JP4660182B2 - Activated energy ray-curable silicone composition and negative pattern forming method using the same - Google Patents

Description

  The present invention relates to a curable silicone composition that can be cured by a hydrosilylation reaction. Specifically, it is easy to prepare and has excellent patterning characteristics, coating properties, and stability, manufacturing of an optical waveguide, a printed wiring board, and a semiconductor chip. The present invention relates to a curable silicone composition having photosensitivity that is useful for pattern formation during production. The present invention also relates to a negative pattern forming method using the curable silicone composition.

  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 (see Patent Document 1), and an organopolysiloxane having a phenol derivative that becomes alkali-soluble by the addition of a photoacid generator (Patent Document 2) Have been proposed).

  However, in order to impart photosensitivity to these organopolysiloxanes, a photosensitive organic functional group or an organic functional group that can be easily decomposed with an acid or a base must be introduced, and the synthesis is complicated. Furthermore, pattern formation using these organopolysiloxanes requires steps such as resist layer formation on the substrate, oxygen or fluorine reactive ion etching, and resist layer removal, which improves pattern formation efficiency. It was sought after.

  In addition, 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.

On the other hand, the use of an organic peroxide and a platinum catalyst in a thermosetting silicone elastomer composition is disclosed in U.S. Pat. No. 4,329,275, U.S. Pat. No. 4,375,523, U.S. Pat. No. 4,487,906. No. 4,451,634, and the use of peroxides in photocatalysts is also known. In particular, US Pat. No. 4,375,523 describes a photocurable composition comprising an organic peroxide and a platinum catalyst, although it is a release coating composition.
Japanese Patent Laid-Open No. 10-246960 JP 2001-154366 A U.S. Pat. No. 4,329,275 U.S. Pat. No. 4,375,523 U.S. Pat. No. 4,487,906 U.S. Pat. No. 4,451,634

  The present invention is a curable silicone composition that forms a crosslink by a hydrosilylation reaction and a radical reaction and is cured, is easy to prepare, has excellent patterning characteristics, applicability and stability, and is irradiated with active energy rays. It is a first object of the present invention to provide a curable silicone composition in which a hydrosilylation catalyst is activated to accelerate a curing reaction to give a cured product having excellent heat resistance, mechanical properties, and optical properties. A second object is to efficiently perform negative pattern formation with high accuracy by utilizing the difference in solubility between the irradiated portion and the non-irradiated portion of the object.

The first object of the present invention is to
(1) The following:
(A) an organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule, and an organohydrogenpolysiloxane or hydrosilane compound having at least two hydrogen atoms bonded to a silicon atom in one molecule; A mixture of these, and
(B) at least one selected from the group consisting of an organopolysiloxane having an alkenyl group bonded to a silicon atom and a hydrogen atom bonded to a silicon atom in the same molecule;
(2) platinum catalyst for promoting hydrosilylation reaction,
(3) a reaction inhibitor for platinum catalyst, and
(4) Achieved by an activated energy ray-curable silicone composition containing an organic peroxide.

The organic peroxide is
(A) General formula:
R ¹ R ² R ³ COOCR ⁴ R ⁵ R ⁶
(Where
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom or an organic group having 1 to 30 carbon atoms)
Peroxides, indicated by
(B) General formula:
R ⁷ R ⁸ R ⁹ COO-X-OOCR ¹⁰ R ¹¹ R ¹²
[Where,
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same or different and each represents a hydrogen atom or an organic group having 1 to 30 carbon atoms,
X is-(CR'R ") _k -,-(CR'R") _l -CR '"" = CR """-(CR'" R "") _m -,-(CR'R ") _{n -C≡C- (CR '"R"}") o - and _{- (CR'R") p -Ar- (} CR'"R"") q -
(Where
k is an integer greater than or equal to 1,
l, m, n, o, p and q are each independently 0 or an integer of 1 or more,
R ', R ", R'", R "", R '"" and R """are the same or different and each represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, or adjacent carbons. Form a 5- or 6-membered ring with or without substituents with the atoms;
Ar represents an arylene group with or without a substituent)
Represents a divalent organic group selected from the group consisting of
Peroxides, indicated by
as well as,
(C) General formula:
R ¹⁷ R ¹⁸ R ¹⁹ SiOOSiR ²⁰ R ²¹ R ²²
(Where
R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are the same or different and represent an organic group having 1 to 30 carbon atoms)
Is preferably selected from the group consisting of peroxides.

More preferably, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , and R ′, R ″, R ′. ", R"", R '""andR""" are the same or different and are each a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are the same or different and are selected from the group consisting of aralkyl groups having 7 to 12 carbon atoms, and are saturated or unsaturated with 1 to 30 carbon atoms. It is selected from the group consisting of a saturated aliphatic hydrocarbon group, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 30 carbon atoms.

  The activated energy ray-curable silicone composition of the present invention preferably further contains a photosensitizer that absorbs the activated energy rays and activates the platinum catalyst for promoting the hydrosilylation reaction. As the photosensitizer, a polycyclic aromatic compound or an aromatic compound having a ketone chromophore can be preferably used.

  The second object of the present invention is to apply the activated energy ray-curable silicone composition onto a substrate to form a silicone layer, selectively irradiate the silicone layer with an activated energy ray, and This is achieved by a negative pattern forming method for removing the film. It is preferable to improve the strength of the pattern formed by heating after pattern formation.

  The silicone composition of the present invention is easy to manufacture because it uses a general-purpose polysiloxane, and has excellent patterning characteristics, applicability and stability, and has negative photosensitivity, so that it can be used for printed wiring boards and semiconductors. This is useful for forming a pattern during chip manufacture, particularly for forming a negative pattern.

  Furthermore, the pattern formation method of the present invention does not require a long and complicated process for pattern formation on the substrate, and can directly form a pattern of a cured silicone product having excellent heat resistance, mechanical properties and optical properties. is there. In particular, the cured silicone has little loss of light transmission and is suitable for optical materials such as optical waveguides.

  The present invention is described in detail below.

  (One of the components (1a): organopolysiloxane having an alkenyl group bonded to a silicon atom)

  The organopolysiloxane which is one of the components (1a) of the present invention needs to have at least two alkenyl groups bonded to silicon atoms in one molecule. The content of the alkenyl group is preferably 0.1 to 10% by weight of the organopolysiloxane, more preferably 1 to 6% by weight.

  The organopolysiloxane may contain a small amount of hydroxyl groups or alkoxy groups. The chemical structure of the organopolysiloxane may include any of a linear structure, a cyclic structure, a network structure, or a three-dimensional structure, and the organopolysiloxane may be a single polymer or a copolymer or two or more types of polymers. It may be a mixture. The molecular weight and viscosity of the organopolysiloxane are not particularly limited, and can be used in the form of raw rubber or solid having a very high viscosity, but usually has a viscosity at 25 ° C. of 10 to 100000 cp. Is used.

Such organopolysiloxanes include the following:
Copolymers of methylvinylsiloxane / dimethylsiloxane blocked with trimethylsiloxy groups at both ends, dimethylpolysiloxane blocked with dimethylvinylsiloxy groups blocked at both ends, dimethylsiloxane / methylphenylsiloxane copolymers blocked with dimethylvinylsiloxy groups at both ends, dimethylvinylsiloxy at both ends Base-blocked dimethylsiloxane / diphenylsiloxane / methylvinylsiloxane copolymer, both ends trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, both ends dimethylvinylsiloxy-blocked methyl (3,3,3-trifluoropropyl) poly Siloxane, dimethylvinylsiloxy group-blocked dimethylsiloxane methyl (3,3,3-trifluoropropyl) siloxane copolymer, CH ₂ = CH (CH ₃ ) ₂ SiO _1/2 units and (CH ₃ ) ₃ SiO _1/2 unit and S Polysiloxane consisting of iO _4/2 units, Organopolysiloxane consisting of 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 units Organopolysiloxane, organopolysiloxane composed of R ₃ SiO _1/2 and RSiO _3/2 units, organopolysiloxane composed of R ₃ SiO _1/2 and R ₂ SiO _2/2 units, R ₃ SiO _1/2 units and Organopolysiloxane consisting of R ₁ SiO _3/2 units and R ₂ SiO _2/2 units, R ₃ SiO _1/2 units, R ₁ SiO _3/2 units, R ₂ SiO _2/2 and SiO _4/2 units Organopolysiloxane composed of RSiO _3/2 units and SiO _4/2 units, Organopolysiloxane composed of R ₃ SiO _1/2 units and SiO _4/2 units (where R is independently alkyl , Aryl, fluoroalkyl or alkenyl having at least two alkenyl groups bonded to a silicon atom in one molecule).

  (Other component (1a): organohydrogenpolysiloxane or silane compound or a mixture thereof)

  The organohydrogenpolysiloxane or silane compound, which is the other of the component (1a) of the present invention, or a mixture thereof is a cross-linking agent for the above organopolysiloxane, which is also the component (1a). Due to the catalytic action, hydrogen atoms bonded to silicon atoms undergo an addition reaction with the lower alkenyl group of the organopolysiloxane and crosslink. Therefore, the organohydrogenpolysiloxane and the silane compound are required to have at least (on average) two hydrogen atoms bonded to a silicon atom in one molecule. The content of hydrogen is preferably 0.1 to 10% by weight of the organohydrogenpolysiloxane, more preferably 0.5 to 2% by weight. As the organic group covalently bonded to the silicon atom other than the hydrogen atom, the same organic group as in the case of the organopolysiloxane can be used. 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 any of a linear structure, a cyclic structure, a network structure, or a three-dimensional structure, and the organohydrogenpolysiloxane may be a single polymer or a copolymer, or two or more types. It may be a mixture of polymers.

Specific examples of the organohydrogenpolysiloxane of this component include trimethylsiloxy group-capped methylhydrogen polysiloxanes at both ends, trimethylsiloxy group-capped dimethylsiloxane / methylhydrogenpolysiloxane copolymers, dimethylsiloxane / methylhydrogens. Siloxane cyclic copolymer, a copolymer comprising (CH ₃ ) ₃ SiO _1/2 units, (CH ₃ ) ₂ HSiO _1/2 units and SiO _4/2 units, (CH ₃ ) ₂ HSiO _1/2 units and RSiO _3/2 copolymer, R'SiO _3/2 unit and R ' ₃ SiO _1/2 unit and SiO _4/2 unit organopolysiloxane, R'SiO _3/2 unit and R' ₂ Organopolysiloxane composed of SiO _2/2 units, Organopolysiloxane composed of R ' ₃ SiO _1/2 and R'SiO _3/2 units, R' ₃ SiO _1/2 units and R ' ₂ SiO _2/2 units from consisting organopolysiloxane, R _'3 SiO _1/2 units and R' ₁ SiO _3/2 units and R _'2 SiO _2/2 units That the organopolysiloxane, R _'3 SiO _1/2 units and R' ₁ SiO _3/2 units and R _'2 SiO _2/2 units and an organopolysiloxane consisting of SiO _4/2 units, R'SiO _3/2 units And organopolysiloxanes composed of R ₄ SiO _2/2 units and R ′ ₃ SiO _1/2 units and SiO _4/2 units (where R ′ is a hydrogen atom, alkyl, aryl or fluoroalkyl). And having at least two silicon-bonded hydrogen atoms in one molecule). Specific examples of the silane compound of this component include, in addition to phenylsilane and diphenylsilane, for example, carbosilane compounds in which a plurality of silicon atoms to which hydrogen atoms are directly bonded exist in the same molecule. , 4-bis (dimethylsilyl) benzene, bis (p-dimethylsilylphenyl) ether, 1,2-bis (dimethyldisilyl) ethane, 1,3,5-tris (dimethylsilyl) benzene, and the like.

  The molecular weight of the organohydrogenpolysiloxane or silane compound is not particularly limited. In order to improve the compatibility with the organopolysiloxane which is one of the components (1a), the organohydrogenpolysiloxane or silane compound is used. Or the viscosity of these mixtures is 0.5-100,000 cp normally at 25 degreeC, Preferably it is 1-10000 cp.

  The compounding amount of the component (1a) is not particularly limited, but the total number of hydrogen atoms bonded to the silicon atom of the organohydrogenpolysiloxane or silane compound and the alkenyl group bonded to the silicon atom of the organopolysiloxane. An amount in which the molar ratio to the total number of the components is in the range of 0.5: 10 to 10: 1 is preferable. If this molar ratio is less than 0.5: 10 or greater than 10: 1, the physical properties of the cured product may be adversely affected.

  (1b) Organopolysiloxane having an alkenyl group bonded to a silicon atom and a hydrogen atom bonded to a silicon atom in the same molecule

  Instead of the component (1a), or together with the component (1a), (1b) organopolysiloxane having hydrogen bonded to silicon in the same molecule as the alkenyl group bonded to silicon can be used. The alkenyl group content is preferably 0.1 to 30% by weight of the organopolysiloxane, and the hydrogen content is preferably 0.1 to 10% by weight of the organopolysiloxane.

  The organopolysiloxane of component (1b) needs to have both alkenyl groups bonded to silicon atoms and hydrogen atoms bonded to silicon atoms in one molecule. In this organopolysiloxane, the alkenyl group bonded to the silicon atom of one organopolysiloxane undergoes an addition reaction with the hydrogen atom bonded to the silicon atom of another organopolysiloxane due to the catalytic action of the component (2) described later to crosslink. . This organopolysiloxane can take any of a linear, branched, cyclic or cage shape. Further, the molecular weight is not particularly limited, and any property from liquid to solid can be used.

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 organopolysiloxanes composed of units and SiO _4/2 units, and organopolysiloxanes composed of CH ₂ = CHSiO _3/2 units and H (CH ₃ ) ₂ SiO _1/2 units. In addition, R''SiO _3/2 units and R '' ₂ SiO _2/2 units; organopolysiloxanes consisting of R '' ₃ SiO _1/2 units and R''SiO _3/2 units, R '' ₃ SiO Organopolysiloxane consisting of _1/2 units, R''SiO _3/2 units and R '' ₂ SiO _2/2 units, R '' ₃ SiO _1/2 units, R''SiO _3/2 units and R ''Organopolysiloxane composed of ₂ SiO _2/2 units and SiO _4/2 units, R''SiO _3/2 units and organopolysiloxane composed of SiO _4/2 units, R'' ₃ SiO _1/2 units and SiO Organopolysiloxane consisting of _4/2 units (R ″ represents an alkenyl group, a hydrogen atom, an alkyl group, an aryl group or a fluoroalkyl group, and has a silicon atom-bonded alkenyl group and a silicon atom-bonded hydrogen atom in one molecule. ) Can also be used.

  When a mixture of the component (1a) and the component (1b) is used, the mixing ratio of the component (1a) and the component (1b) is not particularly limited, and is bonded to the silicon atom described in paragraph [0023]. It may be mixed so that the molar ratio of the hydrogen atom and the alkenyl group bonded to the silicon atom is within the range.

  ((2) component: platinum catalyst for promoting hydrosilylation reaction)

  The catalyst for promoting the hydrosilylation reaction of (2) is an arbitrary platinum catalyst that promotes the addition reaction between the alkenyl group bonded to the silicon atom of component (1a) and / or (1b) and the hydrogen atom bonded to the silicon atom. is there. Specifically, chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum olefin complexes, platinum ketone complexes (Pt (II) bis (2,4-pentanedioate), 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-pentane Geoate)), platinum complexes consisting of cyclopentadiene and its derivatives (cyclopentadienyltriphenylplatinum, cyclopentadienyltrimethylplatinum, cyclopentadienyltriethylplatinum) or platinum complexes of 1,5-cyclooctadiene, platinum And platinum supported on alumina, silica, carbon black, and the like.

  Among these, from the viewpoint of high catalytic activity, for example, a complex of platinum and vinylsiloxane represented by the following chemical formula is preferable. 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.

  The addition amount of this component is 0.1 to 1000 parts by weight, preferably 10 to 200 parts by weight, as platinum metal with respect to 1 million parts by weight of component (1). If the addition amount is less than 0.1 parts by weight, sufficient crosslinking cannot be formed under normal curing conditions, resulting in poor curing or a decrease in pattern resolution. Conversely, if the addition amount exceeds 1000 parts by weight, the composition of the present invention. There is a possibility that the weather resistance and storage stability of the cured product may be lowered.

((3) Reaction inhibitor for platinum catalyst)

  Conventionally, when curing an addition reaction curable organopolysiloxane composition, various curing inhibitors have been used for the purpose of adjusting the curing speed and storage stability. Many compounds have already been proposed as such control agents. For example, U.S. Pat. No. 3,188,300 discloses organophosphorus compounds, U.S. Pat. No. 3,445,420 (Japanese Patent Publication No. 44-31476) and Japanese Patent Application No. 10-358619. Acetylene alcohols, triallyl isocyanurate for US Pat. No. 3,882,083 (Japanese Patent Publication No. 55-41626), hydroxyperoxide for US Pat. No. 4,061,609 (Japanese Patent Publication No. 57-20340), US Pat. (Japanese Patent Publication No. 48-10947) and U.S. Pat. No. 3,923,705 (Japanese Patent Publication No. 63-56563) disclose high vinyl siloxanes.

  In the curable silicone composition of the present invention, a platinum-based catalyst reaction inhibitor is blended in order to prevent undesirable curing during the storage and coating process. As a reaction inhibitor for a platinum-based catalyst, a compound having a carbon-carbon triple bond, particularly a compound having an ethynyl group is preferred. Examples of the compound having an ethynyl group include 1-ethynyl-1-cyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol, methyl-tris (3-methyl Examples include 1-butyne-3-oxo) silane and methyl-vinylbis (3-methyl-1-butyne-3-oxo) silane.

  Although the addition amount of this component is not particularly limited, it is typically 1 to 1000 times, preferably 10 to 1000 times that of platinum metal to be used.

((4) Organic peroxide)

The curable silicone composition of the present invention further contains an organic peroxide. As organic peroxide,
(A) General formula:
R ¹ R ² R ³ COOCR ⁴ R ⁵ R ⁶
(Where
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom or an organic group having 1 to 30 carbon atoms)
Peroxide (B) represented by the general formula:
R ⁷ R ⁸ R ⁹ COO-X-OOCR ¹⁰ R ¹¹ R ¹²
[Where,
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same or different and each represents a hydrogen atom or an organic group having 1 to 30 carbon atoms,
X is-(CR'R ") _k -,-(CR'R") _l -CR '"" = CR """-(CR'" R "") _m -,-(CR'R ") _{n -C≡C- (CR '"R"}") o - and _{- (CR'R") p -Ar- (} CR'"R"") q -
(Where
k is an integer greater than or equal to 1,
l, m, n, o, p and q are each independently 0 or an integer of 1 or more,
R ', R ", R'", R "", R '"" and R """are the same or different and each represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, or adjacent carbons. Form a 5- or 6-membered ring with or without substituents with the atoms;
Ar represents an arylene group with or without a substituent)
Represents a divalent organic group selected from the group consisting of
Peroxides, indicated by
And / or
(C) General formula:
R ¹⁷ R ¹⁸ R ¹⁹ SiOOSiR ²⁰ R ²¹ R ²²
(Where
R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are the same or different and represent an organic group having 1 to 30 carbon atoms)
The peroxide shown by can be used suitably.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , and R ′, R ″, R ′ ″, R ″ ", R '""andR""" are the same or different and each represents a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and 7 to 7 carbon atoms. It can be selected from the group consisting of 12 aralkyl groups.

  Examples of the saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, sec-butyl group, t-butyl group, and pentyl. And alkyl groups such as a hexyl group. Examples of the alicyclic hydrocarbon group having 5 to 12 carbon atoms include cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group and phenethyl group.

Moreover, R <^17> , R <^18> , R <^19> , R <^20> , R <^21> and R < ²² > are the same or different and are a C1-C30 saturated or unsaturated aliphatic hydrocarbon group, C5-C12 alicyclic ring It can be selected from the group consisting of a formula hydrocarbon group, an alkoxy group having 1 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 30 carbon atoms.

  Examples of the saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, sec-butyl group, and t-butyl. Group, alkyl group such as pentyl group and hexyl group, alkenyl group such as vinyl group, allyl group and isopropenyl group, and alkynyl group such as ethynyl group, propynyl group and butynyl group. Examples of the alicyclic hydrocarbon group having 5 to 12 carbon atoms include cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. Examples of the aromatic hydrocarbon group having 6 to 30 carbon atoms include a phenyl group and a naphthyl group.

  Ar in the definition of the general formula (B) includes, for example, a phenylene group substituted or unsubstituted with one or more of the above alkyl groups. In addition, examples of the 5- or 6-membered ring in the definition of the general formula (B) include cyclopentane or cyclohexane substituted or unsubstituted with one or more of the above alkyl groups.

  More specifically, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, Pers such as 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane and 2,2-bis (t-butylperoxy) butane Oxyketal compounds, bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5- (t-butylperoxy) hexane, di-t-butyl peroxide, t -Dialkyl peroxide compounds represented by butylcumyl peroxide and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 It can be mentioned, and as the silyl peroxide compounds, bis trimethylsilyl peroxide, and the like bis dimethylphenylsilyl peroxide. Such a peroxide can be used individually by 1 type, or can be used in combination of 2 or more type.

  The amount of the organic peroxide as the component (4) is not particularly limited, but is preferably 0.00001-0.1 part by weight with respect to 100 parts by weight of the component (1). (4) When the added amount of the component is less than 0.00001 part by weight, the effect on photocurability is lowered, and sufficient photopatterning may not be obtained. On the other hand, if it exceeds 0.1 parts by weight, the weather resistance and thermal stability of the resulting cured product may be reduced. In view of the balance between the curability of the composition and the weather resistance and thermal stability of the resulting cured product, the amount of organic peroxide added is preferably 0.0001 to 0.01 part by weight.

  Although not bound by theory, in the curable silicone composition of the present invention, (3) the catalytic action of the platinum-based catalyst for promoting the hydrosilylation reaction is suppressed by (3) the platinum-based catalyst reaction inhibitor. However, it is considered that the suppression is lost by irradiation with a certain activation energy ray, and (2) the catalytic action of the platinum catalyst for promoting the hydrosilylation reaction is recovered. Specifically, the interaction between the (3) platinum-based catalyst reaction inhibitor and (2) the hydrosilylation-promoting platinum-based catalyst is lost by irradiation with a certain activation energy ray, or (3) The complex of the platinum-based catalyst reaction inhibitor and (2) the platinum catalyst for promoting the hydrosilylation reaction is decomposed to produce a highly active platinum-based catalyst, which promotes the hydrosilylation reaction of component (1). However, (1) the crosslinking of the component proceeds, and at the same time, (4) the organic peroxide is decomposed by light irradiation to generate radical active species, and the radical polymerization of vinyl group and SiH group proceeds.

Examples of the activation energy rays used for curing the composition of the present invention include visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, electron rays and γ rays, and particularly visible light and ultraviolet rays. Is preferred. The means for irradiating the activation energy ray 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. Specifically, the 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.

  In addition to the essential components (1) to (4) described above, the curable silicone composition of the present invention may include a photosensitizer, silica particles (inorganic filler), a polymer additive, and / or as required. An organic solvent can be further included.

(Photosensitizer)
The photosensitizer absorbs activation energy rays, particularly ultraviolet rays or visible rays, and transmits the absorbed energy to (2) a platinum-based catalyst for promoting hydrosilylation reaction and / or (3) a reaction inhibitor for platinum-based catalyst. And (2) activating the platinum catalyst for promoting the hydrosilylation reaction.

  As the photosensitizer, any substance having an action of absorbing the activation energy rays and activating the platinum catalyst for promoting the hydrosilylation reaction (2) can be used. Preferred are aromatic compounds or aromatic compounds having a ketone chromophore. Examples of the polycyclic aromatic compound include anthracene and derivatives thereof, pyrene and derivatives thereof, and perylene and derivatives thereof. Examples of aromatic compounds having a ketone chromophore include acetophenone, benzophenone, 2-isopropylthioxanthone, diethylthioxanthone and thioxanthone derivatives; anthraquinone, bromoanthraquinone and anthraquinone derivatives; anthracene, bromoanthracene and anthracene derivatives; perylene and perylene derivatives; Examples include thioxanthene and thioxanthene derivatives; coumarin and ketocoumarin. More preferred photosensitizers are diethyl thioxanthone and bromoanthracene.

  The blending amount of the photosensitizer can be set in an arbitrary range as long as the object and effect of the present invention are not impaired. Typically, it is 0.001 to 5% by weight of the entire composition, particularly 0.01 to It is in the range of 1% by weight.

(Silica particles)
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. Further, the shape of the silica particles is not particularly limited, but is preferably at least one shape selected from the group consisting of a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, and an indefinite shape. However, in order to make the dispersibility better, it is preferable to use spherical silica particles. The average particle size of the silica particles is preferably 0.001 to 20 μm, but the average particle size is preferably 0.001 to 0.2 μm, more preferably 0.001 to 0, particularly from the viewpoint of forming a transparent cured film. 0.01 μm.

  The usage form of the silica particles is not particularly limited. For example, the silica particles can be used in a dry state or a state dispersed in water or an organic solvent. In particular, a dispersion of finely divided silica particles known as colloidal silica can be used directly, and since particularly high transparency is obtained, the use of colloidal silica is preferred. When the colloidal silica dispersion medium is water, the pH is preferably 2 to 13, and more preferably 3 to 7. When the colloidal silica dispersion medium 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. can be used. Preferred organic solvents are methanol, isopropyl alcohol, methyl ethyl ketone, xylene and the like. In addition, you may use the organic solvent which forms a homogeneous system, or a mixed solvent with water as a dispersion medium of colloidal silica.

  By blending the silica particles, shrinkage of the film obtained by curing the silicone composition can be reduced. The blending amount of the silica particles is not particularly limited, but is preferably 10 to 250 parts by weight, for example, 20 to 200 parts by weight, and more preferably 30 to 150 parts by weight with respect to 100 parts by weight of the components (1) to (4). preferable.

(Organic solvent)
The curable silicone composition of the present invention preferably contains a specific organic solvent if 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. Further, the organic solvent can be used as a developer after irradiation with activation energy rays.

  As an organic solvent, an ether organic solvent, an ester organic solvent, a ketone organic solvent, a hydrocarbon organic solvent, an alcohol organic solvent, a nitrogen-containing solvent, a sulfur-containing solvent, and a siloxane organic solvent are used. Although at least one can be selected from the group, usually an organic solvent having a boiling point of 50 to 200 ° C. under atmospheric pressure and capable of uniformly dissolving each component is preferable.

Specific examples of such organic solvents include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, 2,2,4-trimethylpentane, octane, cyclohexane, and methylcyclohexane; benzene, toluene, xylene Aromatic hydrocarbon solvents such as ethylbenzene, n-amylnaphthalene, trimethylbenzene; methanol, ethanol, n-propanol, phenol, cyclohexanol, benzyl alcohol, methylphenylcarbinol, diacetone alcohol, cresol, etc. Monoalcohol solvents: polyhydric alcohol solvents such as ethylene glycol, 1,2-propylene glycol, diethylene glycol, glycerin; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, methyl amyl Tone, trimethylnonanone, cyclohexanone, acetonylacetone, acetophenone, fenchon and other ketone solvents; ethyl ether, isopropyl ether, ethylene oxide, 1,4-dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ether solvents such as diethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, γ-butyrolactone, n-propyl acetate, ethyl acetoacetate, ethylene glycol monomethyl ester, Diethyl oxalate, methyl lactate, ethyl lactate, diethyl malonate, dimethyl phthalate, phthalic acid Ester solvents such as diethyl; nitrogen-containing solvents such as N-methylformamide, acetamide and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide (DMSO) and sulfolane; octamethylcyclo Tetrasiloxane, hexamethyldisiloxane, 1,3-divinyldimethylphenyldisiloxane, 1,5-divinyltetramethyldiphenyltrisiloxane, phenyltris (dimethylvinylsiloxy) silane, (PhSiO _3/2 ) and (Me ₂ ViSiO ₁ One or a combination of two or more siloxane-based organic solvents such as methyl vinyl phenyl siloxane oligomer consisting of _{/ 2} ).

  The type of the organic solvent may be selected in consideration of the application method of the curable silicone composition. For example, when a spin coating method is used because a thin film having a uniform thickness can be easily obtained, examples of the organic solvent used include glycol ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether; ethyl cellosolve acetate Ethylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; esters such as ethyl lactate and ethyl 2-hydroxypropionate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether Methyl isobutyl ketone, 2-heptanone, cyclohexanone and me Ketones are preferred, such as Ruamiruketon, especially ethyl cellosolve acetate, propylene glycol methyl ether acetate, ethyl lactate, methyl isobutyl ketone and methyl amyl ketone preferred.

  The amount of the organic solvent can be set in an arbitrary range as long as the object and effect of the present invention are not impaired.

  In addition to the photosensitizer, silica particles (inorganic filler), polymer additive and / or organic solvent, the curable silicone composition of the present invention is within the range that does not impair the purpose and effect of the present invention. Alternatively, reactive diluents, titanium oxide, leveling agents, wettability improvers, surfactants, plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, silane coupling agents, etc. Additives can be included.

  The curable silicone composition of the present invention can be produced by mixing the essential components (1) to (4) above and, if necessary, the optional components described above using conventional means in the art. it can.

  The curable silicone composition of the present invention has a property of being cured by irradiation with activation energy rays. Therefore, various negative patterns can be formed by using the curable silicone composition of the present invention as a negative photosensitive composition.

  The negative pattern is formed by applying the curable silicone composition of the present invention on a substrate to form a silicone layer, selectively irradiating the silicone layer with activation energy rays, and removing non-irradiated portions of the silicone layer. Can be formed.

  As the substrate, any substrate can be used as long as it has properties such as strength, durability and flexibility necessary for the intended application.

  Examples of the substrate include conductors represented by various metals such as aluminum, zinc, copper, stainless steel, and iron; semiconductors represented by silicon, gallium arsenide compounds, etc .; synthetic resins such as polyethylene terephthalate, polycarbonate, polyvinyl acetal, and polyethylene Or an insulator typified by glass; a paper in which a synthetic resin is melt-coated or a synthetic resin solution is applied; a multilayer substrate in which a conductor layer or a semiconductor layer is provided on a synthetic resin film or glass by a technique such as vacuum deposition or lamination It is done. Of these, a substrate made of silicon and glass is preferable.

  The substrate may be surface-treated for the purpose of improving adhesion to the silicone layer. Such surface treatment depends on the material of the substrate, but examples thereof include brush polishing, ball polishing, electrolytic etching, chemical etching, surface roughening such as liquid honing, sandblasting, and combinations thereof. It is done.

  As a means for applying the curable silicone composition of the present invention on a substrate, a spin coating method, a dipping method, a spray method, a bar coating method, a roll coating method, a curtain coating method, a clavier printing method, a silk screen method, or an ink jet method. Etc. can be used. Among these, it is preferable to use a spin coating method because a coating film having a uniform thickness can be obtained. The thickness of the coating film can be adjusted to 0.1 to 200 μm by adjusting the viscosity of the curable silicone composition using the spin speed, time, organic solvent, and the like. Next, this coating film is dried at 40 to 120 ° C., and the temperature is increased or decreased as necessary, thereby heating for 0 to 5 minutes to form a silicone layer.

  As a method of selectively irradiating the activation energy rays to the silicone layer, for example, the activation energy rays are irradiated to the silicone layer through a photomask having transparency only to a portion corresponding to a predetermined pattern, or For example, a method of directly irradiating activation energy rays only on a predetermined pattern forming portion of the silicone layer using a laser can be mentioned.

  The latent image formed on the silicone layer by irradiation with activation energy rays along a predetermined pattern can be developed by removing the non-irradiated portion of the silicone layer. Various developers can be used to remove the non-irradiated portion, but it is preferable to dissolve and remove the uncured silicone layer of the non-irradiated portion with an organic solvent as described above.

  In addition, it is preferable to raise the intensity | strength of the formed pattern by raising the temperature further as needed at 40-250 degreeC after image development, and heating for 1 to 30 minutes.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. Below, the structure or characteristic of the use component in a table | surface is as follows, respectively.

(1a) Component: Organopolysiloxane having an alkenyl group bonded to a silicon atom 1) Siloxane polymer 1: Vinyl content 1.2 w%
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

(1a) Component: Organohydrogenpolysiloxane having a hydrogen atom bonded to a silicon atom 1) Crosslinking agent 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

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

(2) Component: Platinum catalyst for promoting hydrosilylation reaction 1) Pt: Platinum diluted with toluene as a complex compound of divinyltetramethyldisiloxane and platinum (II) chloride by the production method described in US Pat. No. 5,175,325 1.9w% solution as metal

(3) Component: Reaction inhibitor for platinum catalyst Reaction inhibitor 1: 1-ethynyl-1-cyclohexanol.
Reaction inhibitor 2: Methyl-tris (3-methyl-1-butyne-3-oxo) silane

(4) Component: Organic peroxide 1): An alcohol solution of dicumyl peroxide having a structure of (C ₆ H ₅ (CH ₃ ) ₂ COOC (CH ₃ ) ₂ C ₆ H ₅ ) (solid content 20 weight%)
2) of 2,5-dimethyl-2,5-bis (t-butylpaoxy) hexyne-3 having the structure of (CH ₃ ) ₃ COOC (CH ₃ ) ₂ CC (CH ₃ ) ₂ COOC (CH ₃ ) ₃ ) Alcohol solution (solid content 20% by weight)

Solvent: Toluene

Photosensitizer: Anthracene

(Examples 1-7)
(1a) Siloxane polymers 1 to 3 corresponding to component, crosslinking agents 1 to 4, (1b) Siloxane polymer 4 corresponding to component, (2) Pt corresponding to component, Reaction inhibitor 1 corresponding to (3) component The curable silicone compositions of Examples 1 to 7 were prepared by mixing the peroxides 1 to 2 corresponding to the components (2) and (4), the photosensitizer and the solvent in the proportions shown in Table 1 below. did.

(Comparative Examples 1-2)
As Comparative Example 1, the same curable silicone composition as in Example 1 was prepared except that the reaction inhibitor 1 was not included. Furthermore, as Comparative Example 2, a curable silicone composition identical to that of Example 1 was prepared except that peroxide 1 was not included.

  The composition of Comparative Example 1 had poor storage stability at room temperature, and curing proceeded within 30 minutes. On the other hand, the composition of Example 1-7 showed storage stability of 3 hours or more at room temperature.

(Pattern formation)
Spin coating was performed on a silicon wafer having a diameter of 10.2 cm at 500 rpm for 10 seconds and at 2000 rpm for 30 seconds to obtain respective coating films of the compositions of Example 1-7 and Comparative Example 1-2. Next, a photomask having a pattern with a line width of 10 to 200 μm was applied, and a pattern was irradiated using a low-pressure mercury lamp (ultraviolet light having a wavelength of 254 to 360 nm) at the dose shown in Table 2, and the temperature After-heating with time. Thereafter, the non-irradiated portion was removed with a toluene solution and development was performed to obtain a negative patterned film. In Examples 3 to 7, preheating was performed at the temperature and time shown in Table 2 before the pattern irradiation. The obtained pattern line width results are also shown in Table 2.

  As is clear from Table 2, in Example 1-7, a highly accurate pattern could be obtained. In Example 4, since the used composition contains a photosensitizer, a highly accurate pattern can be obtained even if the amount of light required is small compared to the composition 3 that does not contain a photosensitizer. did it.

In Comparative Examples 1 and 2, which lacked the reaction inhibitor 1 and the peroxide 1 as compared with Example 1, a highly accurate pattern was not obtained.

Claims (5)

(1) The following:
(A) an organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule, and an organohydrogenpolysiloxane or hydrosilane compound having at least two hydrogen atoms bonded to a silicon atom in one molecule; A mixture of these, and
(B) at least one selected from the group consisting of an organopolysiloxane having an alkenyl group bonded to a silicon atom and a hydrogen atom bonded to a silicon atom in the same molecule;
(2) platinum catalyst for promoting hydrosilylation reaction,
(3) a reaction inhibitor for platinum catalyst, and
(4) (A) General formula:
R ¹ R ² R ³ COOCR ⁴ R ⁵ R ⁶
(Where
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom or an organic group having 1 to 30 carbon atoms)
(B) General formula:
R ⁷ R ⁸ R ⁹ COO-X-OOCR ¹⁰ R ¹¹ R ¹²
[Where,
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same or different and each represents a hydrogen atom or an organic group having 1 to 30 carbon atoms,
X is-(CR'R ") _k -,-(CR'R") _l -CR '"" = CR """-(CR'" R "") _m -,-(CR'R ") _{n -C≡C- (CR '"R"}") o - and _{- (CR'R") p -Ar- (} CR'"R"") q -
(Where
k is an integer of 1 or more, and l, m, n, o, p, and q are each independently 0 or an integer of 1 or more,
R ', R ", R'", R "", R '"" and R """are the same or different and each represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, or adjacent carbons. Form a 5- or 6-membered ring with or without substituents with the atoms;
Ar represents an arylene group with or without a substituent)
Represents a divalent organic group selected from the group consisting of
And (C) the general formula:
R ¹⁷ R ¹⁸ R ¹⁹ SiOOSiR ²⁰ R ²¹ R ²²
(Where
R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are the same or different and each represents an organic group having 1 to 30 carbon atoms). Ultraviolet ray, X-ray, α-ray, β-ray, electron beam or γ-ray curable silicone composition containing a product. The curability according to claim 1, further comprising a photosensitizer that absorbs ultraviolet rays, X-rays, α-rays, β-rays, electron rays or γ-rays and activates (2) a platinum catalyst for promoting hydrosilylation reaction. Silicone composition. The curable silicone composition according to claim 2, wherein the photosensitizer is a polycyclic aromatic compound or an aromatic compound having a ketone chromophore. A curable silicone composition according to any one of claims 1 to 3 is applied on a substrate to form a silicone layer,
The silicone layer is selectively irradiated with ultraviolet rays, X rays, α rays, β rays, electron rays or γ rays ,
A negative pattern forming method comprising removing a non-irradiated portion of the silicone layer.   The negative pattern formation method of Claim 4 which improves the intensity | strength of the formed pattern by further heating after removing the non-irradiation part of the said silicone layer.