JP3295539B2 - Method of forming cured silicone - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a cured silicone product, and more particularly, to a method for forming a cured silicone material capable of curing only a part of an addition-curable silicone composition.

[0002]

2. Description of the Related Art An organopolysiloxane having at least two silicon-bonded alkenyl groups in one molecule, an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, and a catalyst for hydrosilylation reaction. Examples of the method of curing the addition reaction-curable silicone composition to form a silicone cured product include a method of heating the composition, a method of irradiating the composition with ultraviolet light, or a method of irradiating the composition with ultraviolet light. And a method of heating an object (see JP-A-60-177929 and JP-A-61-162561).

[0003]

However, it is difficult to cure only a part of the addition-curable silicone composition by the method of heating the addition-curable silicone composition. It was even more difficult to do. Also, it was difficult to cure only a part of the composition by the methods disclosed in JP-A-60-177029 and JP-A-61-162561.

The present inventors have conducted intensive studies on the above-mentioned problems and found that the addition-curable silicone composition having a silicon-bonded aryl group has a total irradiation amount of at least 0.1.
By irradiating with ultraviolet rays of J / cm ² , it was found that the composition was no longer cured by heating or the curability was significantly reduced, and the present invention was reached. That is, an object of the present invention is to provide a method for forming a cured silicone product that can cure only a part of the addition reaction-curable silicone composition.

[0005]

Means for Solving the Problems and Action Thereof One of the formation methods of the present invention is that a part of an addition-curable silicone composition having a silicon-bonded aryl group has a total irradiation amount of at least 0.1 J / cm ^2. After irradiating the composition with ultraviolet light, the composition is heated so that the total irradiation amount of the composition and / or ultraviolet light in the unirradiated part is 0.1 J / cm ^2.
Curing only the UV-irradiated portion of the composition which is less than the UV-irradiated portion, and another forming method of the present invention provides a method for curing a portion of an addition-reaction-curable silicone composition having a silicon-bonded aryl group in a total irradiation amount. Is at least 0.1 J / c
By heating the composition while irradiating ultraviolet rays of m ^{2, only} the composition of the ultraviolet ray non-irradiated portion and / or the ultraviolet ray-irradiated portion whose total amount of ultraviolet radiation is less than 0.1 J / cm ² Is cured. Hereinafter, the method for forming the silicone cured product of the present invention will be described in detail.

It is essential that the addition reaction-curable silicone composition that can be used in the formation method of the present invention has a silicon-bonded aryl group. Examples of such an addition reaction-curable silicone composition include (A) an organopolysiloxane having at least two silicon-bonded alkenyl groups in one molecule, and (B) at least two silicon atoms in one molecule. An addition reaction-curable silicone composition comprising an organopolysiloxane having a bonded hydrogen atom and a catalyst for a hydrosilylation reaction in a catalytic amount, wherein at least one of the component (A) and the component (B) has a silicon-bonded aryl group. In the case where none of the above components (A) and (B) has a silicon-bonded aryl group,
In addition to the addition reaction-curable silicone composition,
(D) An addition reaction-curable silicone composition comprising an organosilicon compound having a silicon-bonded aryl group is included.

The organopolysiloxane of the component (A) must have at least two silicon-bonded alkenyl groups in one molecule. As the silicon-bonded alkenyl group in the component (A), for example, a vinyl group, an allyl group,
Examples thereof include a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group, and a vinyl group is particularly preferable. The bonding position of the alkenyl group in the component (A) is not particularly limited.
Molecular chain ends and / or molecular chain side chains are included.
As the silicon-bonded organic group other than the alkenyl group in the component (A), for example, a methyl group, an ethyl group, a propyl group,
Alkyl groups such as butyl group, pentyl group, hexyl group and heptyl group; aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group; aralkyl groups such as benzyl group and phenethyl group; chloromethyl group and 3-chloropropyl Group,
Examples include a halo-substituted alkyl group such as a 3,3,3-trifluoropropyl group, and a methyl group and a phenyl group are particularly preferable. The molecular structure of the component (A) is not particularly limited, and includes, for example, linear, branched, cyclic, net-like, and partially branched linear chains. Particularly, since the obtained silicone cured product becomes elastomeric. Requires that at least one of the components (A) and (B) be linear. In the forming method of the present invention, the viscosity of the component (A) at 25 ° C is not particularly limited, but is preferably in the range of 1 to 500,000 centipoise, and more preferably 5 to 10 centipoise.
It is in the range of 000 centipoise. This is (A)
If the viscosity of the component at 25 ° C. is less than 1 centipoise, the mechanical strength of the resulting cured silicone product is significantly reduced. If it exceeds 500,000 centipoise, the resulting addition-curable silicone composition This is because the workability of handling the material is significantly reduced.

The organopolysiloxane of the component (A) includes, for example, a dimethylsiloxane / methylvinylsiloxane copolymer having a trimethylsiloxy group at both ends of a molecular chain,
Methyl vinyl polysiloxane blocked with trimethylsiloxy group at both ends of molecular chain, dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer blocked at both ends of molecular chain, dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of molecular chain, molecular chain Methylvinylpolysiloxane with dimethylvinylsiloxy groups at both ends, dimethylsiloxane / methylvinylsiloxane copolymer with dimethylvinylsiloxy groups at both ends, dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane with dimethylvinylsiloxy groups at both ends copolymer, wherein: the siloxane units of the formula R ¹ ₃ SiO _1/2: siloxane units represented by the formula R ^{1 ₂} R ₂ SiO _1/2: Oruganopo consisting of siloxane units represented by SiO _4/2 Polysiloxane copolymer, R ^{1 ₂} R ₂ S
An organopolysiloxane copolymer comprising a siloxane unit represented by iO _1/2 and a siloxane unit represented by SiO _4/2 , a siloxane unit represented by the formula: R ¹ R ² SiO _2/2 and a formula: R ¹ SiO ₃ Siloxane unit represented by _{/ 2} or R
Examples thereof include an organopolysiloxane copolymer comprising a siloxane unit represented by ² SiO _3/2 and a mixture of two or more of these organopolysiloxanes. Where R
¹ is a monovalent hydrocarbon group other than an alkenyl group, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group; a phenyl group, a tolyl group, a xylyl group, Aryl groups such as a naphthyl group; aralkyl groups such as a benzyl group and a phenethyl group; and halo-substituted alkyl groups such as a chloromethyl group, a 3-chloropropyl group and a 3,3,3-trifluoropropyl group. In the above formula, R ² is an alkenyl group, for example, a vinyl group, an allyl group, a butenyl group, a pentenyl group,
A hexenyl group and a heptenyl group are exemplified.

The organopolysiloxane of the component (B) must have at least two silicon-bonded hydrogen atoms in one molecule. The bonding position of the silicon-bonded hydrogen atom in the component (B) is not particularly limited, and examples thereof include a molecular chain terminal and / or a molecular chain side chain. As the silicon-bonded organic group in the component (B), for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group; a phenyl group, a tolyl group, a xylyl group, Aryl groups such as naphthyl group; aralkyl groups such as benzyl group and phenethyl group; chloromethyl group;
Examples include a halo-substituted alkyl group such as a 3-chloropropyl group and a 3,3,3-trifluoropropyl group, and a methyl group and a phenyl group are particularly preferable. The molecular structure of the component (B) is not particularly limited, and includes, for example, linear, branched, cyclic, net-like, and partially branched linear chains. Particularly, since the obtained silicone cured product becomes elastomeric. It is preferable that at least one of the component (A) and the component (B) is linear. In the forming method of the present invention, 25% of the component (B)
Although the viscosity at ° C is not particularly limited,
It is within the range of ５００500,000 centipoise, and more preferably within the range of 5１００100,000 centipoise. This is because if the viscosity of the component (B) at 25 ° C. is less than 1 centipoise, the mechanical strength of the obtained cured silicone product is significantly reduced, and if it exceeds 500,000 centipoise. This is because the handling efficiency of the addition reaction-curable silicone composition is significantly reduced.

Examples of the organopolysiloxane of the component (B) include, for example, methylhydrogenpolysiloxane having a trimethylsiloxy group at both ends of a molecular chain, and dimethylsiloxane having a trimethylsiloxy group at both ends of a molecular chain.
Methyl hydrogen siloxane copolymer, molecular chain terminal trimethylsiloxy group-blocked dimethyl siloxane / methyl hydrogen siloxane / methyl phenyl siloxane copolymer, molecular chain terminal dimethyl hydrogen siloxy group-blocked dimethyl polysiloxane, molecular chain terminal dimethyl hydrogen siloxy group dimethylsiloxane-methylphenylsiloxane copolymers, both molecular terminals with dimethylhydrogensiloxy groups at methylphenyl polysiloxane, formula siloxane units of the formula _{^{R 1 3 SiO 1/2: R 1}} 2 siloxane units of the formula HSiO _1/2: organopolysiloxane copolymers composed of siloxane units represented by SiO _4/2, represented by siloxane units and SiO _4/2 represented by R ¹ ₂ HSiO _1/2 O consisting of siloxane units Ganoderma polysiloxane copolymer,
The siloxane unit represented by the formula: R ¹ HSiO _2/2 and the formula: R
¹ Siloxane unit represented by SiO _3/2 or HSiO
Examples thereof include an organopolysiloxane copolymer comprising a siloxane unit represented by _3/2 , and a mixture of two or more of these organopolysiloxanes. In the formula, R ¹ is a monovalent hydrocarbon group other than an alkenyl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group,
Alkyl groups such as hexyl group and heptyl group; phenyl group,
Aryl groups such as tolyl, xylyl and naphthyl groups; aralkyl groups such as benzyl group and phenethyl group; and halo-substituted alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group. No.

In the above composition, the amount of the component (B) is not particularly limited, but the amount of the silicon-bonded hydrogen atom in the component (B) per mole of the silicon-bonded alkenyl group in the component (A) is one. The amount is preferably in the range of 0.1 to 10 mol. This is because when the amount of the silicon-bonded hydrogen atom in the component (B) is less than 0.1 mole relative to 1 mole of the silicon-bonded alkenyl group in the component (A), the unirradiated portion and / or the total This is because the addition reaction-curable silicone composition in the UV-irradiated portion where the irradiation amount is less than 0.1 J / cm ² is not sufficiently cured by heating. This is because physical properties change over time.

The catalyst for hydrosilylation reaction of the component (C) has a UV-irradiated portion and / or a total UV irradiation dose of 0.5.
It is a catalyst for curing the addition reaction-curable silicone composition of the ultraviolet ray irradiated portion, which is less than 1 J / cm ² , by heating. As the catalyst for the hydrosilylation reaction of the component (C),
For example, a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst can be mentioned, and a platinum-based catalyst is particularly preferable. Examples of the platinum-based catalyst include platinum fine powder, platinum black, fine silica powder carrying platinum, activated carbon carrying platinum, chloroplatinic acid, platinum tetrachloride, an alcohol solution of chloroplatinic acid, and a complex of platinum and an olefin. A complex of platinum and an alkenyl siloxane such as divinyltetramethyldisiloxane, a polystyrene resin, a nylon resin, an acrylic resin, a polycarbonate resin, a silicone resin or the like containing these platinum or a platinum-based compound having a particle diameter of less than 10 μm. Thermoplastic resin powder;

In the above composition, the amount of the component (C) is a catalytic amount. Specifically, in the addition-reaction-curable silicone composition, the content of the metal in the component (C) is expressed in weight units. The amount is preferably in the range of 0.1 to 1000 ppm, and more preferably in the range of 1 to 500 ppm. This is because, in the addition reaction-curable silicone composition, when the content of the metal in the component (C) is less than 0.1 ppm by weight, the curing rate of the obtained composition is significantly reduced. And this is 1
This is because if it exceeds 000 ppm, it is uneconomical.

The addition reaction-curable silicone composition which can be used in the formation method of the present invention comprises the above-mentioned component (A) and
It is necessary that at least one of the components (B) has a silicon-bonded aryl group, but when neither the component (A) nor the component (B) has a silicon-bonded aryl group, the above composition It is necessary to further blend (D) an organosilicon compound having a silicon-bonded aryl group to the product. Even when at least one of the components (A) and (B) has a silicon-bonded aryl group, the component (D) can be added in order to further enhance the effects of the present invention. Examples of the organosilicon compound (D) include silanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, phenyltrimethylsilane, and diphenyldimethylsilane. Compounds: Tetramethyldiphenyldisiloxane, pentamethylphenyldisiloxane, methylphenylsiloxane oligomer having both ends of molecular chain trimethylsiloxy group, methylphenylsiloxane oligomer having both ends of hydroxyl group, and dimethylsiloxane oligomer having both ends of molecular chain dimethylphenylsiloxy group Organosiloxane oligomers such as trimethylsiloxy group-blocked methyl phenyl siloxane polymer at both ends of molecular chain, hydroxyl-blocked methyl group at both ends of molecular chain Phenyl siloxane polymers, organopolysiloxanes such as dimethylpolysiloxane with both molecular chain terminals phenyl siloxy group-blocked dimethylsiloxane polymer.

In the above composition, the amount of the component (D) is preferably in the range of 0.1 to 1000 parts by weight based on 100 parts by weight of the component (A). This is because when neither the component (A) nor the component (B) has a silicon-bonded aryl group, the amount of the component (D) is less than 0.1 part by weight based on 100 parts by weight of the component (A). If not, the object of the present invention cannot be achieved, and if it exceeds 1000 parts by weight, the ultraviolet irradiation where the ultraviolet irradiation is not irradiated and / or the total irradiation amount of the ultraviolet is less than 0.1 J / cm ^2. This is because the addition reaction-curable silicone composition at a portion cannot be sufficiently cured.

[0016] The addition reaction-curable silicone composition which can be used in the forming method of the present invention includes, as other optional components, storage stability and handling of the composition as long as the object of the present invention is not impaired. A curing inhibitor for improving the properties can be blended. As the curing inhibitor, for example, 3-methyl-1-butyn-3-ol,
Alkyne alcohols such as 3,5-dimethyl-1-hexyn-3-ol and phenylbutynol; 3-methyl-3
Enein compounds such as -penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane; 1,3,5,7-tetramethyl-1,
3,5,7-tetrahexenylcyclotetrasiloxane and benzotriazole.

Further, the addition reaction-curable silicone composition which can be used in the formation method of the present invention contains, as long as the object of the present invention is not impaired, other optional components such as tetramethoxysilane, tetraethoxysilane, and the like. Dimethyldimethoxysilane, methyltrimethoxysilane,
Methyltriethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane,
3-methacryloxypropyltrimethoxysilane, 3-
Adhesives such as aminopropyltrimethoxysilane, 3- (2-aminoethyl) -aminopropyltrimethoxysilane, hexamethoxydisilylethane, hexamethoxydisilylpropane; fumed silica, precipitated silica, titanium dioxide, carbon Inorganic fillers such as black, alumina, quartz powder and the like, and inorganic fillers obtained by surface-treating these inorganic fillers with organosilicon compounds such as organoalkoxysilanes, organochlorosilanes and organosilazanes; acetophenone, benzophenone, trimethylsilylated benzophenone , Propiophenone, 3-methylacetophenone, 4-methylacetophenone, benzoin ethyl ether, (4-isopropyl) phenyl-1-hydroxy-isopropylketone,
Photosensitizers such as 4-allylacetophenone, 3-benzylacetophenone, 4-methoxybenzophenone, triphenylamine and azoisobutyronitrile can be blended.

In the forming method of the present invention, first, a part of the addition reaction-curable silicone composition having a silicon-bonded aryl group is irradiated with ultraviolet rays. In order to irradiate the addition reaction-curable silicone composition with ultraviolet light, the composition may be applied to a base material such as glass, ceramic, copper, iron, aluminum, silicon, and plastic. preferable. Further, in the forming method of the present invention, it is necessary to irradiate ultraviolet rays so that the total irradiation amount is at least 0.1 J / cm ² . This is disclosed in
As in the examples described in JP-A-177029 and JP-A-61-162561, addition-curable silicone compositions having a silicon-bonded aryl group have a total irradiation amount of less than 0.1 J / cm ^2. Irradiation of UV light,
The UV irradiation part and / or the total irradiation amount of UV light is 0.
This is because the curability of the composition in an ultraviolet-irradiated portion of less than 1 J / cm ² cannot be significantly reduced, and the object of the present invention cannot be achieved. The total irradiation amount of the ultraviolet rays can be obtained by an ultraviolet illuminometer. The method of irradiating a part of the addition reaction-curable silicone composition with ultraviolet light is not particularly limited. For example, a method of irradiating through a plate partially shielding ultraviolet light, preferably, a pattern is formed so as to shield ultraviolet light. And a method of irradiating only an arbitrary portion of the composition with an ultraviolet ray using an ultraviolet spotlight irradiating apparatus.

The light source capable of irradiating the ultraviolet light which can be used in the forming method of the present invention is not particularly limited. Examples thereof include a hydrogen discharge tube, a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a xenon lamp, and a chemical. Lamps and carbon arc lamps. In the forming method of the present invention, the wavelength of the ultraviolet light is not particularly limited, particularly,
Ultraviolet light having a wavelength in the range of 250 to 400 nm is preferred. In the formation method of the present invention, the conditions for irradiating the addition reaction-curable silicone composition with ultraviolet light are not particularly limited. For example, a method of irradiating the composition with ultraviolet light under cooling, at room temperature or under heating, Irradiation may be performed in an atmosphere of an inert gas such as a gas or an argon gas, in air, or under vacuum. When irradiating the addition reaction-curable silicone composition with ultraviolet light while heating, it is necessary to take care not to cure the composition before the total irradiation amount becomes at least 0.1 J / cm ^2. For this purpose, a sufficient amount of a curing inhibitor is incorporated into the composition, or the total irradiation amount of ultraviolet rays is at least 0.1% before the composition is cured by heat.
It is necessary to irradiate quickly so as to be J / cm ² . In the formation method of the present invention, the addition reaction-curable silicone composition is heated while irradiating ultraviolet rays, and after irradiating the ultraviolet rays, is continuously heated, so that the ultraviolet ray non-irradiated portion and / or the total amount of ultraviolet rays is 0.1 J. / Cm ² can cure only the composition at the UV-irradiated portion.

Subsequently, the UV-irradiated addition-curable silicone composition is heated so that the UV-irradiated portion and / or the total UV irradiation amount is 0.1 J / cm ^2.
Only the UV-irradiated portion of the composition which is less than the above can be cured. The heating conditions are not particularly limited, and for example, heating is preferably performed in a temperature range of 50 to 250 ° C, and more preferably in a temperature range of 100 to 150 ° C. Further, in order to heat the addition reaction-curable silicone composition, for example, a heating device such as an infrared irradiation device and a hot air circulation oven can be used.

In this way, only the addition-curable silicone composition in the UV-irradiated portion and / or the UV-irradiated portion having a total UV irradiation amount of less than 0.1 J / cm ² is cured by heating, and then cured. The cured silicone composition can be developed by removing the cured composition with an organic solvent or the like. The organic solvent that can be used is not particularly limited as long as it can sufficiently dissolve the addition reaction-curable silicone composition, and examples thereof include toluene, xylene, methyl isobutyl ketone, acetone, methyl ethyl ketone, hexane, heptane, octane, and isopropyl acetate. Butyl acetate and isoamyl acetate.

According to the forming method of the present invention, it is possible to form a patterned silicone cured product.
For example, the present invention can be applied to a printing technique, and further can be used as a method for forming an insulating layer by a photolithography technique in manufacturing a semiconductor device or a pattern forming method by a two-layer resist method.

[0023]

EXAMPLES The method for forming a cured silicone product of the present invention will be described in detail with reference to examples. In the examples, the value of the viscosity is a value measured at 25 ° C.

[Reference Example 1] 100 parts by weight of a dimethylsiloxane-methylphenylsiloxane copolymer (vinyl group content = 0.24% by weight) having a dimethylvinylsiloxy group at both ends of a molecular chain having a viscosity of 2,000 centipoise, specific surface area Is a methylhydrogensiloxane / dimethylsiloxane copolymer capped with trimethylsiloxy groups at both ends of molecular chains having a viscosity of 5 centipoise and 10 m parts of fumed silica of 200 m ² / g (silicon-bonded hydrogen atom content = 0.75
2.3% by weight of chloroplatinic acid and 1,1,3,3-
Complex with tetramethyl-1,3-divinyldisiloxane (In this composition, the content of platinum metal is 2.5 pp by weight.
m) and 0.1 part by weight of 3-methyl-1-butyn-3-ol were uniformly mixed to prepare an addition-curable silicone composition.

After the addition reaction-curable silicone composition is poured into an aluminum cup so as to have a thickness of 5 mm, ultraviolet light is applied by a 120 W / cm high-pressure mercury lamp so that the total irradiation amount is 1.3 J / cm ^2. Was irradiated. After irradiation with ultraviolet light, the surface of the composition was slightly thickened, but did not form a film, and the bottom of the composition was not even thickened. The composition is then added to 15
When heated in a hot air circulating oven at 0 ° C for 1 hour,
Although the surface of the composition was slightly thickened, it did not form a film, and the bottom of the composition was slightly thickened, but the composition was completely dissolved in toluene. .

Reference Example 2 The addition reaction-curable silicone composition prepared in Reference Example 1 was poured into an aluminum cup so as to have a thickness of 5 mm, and the total irradiation amount was reduced to 0 by a 120 W / cm high-pressure mercury lamp. Ultraviolet irradiation was performed so as to be 0.09 J / cm ² . After UV irradiation, the composition did not thicken at all. Next, when this composition was heated in a hot air circulating oven at 150 ° C. for 1 hour, although the surface had some tackiness, the whole was completely cured to form an elastomeric silicone cured product. The cured silicone did not dissolve in toluene.

Example 1 The addition reaction-curable silicone composition prepared in Reference Example 1 was applied on a glass plate to a thickness of 2 mm, and then applied through a patterned mask to 120 W.
/ Cm high-pressure mercury lamp, the total irradiation amount is 1.3 J / cm
^The sample was irradiated with ultraviolet rays so as to be ² . 15 after UV irradiation
The mixture was heated in a hot air circulating oven at 0 ° C. for 1 hour. Thereafter, when this glass plate was washed with toluene, only the portion of the composition which had not been irradiated with ultraviolet rays was cured, and the patterned silicone elastomer cured product was developed. The pattern of the cured silicone product faithfully reproduced the pattern of the mask used.

Example 2 The addition-reaction-curable silicone composition prepared in Reference Example 1 was applied on a glass plate to a thickness of 2 mm, and then applied through a patterned mask to 120 W.
/ Cm high-pressure mercury lamp, the total irradiation amount is 1.3 J / cm
It heated to 160 degreeC, irradiating ultraviolet rays so that it might become set to ^2, and after irradiating ultraviolet rays, it continued heating at 160 degreeC for 1 hour.
Thereafter, when this glass plate was washed with toluene, only the composition in the unirradiated portion of the ultraviolet ray was cured,
The patterned elastomeric silicone cured product was developed. The pattern of the cured silicone product faithfully reproduced the pattern of the mask used.

[Comparative Example 1] Dimethylvinylsiloxane-blocked dimethylpolysiloxane having both ends of a molecular chain having a viscosity of 2,000 centipoise (vinyl group content = 0.24% by weight)
00 parts by weight, 10 parts by weight of fumed silica having a specific surface area of 200 m ² / g, and a methyl hydrogen siloxane / dimethyl siloxane copolymer capped with trimethylsiloxy groups at both ends of a molecular chain having a viscosity of 5 centipoise (silicon-bonded hydrogen atom content = 2.3 parts by weight of a complex of chloroplatinic acid and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (in the present composition, the content of platinum metal is 2.5 ppm in units) and 3-methyl-
0.1 part by weight of 1-butyn-3-ol was uniformly mixed to prepare an addition-curable silicone composition.

After the addition reaction-curable silicone composition is applied on a glass plate to a thickness of 2 mm, it is applied with a high-pressure mercury lamp of 120 W / cm through a patterned mask.
Ultraviolet irradiation was performed so that the total irradiation amount was 0.09 J / cm ² . After the ultraviolet irradiation, the composition was heated for 1 hour in a hot air circulating oven at 150 ° C., whereby the entire composition was cured to form an elastomeric silicone cured product. The silicone cured product was washed with toluene, but the patterned silicone cured product could not be developed.

Comparative Example 2 (Methods of JP-A-60-177029 and JP-A-61-162561) Reference Example 1
Is applied on a glass plate to a thickness of 2 mm, and a total irradiation amount of 0.01 J / cm ² is applied by a high-pressure mercury lamp of 120 W / cm through a patterned mask. UV light was applied to obtain After the ultraviolet irradiation, the composition was heated for 1 hour in a hot air circulating oven at 150 ° C., whereby the entire composition was cured to form an elastomeric silicone cured product. The silicone cured product was washed with toluene, but the patterned silicone cured product could not be developed.

Example 3 Dimethylvinylsiloxane-endblocked dimethylpolysiloxane having a molecular weight of 2,000 centipoise at both ends of a dimethylvinylsiloxy group (vinyl content = 0.24% by weight)
00 parts by weight, 10 parts by weight of fumed silica having a specific surface area of 200 m ² / g, and a methyl hydrogen siloxane / dimethyl siloxane copolymer capped with trimethylsiloxy groups at both ends of a molecular chain having a viscosity of 5 centipoise (silicon-bonded hydrogen atom content = (0.75% by weight) 2.3 parts by weight, phenyltrimethoxysilane 12.5 parts by weight, chloroplatinic acid and 1,
Complexes with 1,3,3-tetramethyl-1,3-divinyldisiloxane (in the present composition, the content of platinum metal is 2.5 ppm by weight) and 3-methyl-1-butyne- 0.1 part by weight of 3-ol was uniformly mixed to prepare an addition reaction-curable silicone composition.

After applying the addition reaction-curable silicone composition to a thickness of 2 mm on a glass plate, a 120 W / cm high-pressure mercury lamp was applied through a patterned mask.
Ultraviolet irradiation was performed so that the total irradiation amount was 1.0 J / cm ² . After the irradiation with the ultraviolet rays, the mixture was heated in a hot air circulation oven at 150 ° C. for 1 hour. Thereafter, when this glass plate was washed with toluene, only the portion of the composition which had not been irradiated with ultraviolet rays was cured, and the patterned silicone elastomer cured product was developed. The pattern of the cured silicone product faithfully reproduced the pattern of the mask used.

[0034]

The method for forming a cured silicone product of the present invention has the characteristic that only a part of the addition reaction-curable silicone composition can be cured, and is useful as a method for forming a pattern using a cured silicone product. .

Continuation of the front page Examiner Eiichi Sawa (56) References JP-A-7-278328 (JP, A) JP-A-1-201337 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08J 3/00-3/28 C08J ^7/ 00-7/18

Claims (3)

(57) [Claims] 1. A part of an addition-reaction-curable silicone composition having a silicon-bonded aryl group is irradiated with an ultraviolet ray having a total irradiation amount of at least 0.1 J / cm ² , and the composition is heated so that the ultraviolet ray is not irradiated. A method for forming a cured silicone, comprising curing only the composition of the irradiated portion and / or the composition of the ultraviolet irradiated portion having a total irradiation amount of ultraviolet light of less than 0.1 J / cm ² . 2. A part of the addition reaction-curable silicone composition having a silicon-bonded aryl group is irradiated with ultraviolet rays having a total irradiation amount of at least 0.1 J / cm ² , thereby heating the composition to prevent irradiation with ultraviolet rays. A method of forming a cured silicone product, comprising curing only a portion of the composition and / or a portion of the ultraviolet ray irradiated with an ultraviolet ray having a total irradiation amount of less than 0.1 J / cm ² . 3. The method according to claim 1, wherein the addition reaction-curable silicone composition having a silicon-bonded aryl group is applied to a substrate, and then the total irradiation amount is at least 0.5 through a patterned mask.
A pattern-formed cured silicone characterized in that the composition is heated after irradiating with 1 J / cm ² ultraviolet rays or while irradiating the ultraviolet rays, thereby curing only the unexposed parts of the composition. Formation method.