a crosslinking agent of component (i), and (iv) the hydrogen atom bonded to the silicon atom is converted to a lower alkenyl group of component (i) by the catalytic action of component. Addition reaction and cure. Therefore, it is necessary to have at least two hydrogen atoms bonded to silicon atoms in one molecule. The organic group covalently bonded to the silicon atom other than the hydrogen atom is the same as that exemplified in the section of the organopolysiloxane of the component (i). The organic group is not limited to one type, and two or more types may be mixed. The chemical structure of the organohydrogenpolysiloxane may include a linear structure, a cyclic structure, a network structure, or a three-dimensional structure, and may be a single polymer or copolymer of these, or a mixture of two or more types of polymers. Further, it may be a single molecule having a low molecular weight SiH group, that is, a silane compound.

  An organopolysiloxane in which the organopolysiloxane having an alkenyl group bonded to a silicon atom and the organohydrogenpolysiloxane are formed in the same molecule can also be used.

  The molecular weight of this component is not particularly limited, but in order to improve the compatibility with component (i), the viscosity of this organohydrogenpolysiloxane is usually 0.5 to 100,000 cp at 25 ° C., preferably 1 to 10,000 cp. The amount of addition is such that the molar ratio of the total number of hydrogen atoms bonded to the silicon atom of component (ii) and the total number of alkenyl groups bonded to the silicon atom of component (i) is 0.5: 1 to 20: 1. It is preferable. This is because when the molar ratio is less than 0.5: 1 or larger, the physical properties of the cured product are adversely affected.

Specific examples of the component (ii) include trimethylsiloxy group-capped methylhydrogen polysiloxane at both terminals, trimethylsiloxy group-capped dimethylsiloxane / methylhydrogenpolysiloxane copolymer, dimethylsiloxane / methylhydrogensiloxane cyclic copolymer Copolymer, (CH ₃ ) ₃ SiO _1/2 unit, (CH ₃ ) ₂ HSiO _1/2 unit and SiO _4/2 unit copolymer, (CH ₃ ) ₂ HSiO _1/2 unit and R′SiO _{3 / 2} units of copolymer (R ′ = aryl, vinyl, hexenyl, allyl, methyl, ethyl and hydrogen atoms).
Single molecule silane compounds include 1,4-bis (dimethylsilyl) benzene, bis (p-dimethylsilylphenyl) ether, 1,2-bis (dimethyldisilyl) ethane, 1,3,5-tris (dimethyl) And silyl) benzene.

((Iii) component: organopolysiloxane having an alkenyl group bonded to a silicon atom and a hydrogen atom)
The organopolysiloxane of component (iii) of the present invention must have both an alkenyl group bonded to a silicon atom and a hydrogen atom bonded to a silicon atom in one molecule. The silicon-bonded alkenyl group is cured by addition reaction with the silicon-bonded hydrogen atom in the other organopolysiloxane. At this time, it is not always necessary to add a crosslinking agent as the component (ii).
This organopolysiloxane is a linear or branched polymer and has various properties from liquid to solid. Further, the molecular weight is not particularly limited.
Examples of such an organopolysiloxane include a copolymer of trimethylsiloxy group-capped methylvinylsiloxane / methylhydrogen / dimethylsiloxane, a dimethylvinylsiloxy group-capped methylhydrogen / dimethylpolysiloxane, and dimethylvinylsiloxy at both ends. Group-blocked methylhydrogen / dimethylsiloxane / methylphenylsiloxane copolymer, both ends dimethylvinylsiloxy group-blocked methylhydrogen / dimethylsiloxane / diphenylsiloxane / methylvinylsiloxane copolymer, both ends dimethylvinylsiloxy group-blocked methylhydrogen・ Methyl (3,3,3-trifluoropropyl) polysiloxane, dimethylvinylsiloxy group-blocked methylhydrogen, dimethylsiloxane, methyl (both ends) , 3,3-trifluoropropyl) siloxane _{copolymers, CH 2 = CH (CH 3} ) 2 SiO 1/2 units and H (CH _{3) 2} SiO _1/2 units and (CH _{3) 3} SiO _1/2 Examples thereof include polysiloxane composed of units and SiO _4/2 units, polysiloxane composed of CH ₂ = CHSiO _3/2 units and H (CH ₃ ) ₂ SiO _1/2 units, and the like. Furthermore, R''SiO _3/2 units and R '' ₂ SiO _2/2 units; R '' ₃ SiO _1/2 units and R''SiO _3/2 units; R '' ₃ SiO _1/2 units; R''SiO _3/2 units and R '' ₂ SiO _2/2 units; R '' ₃ SiO _1/2 units and R''SiO _3/2 units and R '' ₂ SiO _2/2 units and SiO _{4 / 2} units; R ″ SiO _3/2 units and SiO _4/2 units; R ″ ₃ SiO _1/2 units and SiO _4/2 units in one molecule consisting of silicon atom bonded alkenyl groups and silicon atom bonded hydrogen An organopolysiloxane having an atom (R ″ represents an alkenyl group, an alkyl group, an aryl group or a fluoroalkyl group other than a hydrogen atom).

((Iv) component: catalyst component for hydrosilylation)
Hydrosilylation catalyst component (iv) is a combination of (1) a catalyst for hydrosilylation and an onium salt that suppresses this catalytic action under light irradiation, or (2) a catalyst for hydrosilylation and an onium salt. This product is a reaction product of which the catalytic action is restored under light irradiation.
(Hydrosilylation catalyst)
The catalyst for hydrosilylation used in component (iv) can be crosslinked by an addition reaction between an alkenyl group bonded to the silicon atom of component (i) and a hydrogen atom bonded to the silicon atom of component (ii). All catalysts. For example, platinum-based catalyst, palladium-based catalyst or rhodium-based catalyst. Specifically, chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum olefin complex, platinum ketone complex (Pt (II) bis (2,4-pentane) Geoate), Pt (II) bis (2,4-hexanedioate), Pt (II) bis (1-phenyl-1,3-butanedioate), Pt (II) bis (1,1,1, 5,5,5-hexafluoro-2,4-pentanedioate)), cyclopentadiene and platinum complexes (cyclopentadienyltriphenylplatinum, cyclopentadienyltrimethylplatinum, cyclopentadienyltriethylplatinum) ) Or a platinum complex of 1,5-cyclooctadiene, a complex of platinum and vinylsiloxane, platinum supported on alumina, silica, carbon black, etc., tetrakis (triphenylphosphine) palladium, and the like. The addition amount of this component is 0.1 to 1000 parts by weight, preferably 1.0 to 100 parts by weight as a platinum-based metal with respect to 1 million parts by weight of the total amount of component (i) and component (ii). However, if the addition amount is less than 0.1 parts by weight, the physical properties of the resulting platinum catalyst or platinum compound-containing silicone cured product deteriorate, and if the addition amount is 100 parts by weight or more, the storage stability of the composition of the present invention decreases. This is because there is a case of doing.

  Of these, from the viewpoint of high platinum catalyst activity, for example, a complex of platinum and vinylsiloxane represented by the following chemical formula is preferred. This platinum catalyst is described in US Pat. No. 3,419,593 and US Pat. No. 5,175,325, and US Pat. No. 3,775,452 describes improvements in the stability of this catalyst.

  In order to prevent undesired curing from occurring during the steps of storage and application of the curable silicone composition, a catalyst and a usual curing inhibitor such as a hydroxyketone, hydroxyalkyne and dienyl may be used in combination.

(Hydrosilylation catalyst component (1) -hydrosilylation inhibitor that inhibits hydrosilylation by light irradiation)
Another component used together with the hydrosilylation catalyst in component (iv) is an onium salt that inhibits hydrosilylation by light irradiation. Specific examples include hydrosilylation catalyst inhibitors that generate phosphine, sulfite, amine, organic acid, inorganic acid, and the like by light irradiation.

  The photoreaction of the hydrosilylation catalyst inhibitor comprising such an onium salt proceeds by irradiating light having a wavelength corresponding to the absorption wavelength of the hydrosilylation catalyst inhibitor. Generally, when these hydrosilylation catalyst inhibitors have an aryl group, irradiation with ultraviolet light is suitable, and when they have an alkyl group, irradiation with light having a short wavelength of 200 nm or less is suitable. Yes.

  Such a substance that inhibits hydrosilylation is generated by irradiating light having a wavelength corresponding to the absorption wavelength of the catalyst inhibitor for hydrosilylation. Generally, when these hydrosilylation catalyst inhibitors have an aryl group, light having a wavelength of 200 nm or less is suitable. In particular, when having a phenyl group, light having a wavelength of 254 nm is suitable.

The catalyst inhibitor for hydrosilylation which inhibits hydrosilylation by light irradiation in the present invention is preferably selected from the following (A), (B) or (C).
(A) Onium salt represented by the general formula (R ¹ _a R ² _b R ³ _c R ⁴ _d M) ⁺ Y ⁻ :
Here, M is selected from P, I, S, N, Te, Se, As, Sb, Bi, O, Br and Cl. R ¹ , R ² , R ³ and R ⁴ are the same or different groups, a, b, c and d are each an integer of 0 to 3, and Y ⁻ represents an anion. (A + b + c + d) is usually 1 greater than the valence of M. Typical examples are 2 for M = I, 3 for M = S, and 4 for M = P or N.
Here, R ¹ , R ² , R ³ and R ⁴ are preferably selected from the following 1) to 4).
1) C1-C8 saturated or unsaturated aliphatic hydrocarbon group 2) C6-C12 alicyclic hydrocarbon group 3) C1-C8 alkoxy group 4) C6-C30 aroma Group hydrocarbon group

Y ^- is preferably selected from the following 1) to 3).
1) halide ions ^{(F -, Cl -, Br} - or I ^-)
2) Anions containing transition metals or metalloids. Examples of the transition metal include Sb, Fe, Sn, Bi, Al, and Si. Examples of metalloids include B, P, and As.
3) Anions other than the above

Specific examples of Y ⁻ include F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , RO ⁻ , RCOO ⁻ , BF ₄ ⁻ , BPh ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , SbF ₆ ⁻ , AsF _{6 ^{-, SbCl 6 -, HSO 4}} -, FeCl 4 -, SnCl 6 2-, 2- , and the like SiF ₆ ^2-and BiCl _5.

  Examples of the onium salt used in the present invention include phosphonium salts, iodonium salts, sulfonium salts, ammonium salts, oxonium salts, nitronium salts, nitrosonium salts, diazonium salts, selenium salts, and stannonium salts.

  As phosphonium salts, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, boron tetrafluoride benzyltriphenylphosphonium, hexafluoroantimonybenzyltriphenylphosphonium, (p-butoxybenzyl) triphenylphosphonium bromide, (p-butoxybenzyl) ) Triphenylphosphonium chloride, (p-methoxybenzyl) triphenylphosphonium chloride, (dimethoxybenzyl) triphenylphosphonium bromide, (p-dimethylaminobenzyl) triphenylphosphonium chloride, boron tetrafluoride (p-butoxybenzyl) triphenyl Phosphonium, antimony hexafluoride (p-butoxybenzyl) triphenylphosphonium, tetraphenylboron (p-butoxy) Ndyl) triphenylphosphonium, (p-butoxybenzyl) triphenylphosphonium acetate, tetra (perfluorophenyl) boron (p-butoxybenzyl) triphenylphosphonium, iodide (p-butoxybenzyl) triphenylphosphonium, phenacyltriphenyl Phosphonium bromide, phenacyltriphenylphosphonium chloride, ethoxycarbonylmethyltriphenylphosphonium, naphthalenylmethyltriphenylphosphonium chloride, fluorenyltriphenylphosphonium chloride, anthracenylmethyltriphenylphosphonium chloride, anthracenylmethyltriphenylphosphonium Bromide, pyrenylmethyltriphenylphosphonium bromide, pyrenylmethyltriphenylphosphonium Chloride and the like.

  As an iodonium salt, diphenyliodonium chloride, diphenyliodonium bromide, tetra (perfluorophenyl) boron diphenyliodonium, boron tetrafluoride diphenyliodonium; [phenyl-p- (2-hydroxytetradecyloxy) phenyl] iodonium hexafluoroantimonate, [Phenyl-p- (2-hydroxytetradecyloxy) phenyl] iodonium chloride, [phenyl-p- (2-hydroxytetradecyloxy) phenyl] iodonium bromide, tetra (perfluorophenyl) boron [phenyl-p- (2 -Hydroxytetradecyloxy) phenyl] iodonium, bis (p-dodecylphenyl) iodonium hexafluoroantimonate, bis (p-dodecylphenyl) io Donium chloride, bis (p-dodecylphenyl) iodonium bromide, boron tetrafluoride bis (p-dodecylphenyl) iodonium, tetra (perfluorophenyl) boron bis (p-dodecylphenyl) iodonium, (pn-decyloxy) Phenyl) phenyliodonium hexafluoroantimonate, [p- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium trifluoromethanesulfonate, [p- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexa Fluorophosphate, [p- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium tetrakis (pentafluorophenyl) borate, bis (pt-butylphenyl) iodonium hexa Fluoroantimonate, bis (pt-butylphenyl) iodonium hexafluorophosphate, bis (pt-butylphenyl) iodonium trifluoromethanesulfonate, bis (pt-butylphenyl) iodonium tetrafluoroborate, bis (dodecyl) Phenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium trifluoromethanesulfonate, and the like.

  As the sulfonium salt, (p-butoxybenzyl) diphenylsulfonium bromide, (p-butoxybenzyl) diphenylsulfonium chloride, boron tetrafluoride (p-butoxybenzyl) diphenylsulfonium, antimony hexafluoride (p-butoxybenzyl) diphenylsulfonium, Tetraphenylboron (p-butoxybenzyl) diphenylsulfonium, (p-butoxybenzyl) diphenylsulfonium acetate, trimethylsulfonium iodide, diphenylmethylsulfonium tetrafluoride, diphenylmethylsulfonium iodide, dibenzylmethylsulfonium bromide, benzyldiphenylsulfonium Chloride, benzyldodecylmethylsulfonium bromide, iodide (3-methyl-2-butenyl) tetramethyle Sulfonium hexafluoride antimonate (2-butenyl) tetramethylene sulfonium, methyl octyl phenacyl sulfonium bromide, benzyl methyl octyl sulfonium bromide, benzyl iodide dodecyl methyl sulfonium, and the like benzyl iodide dodecyl methyl sulfonium.

  As ammonium salts, (p-butoxybenzyl) triphenylammonium bromide, (p-butoxybenzyl) triphenylammonium chloride, boron tetrafluoride (p-butoxybenzyl) triphenylammonium, antimony hexafluoride (p-butoxybenzyl) ) Triphenylammonium, tetraphenylboron (p-butoxybenzyl) triphenylammonium, (p-butoxybenzyl) triphenylammonium acetate, benzyltrimethylammonium iodide, benzyldiphenylmethylammonium tetrafluoride, benzyldiphenylmethylammonium iodide Dibenzyldimethylammonium bromide, benzyltriphenylammonium chloride, benzyldimethyldodecylammonium bromide, Di (3-methyl-2-butenyl) tetramethylene ammonium, antimony hexafluoride di (2-butenyl) tetramethylene ammonium, dimethyloctylphenacyl ammonium bromide, benzyldimethyloctylammonium bromide, benzyldimethyldodecylammonium iodide, iodine Benzyldimethyldodecylammonium chloride and the like.

As oxonium salt, boron tetrafluoride trimethyloxonium and the like; as nitronium salt, boron tetrafluoride nitronium; as nitrosonium salt, boron tetrafluoride nitrosonium; as diazonium salt, p-methoxybenzenediazonium chloride, Examples thereof include p-butoxybenzenediazonium chloride.
These onium salts can be used alone or in combination of two or more.

Among the onium salts (A), those selected from the following a to d are particularly preferable.
^{a (R 1 R 2 R 3} R 4 P) + Y -
^{b (R 1 R 2 I)} + Y -
^{c (R 1 R 2 R 3} S) + Y -
^{d (R 1 R 2 R 3} R 4 N) + Y -
In the formula, R ¹ , R ² , R ³ and R ⁴ are independently defined as described above. Y ^- is representative of the anion.

Examples of the component (iv) used in the present invention as the catalyst inhibitor for hydrosilylation of component (B) include the following.
(B) Compound represented by the general formula [R ⁵ R ⁶ R ⁷ R ⁸ P ⁺ (CR ⁹ R ¹⁰ ) _n ] X ⁻ L ₃ :
Here, R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently selected from alkyl having 1 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms or aralkyl group having 6 to 30 carbon atoms. R ⁹ and R ¹⁰ are independently a hydrogen atom, a halogen atom selected from F, Cl, Br or I, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 6 to 30 carbon atoms. , An acyl group having 2 to 6 carbon atoms, an aryloyl group having 6 to 30 carbon atoms, and a cyano group. X is a boron atom or an aluminum atom. L is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 6 to 30 carbon atoms, an alkoxy group having 6 to 30 carbon atoms, or an alkoxy group having 6 to 30 carbon atoms. Group, an aryloxy group having 6 to 30 carbon atoms, an acyloxy group having 6 to 30 carbon atoms, and an aryloyl group having 6 to 30 carbon atoms. n is an integer of 1-6.

Examples of (C) as the catalyst inhibitor for hydrosilylation used in the present invention include the following.
(C) Compound represented by general formula (R ¹¹ R ¹² R ¹³ S ⁺ ═Y) Y ⁻ :
Here, R ¹¹ , R ¹² and R ¹³ are aromatic hydrocarbons having 6 to 12 carbon atoms. Y ⁻ represents an anion.

  The amount of component (iv) added is not particularly limited, but is usually preferably 1 to 10,000 parts by weight with respect to 1 million parts by weight of the total amount of component (i) and component (ii). If the amount of component (iv) added is less than 1.0 part by weight, the effect on photocurability will be reduced, and sufficient photopatterning will not be obtained. On the other hand, when it exceeds 10,000 parts by weight, the weather resistance and thermal stability of the resulting cured product tend to be lowered. Therefore, in view of the balance between photopatterning curability and the obtained weather resistance and thermal stability, the component (iv) should be added in an amount of 1.0 to 500 times by weight with respect to the platinum-based metal catalyst. More desirable.

  The curable silicone composition is a radical generator (photopolymerization initiator, initiator), photosensitizer, reactive diluent, silica particles (inorganic filler), as long as the object and effect of the present invention are not impaired. It is also preferable to contain titanium oxide, a leveling agent, a wettability improver, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupling agent, and a polymer additive. Hereinafter, main additives will be described in detail.

(Radical generator)
The radical generator is a compound that is decomposed by radiation such as ultraviolet rays to generate radicals, and the radicals initiate a polymerization reaction of radical polymerizable groups. For example, acetophenone, acetophenone benzyl ketal, anthraquinone, 2-hydroxy-1- (4-isopropylphenyl) -2-methylpropan-1-one, carbazole, xanthone, 4-chlorobenzophenone, 4,4′-diaminobenzophenone, 1, 1-dimethoxydeoxybenzoin, 3,3′-dimethyl-4-methoxybenzophenone, thioxanthone compound, 2-methyl-1- (p-methylthiophenyl) -2-morpholinopropan-2-one, 2-benzyl-2 -Dimethylamino-1- (p-morpholinophenyl) -butan-1-one, triphenylamine, diphenyl (2,4,6-trimethylbenzyl) phosphine oxide, bis- (2,6-dimethoxybenzoyl) -2 , 4,4-Trimethylpentyljo Sphine oxide, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, benzophenone derivatives, Michler's ketone, Examples include 3-methylacetophenone, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone (BTTB), dialkyl peroxide compounds, parkmill D, and trimethylsilyl peroxide. Such radical generators can be used singly or in combination of two or more.

(Photosensitizer)
The photosensitizer absorbs energy rays such as light, and is used to improve the sensitivity of light, or to impart activity as a hydrosilylation catalyst to long-wavelength ultraviolet light or visible light. When the photosensitizer is exposed to light, light energy can be transferred to the platinum complex or the catalyst inhibitor for hydrosilylation so as to exert a light effect in hydrosilylation. These photosensitizers include polycyclic aromatic compounds such as anthracene and derivatives thereof, pyrene and derivatives thereof, and perylene and derivatives thereof. Or aromatic compounds having a ketone chromophore, such as acetophenone, benzophenone, 2-isopropylthioxanthone, diethylthioxanthone and thioxanthone derivatives; anthraquinone, bromoanthraquinone and anthraquinone derivatives; anthracene, bromoanthracene and anthracene derivatives; perylene and perylene derivatives; Examples include xanthene and thioxanthene derivatives; coumarin and ketocoumarin. More preferred photosensitizers are diethyl thioxanthone and bromoanthracene.

(Silica particles)
By adding silica particles to the curable silicone composition, the curing shrinkage of the resulting cured film can be gradually reduced. The amount of silica particles added is not particularly limited, but is preferably 10 to 250 parts by weight, particularly 20 to 200 parts by weight, and more preferably 30 to 150 parts by weight with respect to 100 parts by weight of component (A).

  The silica particle should just be a particle | grains which have a silica as a main component, and may contain components other than a silica. Examples of components other than silica include alkali metal oxides, alkaline earth metal oxides, and oxides such as Ti, Zr, Al, B, Sn, and P. The average particle diameter of the silica particles is preferably 0.001 to 20 μm, but the average particle diameter is preferably 0.001 to 0.2 μm, more preferably 0.001 to 0.2 μm from the point that a transparent cured film is formed. 01 μm.

  Furthermore, the shape of the silica particles is not particularly limited, but is preferably at least one shape selected from the group consisting of spherical, hollow, porous, rod-like, plate-like, fibrous, and irregular shapes. However, in order to make the dispersibility better, it is preferable to use spherical silica particles. The method of using the silica particles is not particularly limited, but can be used in a dry state, for example, or can be used in a state dispersed in water or an organic solvent.

  A dispersion of finely divided silica particles known as colloidal silica can also be used directly. In particular, use of colloidal silica is preferable because high transparency can be obtained. When the dispersion solvent of colloidal silica is water, the pH is preferably 2 to 13, and more preferably 3 to 7. When the colloidal silica dispersion solvent is an organic solvent, the organic solvent is methanol, isopropyl alcohol, ethylene glycol, butanol, ethylene glycol monopropyl ether, methyl ethyl ketone (MEK), methyl isobutyl ketone, toluene, xylene, dimethylformamide (DMF) Etc., and a mixed solvent of these with an organic solvent or water that forms a homogeneous system may be used. Preferred organic solvents are methanol, isopropyl alcohol, methyl ethyl ketone, xylene and the like.

  As polymer additives, epoxy resin, acrylic resin, polyamide resin, polyamideimide resin, polyurethane resin, polybutadiene resin, polychloroprene resin, polyether resin, polyester resin, styrene-butadiene block copolymer, petroleum resin, xylene resin, An organic resin (polymer or oligomer) such as a ketone resin, a cellulose resin, a fluorine polymer, a silicone polymer, or a polysulfide polymer, or a compound in which these organic resins (polymer or oligomer) are modified with a hydrolyzable silyl group It is preferable.

  The curable silicone composition used in the present invention may contain a specific organic solvent as necessary. By blending a specific organic solvent, the storage stability of the curable silicone composition is improved, an appropriate viscosity can be obtained, and a patterned film having a uniform thickness can be formed. It can also be used as a developer after irradiation.

Examples of such organic solvents include ether-based organic solvents, ester-based organic solvents, ketone-based organic solvents, hydrocarbon-based organic solvents, alcohol-based organic solvents, nitrogen-containing solvents, sulfur-containing solvents, and siloxane-based organic solvents. Although at least one can be selected from the group consisting of: Usually, an organic solvent having a boiling point of 50 to 200 ° C. under atmospheric pressure and uniformly dissolving each component is preferable. For example, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, 2,2,4-trimethylpentane, octane, cyclohexane, and methylcyclohexane; aromatics such as benzene, toluene, xylene, ethylbenzene, n-amylnaphthalene, and trimethylbenzene Hydrocarbon solvents; methanol, ethanol, n-propanol, phenol, cyclohexanol, benzyl alcohol, methyl phenyl carbinol, diacetone alcohol, cresol, and other mono alcohol solvents; ethylene glycol, 1,2- Polyhydric alcohol solvents such as propylene glycol, diethylene glycol, glycerin; acetone, methyl ethyl ketone (MEK), trimethylnonanone, cyclohexanone, acetonylacetone, acetophenone, phenol Ketone solvents such as Chon; ethyl ether, isopropyl ether, ethylene oxide, 1,4-dioxane, dimethyl dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran (THF), Ether solvents such as 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, γ-butyrolactone, n-propyl acetate, ethyl acetoacetate, ethylene glycol monomethyl ester, diethyl oxalate, methyl lactate, diethyl malonate, dimethyl phthalate, Ester solvents such as diethyl phthalate; nitrogenous compounds such as N-methylformamide, acetamide, N-methylpyrrolidone Elementary solvents: sulfur-containing solvents such as dimethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide (DMSO), sulfolane; octamethylcyclotetrasiloxane, hexamethyldisiloxane, 1,3-divinyldimethylphenyldisiloxane, 1,5 -One kind of siloxane organic solvent such as divinyltetramethyldiphenyltrisiloxane, phenyltris (dimethylvinylsiloxy) silane, methylvinylphenylsiloxane oligomer consisting of (PhSiO _3/2 ) and (Me ₂ ViSiO _1/2 ) alone or Two or more types of combinations can be mentioned.

  Among these organic solvents, more preferred examples include alcohol organic solvents and ketone organic solvents. This is because the storage stability of the curable silicone composition can be further improved. Particularly preferred organic solvents include at least one organic solvent selected from the group consisting of propylene glycol monomethyl ether, ethyl lactate, methyl isobutyl ketone, methyl amyl ketone, toluene, xylene and methanol.

  The type of the organic solvent is also preferably selected in consideration of the application method of the curable silicone composition. For example, it is preferable to use a spin coating method because a thin film having a uniform thickness can be easily obtained. As an organic solvent to be used, glycol ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether; Ethylene glycol alkyl ether acetates such as cellosolve acetate, propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; esters such as ethyl lactate and ethyl 2-hydroxypropionate; such as diethylene glycol monomethyl ether, diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether Diethylene glycols; methyl isobutyl ketone, 2-heptanone, cyclohexa It is preferable to use the down and ketones such as methyl amyl ketone, particularly ethyl cellosolve acetate, propylene glycol methyl ether acetate, ethyl lactate, it is preferable to use methyl isobutyl ketone and methyl amyl ketone.

(Description of pattern manufacturing process)
As a means for applying the curable silicone composition onto a semiconductor substrate, a spin coating method, a dipping method, a spray method, a bar coating method, a roll coating method, a curtain coating method, a clapper printing method, a silk screen method, an ink jet method, or the like is used. I can do it. Of these, a spin coating method is preferably used because a coating film having a uniform thickness can be obtained. The viscosity of the coating film can be adjusted to 0.1 to 200 μm by adjusting the viscosity by using no solvent or an organic solvent depending on the spin speed, time and composition amount, that is, the components of the composition to be used.

  Next, this coating film is dried at 40 to 120 ° C., and the temperature is increased or decreased as necessary to form a silicone film by heating for 0 to 5 minutes. It is selectively exposed so that a desired pattern can be obtained by vacuum ultraviolet rays, extreme ultraviolet rays, electron beams, X-rays or ion rays, and the silicone film after pattern exposure is developed to expose uncured silicone in an exposed area or an unexposed area. Dissolve the material.

  After development, the patterned silicone film is further heated at 40 to 250 ° C., if necessary, and heated for 1 to 30 minutes to completely cure the silicone film.

Examples of radiation used include visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, and γ rays, and ultraviolet rays are particularly preferable. The means for irradiating radiation is not particularly limited, and various general means can be used. For example, a light source lamp such as a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, or an excimer lamp can be used as the light source. Wavelength 150～800Nm, preferably 200～460Nm, by irradiating a predetermined time under the conditions of illuminance of 1 to 500 mW / cm ^2, it is preferable that the 10~5000mJ / cm ² irradiation amount.
The following examples and comparative examples explain the present invention in more detail.
In the following examples, the structures or characteristics of the components used in the tables are as follows.

(I) Organopolysiloxane having an alkenyl group bonded to a silicon atom as component:
1) Siloxane polymer 1: vinyl content 1.2w%
ViMe ₂ Si (Me ₂ SiO) ₁₄₅ (ViMeSiO) ₃ SiMe ₂ Vi
2) Siloxane polymer 2: vinyl content 1.8w%
(SiO ₂ ) ₅₈ (Me ₃ SiO _1/2 ) ₃₅ (HO _1/2 ) ₃ (ViMe ₂ SiO _1/2 ) ₅
3) Siloxane polymer 3: vinyl content 5.15w%
(ViMe ₂ SiO _1/2 ) ₂₅ (PhSiO _3/2 ) ₇₅

(Ii) Component organohydrogenpolysiloxane having a hydrogen atom bonded to a silicon atom:
1) Crosslinker 1: Hydrogen content 1.05 w%, viscosity at 25 ° C. 30 cst
(Me ₃ SiO) (MeHSiO) ₃₉ (Me ₂ SiO) _16.2 (SiMe ₃ )
2) Crosslinker 2: Hydrogen content 0.12 w%, viscosity 135 cst at 25 ° C.
(Me ₃ SiO) (Me ₂ SiO) ₁₀₃ (MeHSiO) _9.5 (SiMe ₃ )
3) Crosslinking agent 3: Hydrogen content 0.76 w%, viscosity at 25 ° C. 5 cst
(Me ₃ SiO) (Me ₂ SiO) ₃ (MeHSiO) ₅ (SiMe ₃ )
4) Crosslinking agent 4: Hydrogen content 0.54 w%, viscosity at 25 ° C. 70 cst
(Me ₂ HSiO _1/2 ) _0.53 (PhSiO _3/2 ) _0.47

(Iii) Organopolysiloxane having an alkenyl group bonded to a silicon atom and a hydrogen atom as component:
1) Siloxane polymer 4: Hydrogen content 0.32 w%, vinyl content 26.6 w%
(Me ₂ HSiO _1/2 ) ₂₅ (ViSiO _3/2 ) ₇₅

  (Iv) Hydrosilylation catalyst of component: 57 A complex compound of divinyltetramethyldisiloxane and platinum (II) chloride was diluted with divinyltetramethyldisiloxane by the production method described in US Pat. No. 5,175,325 %solution.

(Iv) A reaction inhibitor that suppresses a hydrosilylation catalyst comprising an onium salt of a component:
1) Reaction inhibitor 1: An alcohol solution of benzyltriphenylphosphonium chloride (solid content 20% by weight)
[(C ₆ H ₅ CH ₂ ) (C ₆ H ₅ ) ₃ P] ⁺ Cl ⁻
2) Reaction inhibitor 2: (p-butoxybenzyl) triphenylphosphonium bromide in alcohol (solid content 20% by weight)
[(p-BuOC ₆ H ₄ CH ₂ ) (C ₆ H ₅ ) ₃ P] ⁺ Br ^‐
3) Reaction inhibitor 3: [Phenyl-p- (2-hydroxytetradecyloxy) phenyl] iodonium hexafluoroantimonate solution (solid content 20% by weight)
_{[(C 6 H 5) (} p- (C 12 H 25 CH (OH) CH 2 O) C 6 H 4) I] + SbF 6 -
4) Reaction inhibitor 4: Dodecyl alcohol solution of bis (p-dodecylphenyl) iodonium hexafluoroantimonate (solid content 36.8% by weight)
_{[(pC 12 H 26 C 6} H 4) 2 I] + SbF 6 -
5) Reaction inhibitor 5: naphthylmethyltriphenylphosphonium chloride:
[(C ₁₀ H ₇ CH ₂ ) (C ₆ H ₅ ) ₃ P] ⁺ Cl ^- alcohol solution (solid content 20% by weight)
6) Reaction inhibitor 6: Fluorenyltriphenylphosphonium chloride:
[(C ₁₃ H ₉ CH ₂ ) (C ₆ H ₅ ) ₃ P] ⁺ Cl ^- alcohol solution (solid content 20% by weight)
7) Reaction inhibitor 7: Anthracenylmethyltriphenylphosphonium chloride:
_{[(C 14 H 9 CH 2} ) (C 6 H 5) 3 P] + Cl - alcohols - Le solution (solid content 20 wt%)
8) Reaction inhibitor 8: (p-methoxyphenyl) diphenylsulfonium hexafluoroantimonate:
_{[(p-MeOC 6 H 4} ) (C 6 H 5) 2 S] + SbF 6 - alcohol - Le solution (solid content 11 wt%)
9) Reaction inhibitor 9: (p-methoxybenzyl) dimethylphenylammonium hexafluoroantimonate:
_{[(p-MeOC 6 H 4} CH 2) (C 6 H 5) (CH 3) 2 N] + SbF 6 - alcohol - Le solution (solid content of 5 wt%)

Solvent 1: Toluene solvent 2: Mesitylene

Photosensitizer 1: 2-Isopropylthioxanthone photosensitizer 2: Anthracene photosensitizer 3: Acetophenone photosensitizer 4: Benzophenone photosensitizer 5: Pyrene

(Iv) Hydrosilylation catalyst component (1):
A catalyst containing a hydrosilylation catalyst and an onium salt as an inhibitor.
(Formulation example 1)
(I) Component alkenyl group-containing polysiloxane, (ii) Component organohydrogenpolysiloxane, (iii) Component organopolysiloxane, (iv) Component platinum catalyst and onium salt as inhibitor described in Table 1 below, and optionally Photosensitizers and solvents were blended in the proportions shown in Table 1 below to prepare curable silicone compositions of Examples 1-14. For comparison, the composition of Comparative Example 1 was also prepared.

(Examples 1-14 and Comparative Example 1)
Using the hydrosilylation catalyst component (1) prepared according to Formulation Example 1, a storage stability test and a pattern formation test were performed. The results are shown in Tables 1 and 2.

The composition of Comparative Example 1 had poor storage stability at room temperature, and curing proceeded within 1 hour. On the other hand, the compositions of Examples 1, 12 and 13 showed storage stability at room temperature for 3 hours or more, indicating that the onium salt compound is effective as a reaction inhibitor.
Moreover, the curable silicone composition of the same composition as Example 4 was prepared as a comparative example except not mix | blending the reaction inhibitor 4. FIG. The resulting composition proceeded to cure within 2 hours at room temperature. In contrast, the composition of Example 4 exhibited storage stability for 3 weeks or more. The compositions of Examples 2, 3, and 5-11 show storage stability for over 2 weeks. This indicates that the onium salt compound is effective as a reaction inhibitor.

(Example of pattern formation process)
As a typical example, the pattern forming process will be described using the curable silicone composition shown in Example 2. Spin coating was performed on a silicone wafer at 500 rpm for 10 seconds and at 2000 rpm for 30 seconds. Next, the coating film was heated at 120 ° C. for 2 minutes and dried to form a tack-free layer, and then a photomask was applied thereto and irradiated with 400 mJ / cm ² using a low-pressure mercury lamp. Heat at 4 ° C. for 4 minutes. Thereafter, etching was performed with a toluene solution to obtain a positive patterned film. Further, the film was baked at 200 ° C. for 30 minutes to complete the curing.
About Examples 1-13, pattern formation was performed on the conditions shown in the following Table 2 using the curable silicone composition shown in Table 1. The evaluation results for the obtained product are also shown in Table 2.

  As shown in Table 2, in Examples 4, 5, 6, 10, and 11, since the composition contains a photosensitizer, the amount of light required may be less than that of the composition that does not contain it.

  In the comparative example, a curable silicone composition similar to that in Example 1 was used, and a curable silicone composition not containing an onium salt as a catalyst inhibitor for hydrosilylation was used. The film could not be obtained.

(Iv) Hydrosilylation catalyst component (2):
Reaction products with onium salts as hydrosilylation catalysts and inhibitors that restore hydrosilylation catalytic activity upon light irradiation.
The hydrosilylation catalyst component (2) of the component (iv) used in the present invention that activates hydrosilylation by light irradiation loses the delayed effect of the onium salt by constant light irradiation. Specifically, the interaction between the hydrosilylation inhibitor and the platinum complex is lost by light irradiation, or the hydrosilylation catalyst inhibitor and the platinum complex are decomposed. This produces a catalytically active species of platinum that appears to promote hydrosilylation.

The onium salt used as a photoreaction inhibitor is a (R ¹ R ² R ³ R ⁴ P) ⁺ Y ^- type compound, and an electron such as an alkoxy group or an alkylamino group is provided to the aromatic ring bonded to the phosphorus atom. A compound having a functional substituent is preferred. For example, alkoxy-substituted benzyl group, alkylamino group and the like. In general, the amount used is preferably 0.1 to 500 times that of platinum, but more preferably 3 to 50 times in view of curing efficiency and physical properties after curing.
The same photocatalytic activity can be obtained by heat-treating the onium salt and the platinum catalyst, or by leaving it at room temperature without heating, or mixing the onium salt and the platinum catalyst in the silicone composition and subjecting it to appropriate heat treatment. A composition having is obtained.

(Iv) Hydrosilylation catalyst component (2):
Production of hydrosilylation catalyst and onium salt reacted.
(Formulation example 2)
In the production method described in US Pat. No. 5,175,325, a complex compound of divinyltetramethyldisiloxane and platinum (II) chloride was diluted with divinyltetramethyldisiloxane to 10 g of a 57% solution (p-butoxybenzyl). A methoxyethanol solution (solid content: 43%) of triphenylphosphonium bromide is added at a molar ratio of 10 to platinum and heated at 60 to 70 ° C. for 30 minutes. The obtained reaction product is used in the following Examples 15 to 20 and Comparative Example 2 as the hydrosilylation catalyst component (2).

The manufacturing process of the catalyst composition is omitted, and a methanol solution (solid content 20%) and platinum of (p-butoxybenzyl) triphenylphosphonium bromide and platinum are added directly at the compounding stage of the cured composition, and 2 to 50 to 60 ° C. The same effect can be obtained by heating for 3 hours.
The case of sulfonium is the same as that of phosphonium.
In the case of iodonium, the molar ratio is preferably 1 to 50 without heating.

(Examples 15 to 21 and Comparative Example 2)
(I) component alkenyl group-containing organopolysiloxane, component (ii) organohydrogenpolysiloxane, hydrosilylation catalyst component (2) obtained in Formulation Example 2, and a photosensitizer if desired. The curable silicone compositions of Examples 15 to 21 and Comparative Example 2 were prepared by mixing at the ratios shown in Table 3 below, respectively, and a storage stability test and a pattern formation test were performed. The results are shown in Table 4.

  The composition of Comparative Example 2 had poor storage stability at room temperature, and curing proceeded within 1 hour. On the other hand, since the compositions of Examples 15 to 21 showed storage stability at room temperature for 1 month or longer, it can be seen that the onium salt compound is effective as a catalyst inhibitor for hydrosilylation.

(Example of pattern formation process)
As a typical example, the pattern forming process will be described using the curable silicone composition shown in Example 18. Spin coating was performed on a silicone wafer through a 0.45 μm filter for 10 seconds at 500 rpm and 30 seconds at 2000 rpm. Next, the coating film was heated at 110 ° C. for 1 minute and dried to form a tack-free layer, and then a photomask was applied thereto and irradiated with 100 mJ / cm ² using a low-pressure mercury lamp, and further 140 ° C. For 3 minutes. Thereafter, etching was performed with a toluene solution to obtain a negative patterned film. Further, the film was baked at 200 ° C. for 30 minutes to complete the curing.
About Examples 15-21, pattern formation was performed on the conditions shown in Table 4 using the curable silicone composition shown in Table 3. Table 4 also shows the evaluation results for the obtained products.

  In Comparative Example 2, a curable silicone composition similar to Example 15 was used, and a curable silicone composition not containing an onium salt that was a catalyst inhibitor for hydrosilylation was used. A converted film was not obtained.

Claims (15)

Curable silicone composition containing the following components (i), (ii) and (iv) or containing the following components (iii) and (iv):
(I) an organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule;
(Ii) an organohydrogenpolysiloxane or hydrosilane compound having at least two hydrogen atoms bonded to a silicon atom in one molecule;
(Iii) an organopolysiloxane having an alkenyl group bonded to a silicon atom and a hydrogen atom;
(Iv) Hydrosilylation catalyst component comprising (1) a hydrosilylation catalyst and an onium salt as an inhibitor, or (2) a reaction product of the hydrosilylation catalyst and the onium salt. What is chosen from things.   The curable silicone composition according to claim 1, wherein the catalyst component (1) suppresses hydrosilylation under light irradiation.   The curable silicone composition according to claim 1, wherein the catalyst component (2) promotes hydrosilylation under light irradiation. The curable silicone composition according to claim 1 or 2, wherein the onium salt contained in the catalyst component (1) is selected from the group consisting of the following (A), (B) and (C):
(A) Onium salt represented by the general formula (R ¹ _a R ² _b R ³ _c R ⁴ _d M) ⁺ Y ⁻ :
Here, M is selected from P, I, S, N, Te, Se, As, Sb, Bi, O, Br and Cl. R ¹ , R ² , R ³ and R ⁴ are the same or different organic groups having 1 to 30 carbon atoms, a, b, c and d are each an integer of 0 to 3, and Y ⁻ represents an anion. (A + b + c + d) is one greater than the valence of M.
(B) Compound represented by the general formula [R ⁵ R ⁶ R ⁷ R ⁸ P ⁺ (CR ⁹ R ¹⁰ ) _n ] X ⁻ L ₃ :
Here, R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 6 to 30 carbon atoms. R ⁹ and R ¹⁰ are independently a hydrogen atom, a halogen atom selected from F, Cl, Br or I, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 6 to 30 carbon atoms. , An acyl group having 2 to 6 carbon atoms, an aryloyl group having 6 to 30 carbon atoms, and a cyano group. X is a boron atom or an aluminum atom.
L is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or 6 to 30 carbon atoms. It is selected from an aryloxy group, an acyloxy group having 2 to 30 carbon atoms, and an aryloyl group having 6 to 30 carbon atoms. n is an integer of 1-6.
(C) A compound represented by the general formula (R ¹¹ R ¹² R ¹³ S ⁺ = O) Y ⁻ .
Here, R ¹¹ , R ¹² and R ¹³ are aromatic hydrocarbons having 6 to 12 carbon atoms. The curable silicone composition according to claim 2, wherein the onium salt (A) is selected from the following a to d:
a (R ¹ R ² R ³ R ⁴ P) ⁺ Y ⁻ ;
b (R ¹ R ² I) ⁺ Y ⁻ ;
c (R ¹ R ² R ³ S) ⁺ Y ⁻ ;
d (R ¹ R ² R ³ R ⁴ N) ⁺ Y ⁻ .
In the formula, R ¹ , R ² , R ³ and R ⁴ are each independently a saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 6 to 12 carbon atoms, or 1 carbon atom. It is selected from -12 alkoxy groups or C6-C30 aromatic hydrocarbon groups.
Y ⁻ is an anion containing any of the following:
1) Halide ion (F ⁻ , Cl ⁻ , Br ⁻ or I ⁻ );
2) RO ⁻ , RCOO ⁻ (R is a hydrogen atom, aryl or alkyl);
3) Transition metal, lanthanoid metal or metalloid. (I) The organopolysiloxane according to claim 1 is an organopolysiloxane comprising RSiO _3/2 units, R ₃ SiO _1/2 units and SiO _4/2 units, RSiO _3/2 units and R ₂ SiO _2/2. Unit: R ₃ SiO _1/2 and RSiO _3/2 units; R ₃ SiO _1/2 and R ₂ SiO _2/2 units; R ₃ SiO _1/2 units, R ₁ SiO _3/2 units and R ₂ SiO _{2 / 2} unit organopolysiloxane or R ₃ SiO _1/2 unit and R ₁ SiO _3/2 unit, R ₂ SiO _2/2 and organopolysiloxane containing SiO _4/2 , RSiO _3/2 unit and SiO _4/2 unit; an organopolysiloxane composed of R ₃ SiO _1/2 unit and SiO _4/2 unit (where R is alkyl, aryl, fluoroalkyl or alkenyl, at least two per molecule) Having an alkenyl group bonded to silicon).   The curable silicone composition according to claim 1, wherein the onium salt that reacts with the hydrosilylation catalyst in the catalyst component (2) is the one according to claim 4 or 5. (Ii) The organohydrogenpolysiloxane or organopolysiloxane according to claim 1 is an organopolysiloxane comprising R′SiO _3/2 units, R ′ ₃ SiO _1/2 units and SiO _4/2 units, R′SiO _3/2 units and R ' ₂ SiO _2/2 units; R' ₃ SiO _1/2 and R'SiO _3/2 units; R ' ₃ SiO _1/2 and R' ₂ SiO _2/2 units; R ' ₃ Organopolysiloxane containing SiO _1/2 units and R ′ ₁ SiO _3/2 units and R ′ ₂ SiO _2/2 units or R ′ ₃ SiO _1/2 units and R ′ ₁ SiO _3/2 units and R ′ ₂ Organopolysiloxane containing SiO _2/2 and SiO _4/2 , R'SiO _3/2 unit and SiO _4/2 unit; Organopoly containing R ' ₃ SiO _1/2 unit and SiO _4/2 unit The curable silicone composition according to claim 1, which is a siloxane (wherein R 'is a hydrogen atom, alkyl, aryl or fluoroalkyl, and has at least two silicon-bonded hydrogen atoms in one molecule). . The organopolysiloxane of component (iii) according to claim 1 comprises R ″ SiO _3/2 units and R ″ ₂ SiO _2/2 units; R ″ ₃ SiO _1/2 units and R ″ SiO _{3 / 2} units; R '' ₃ SiO _1/2 units and R''SiO _3/2 units and R '' ₂ SiO _2/2 units; R '' ₃ SiO _1/2 units and R''SiO _3/2 units and R '' ₂ SiO _2/2 units and SiO _4/2 units; R''SiO _3/2 units and SiO _4/2 units; R 'consists of' ₃ SiO _1/2 units and SiO _4/2 units 1 Organopolysiloxane having a silicon-bonded alkenyl group and a silicon-bonded hydrogen atom in the molecule (R ″ represents an alkenyl group, an alkyl group, an aryl group or a fluoroalkyl group other than a hydrogen atom).   Contains a photosensitizer or radical generator that can transmit light energy to the hydrosilylation catalyst component so that it will exhibit a light effect on hydrosilylation when exposed to long-wavelength ultraviolet or visible light. The curable silicone composition according to claim 1.   The curable silicone composition according to claim 10, wherein the photosensitizer is a polycyclic aromatic compound or an aromatic compound having a ketone chromophore.   The curable silicone composition according to claim 1, 2 or 3 is applied on a substrate to form a silicone layer, and a pattern mask is applied to the layer to irradiate light, or only the pattern forming portion is irradiated directly. Then, after the silicone layer is heat-cured, a pattern forming method comprising removing an uncured portion.   13. The pattern forming method according to claim 12, wherein the curable silicone composition according to claim 1, 2 or 3 is applied on a substrate to form a silicone layer and irradiated with light, or only on a pattern forming portion. A method for forming a positive pattern, comprising directly irradiating, then heat-curing the silicone layer, and removing uncured portions.   13. The pattern forming method according to claim 12, wherein the curable silicone composition according to claim 1, 2 or 3 is applied on a substrate to form a silicone layer and irradiated with light, or only on a pattern forming portion. A method for forming a negative pattern comprising directly irradiating and then heat-curing the silicone layer and then removing uncured portions.   15. The pattern forming method according to claim 13, wherein the uncured silicone layer is removed and further heated to improve the strength.