JP2008081397A - Method of producing inorganic molded article, and inorganic molded article obtained by the method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method easily producing an inorganic molded article having an intended shape and dimensions, and excellent strength without occurrence of voluminal shrinkage in the production process, and an inorganic molded article obtained by the method. <P>SOLUTION: The method of producing the inorganic molded article composed of a matrix of an inorganic ceramics, and an inorganic filler dispersed in the matrix is characterized in that a solid silicone is turned into the inorganic ceramic by heating a silicone molded article composed of a matrix of the solid silicone, and the inorganic filler dispersed in the matrix in a non-oxidizing atmosphere at a temperature within the range of 400-1,500°C. The inorganic molded article obtained by the method is also provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing an inorganic molded body applicable to a ceramic circuit board, a dielectric ceramic composition, a refractory wire, a dielectric heating coil, an electric equipment insulating ring, an electronic packaging technology, and the like.

  In recent years, the demand for semiconductor technology is increasing due to the increasing demand for mobile phones, flat-screen TVs and the like. As a substrate for mounting a semiconductor, ceramic materials having excellent insulating properties and high thermal conductivity, such as alumina, silicon nitride, glass ceramic, and the like are being used. Among them, the usefulness of glass ceramics (Low Temperature Cofired Ceramics; LTCC) capable of low-temperature sintering that can simultaneously fire conductors with high electrical conductivity such as Ag, Cu, and Au is increasing.

  Further, as a method for producing a glass ceramic substrate by low-temperature firing, it is known that an organic binder resin such as polypropylene carbonate, alkyl methacrylate resin, or PVA is added to a ceramic raw material, and then molded and fired. In this method, a binder resin removing step is required, and at that time, the volume of the molded body is inevitably reduced, and the accompanying strength reduction is a problem.

  Patterning techniques that can be placed on a printed circuit board include lithography and printing methods using photoresist. Lithography methods require steps such as resist coating and removal, but printing methods that do not have such steps are more economical. Is advantageous.

  Thick film pastes that are materials for producing ceramics that can be sintered at low temperature are known (Patent Documents 1, 2, and 3), but organic compounds such as cellulose, PVA, polypropylene carbonate, and alkyl methacrylate are used. Since it is included as a binder, a binder removal step is required, and there is a problem that strength is insufficient due to volume reduction.

  Further, in the method of applying the thick film paste by printing such as screen printing, conventionally, the thick film paste flows between printing and drying, and so-called “sagging” is a problem.

  In Patent Document 4, a coating mainly composed of a silicone compound and a low-melting glass is applied at the time of winding a bare electric wire and the like, and after the winding, the silicon compound is decomposed and mineralized by firing and solidified by melting the low-melting glass. A method of forming an inorganic insulating layer by performing the above is described. More specifically, in the examples, a mixture containing a silicone resin and a low-melting glass powder was diluted with xylene, applied to a wound coil, then air-dried, the silicone resin was cured at 200 ° C., and then fired at 550 ° C. Has been done. Since the firing atmosphere is not described, it is considered that the firing is performed in air. In this method, organic groups are eliminated during firing, and strength is reduced due to volume reduction.

Japanese Patent Laid-Open No. 6-232515 JP-A-9-115331 JP 2004-59358 A JP-A-7-322579

  Therefore, the object of the present invention is to provide inorganic molding that hardly undergoes volume shrinkage during the manufacturing process, and therefore has the intended shape and dimensions, and the desired strength, and is useful as a conductor, dielectric, resistor, etc. It is providing the manufacturing method which can manufacture a body easily, and the inorganic molded object obtained by this method.

  As a result of repeated investigations to solve the above problems, the present inventors have developed an inorganic molded body comprising a matrix made of inorganic ceramics and an inorganic filler dispersed in the matrix, and a method for producing the same.

  That is, the present invention relates to a method for heating a silicone-based molded article comprising a matrix made of solid silicone and an inorganic filler dispersed in the matrix at 400 to 1500 ° C. in a non-oxidizing atmosphere, thereby making the solid silicone inorganic. The present invention provides a method for producing an inorganic molded body comprising a matrix made of inorganic ceramics and the inorganic filler dispersed in the matrix, characterized by being made into ceramics.

  Moreover, this invention provides the inorganic molded object which consists of the matrix which consists of inorganic ceramics obtained by the said manufacturing method, and the inorganic filler disperse | distributed in this matrix.

  According to the production method of the present invention, volume reduction of the silicone molded product hardly occurs in the firing stage, and insufficient strength can be avoided while maintaining the shape and dimensions. Therefore, an inorganic molded body having a desired shape having the desired strength can be obtained.

  In the inorganic molded body of the present invention, the inorganic ceramic portion serving as a matrix is amorphous, that is, obtained as a glass ceramic. Therefore, the method of the present invention can be used as a low-temperature sintering method capable of simultaneously firing conductors having high electrical conductivity.

  Since the production method of the present invention can be produced by molding a silicone-based molded product as a starting material into a required shape from a curable silicone composition, the organic material generally has a molding process stage. In addition, the obtained product has good heat resistance as an inorganic material.

[Silicone moldings]
The silicone-based molded product used as a starting material in the production method of the present invention is composed of a matrix made of solid silicone and an inorganic filler dispersed in the matrix. This silicone-based molded product can be obtained by curing a curable silicone composition containing an inorganic filler.

-Curable silicone composition-
A well-known thing can be used as a curable silicone composition. The curable silicone composition is desirably semi-solid or liquid having plasticity usually at room temperature.

  In the present specification, “room temperature” means a temperature in the range of 15 to 35 ° C. unless otherwise specified.

  Specific examples of the curable silicone composition include heat curable types such as addition curable types; photocurable types such as ultraviolet curable types and electron beam curable types; and condensation curable type silicone compositions.

  In the case of the thermosetting type, the curable silicone composition is cured by heating and converted into a silicone cured product. Examples of the heat curable silicone composition include an addition curable silicone composition.

  Examples of addition-curable silicone compositions include linear organopolysiloxanes having an alkenyl group such as a vinyl group at one or both of the molecular chain terminal portion (one or both ends) and the molecular chain non-terminal portion. And a silicone composition that cures by reacting organohydrogenpolysiloxane with an organohydrogenpolysiloxane in the presence of a platinum group metal catalyst (hydrosilylation addition reaction).

  Examples of the photocurable silicone composition include an ultraviolet curable silicone composition and an electron beam curable silicone composition.

  Examples of the ultraviolet curable silicone composition include a silicone composition that is cured by ultraviolet energy having a wavelength of 200 to 400 nm. In this case, the curing mechanism is not particularly limited. Specific examples thereof include an acrylic silicone-based silicone composition containing an organopolysiloxane having an acryloyl group or a methacryloyl group and a photopolymerization initiator, an organopolysiloxane having a mercapto group-containing organopolysiloxane and an alkenyl group such as a vinyl group. And photopolymerization initiator-containing mercapto-vinyl addition polymerization silicone composition, addition reaction silicone composition using the same platinum group metal catalyst as the thermosetting addition reaction type, and organopolysiloxane having an epoxy group And a cationic polymerization type silicone composition containing an onium salt catalyst, and any of them can be used as an ultraviolet curable silicone composition.

  As the electron beam curable silicone composition, any silicone composition that is cured by radical polymerization that starts by irradiating an electron beam to an organopolysiloxane having a radical polymerizable group can be used.

  Examples of the condensation curable silicone composition include silanol group-blocked organopolysiloxane and organohydrogenpolysiloxane or hydrolyzable silane such as tetraalkoxysilane and organotrialkoxysilane and / or a partially hydrolyzed condensate thereof. A silicone composition that cures by reacting in the presence of a condensation reaction catalyst such as an organotin catalyst, or both ends are trialkoxysiloxy groups, dialkoxyorganosiloxy groups, trialkoxysiloxyethyl groups, dialkoxyorganosiloxyethyls Examples include silicone compositions that cure by reacting an organopolysiloxane blocked with an alkoxy-containing siloxy group or an alkoxy-containing siloxyalkyl group in the presence of a condensation reaction catalyst such as an organotin catalyst. It is possible.

  However, in order to obtain the solid silicone with high dimensional accuracy, an addition-curable silicone composition with a small volume shrinkage is preferable.

  Hereinafter, representative examples of the above-mentioned curable silicone composition will be described in detail focusing on components other than the inorganic filler, but any composition inorganic filler is included as an essential component, and other well-known conventional additions Things can be included as needed.

<Addition-curing silicone composition>
As an addition-curable silicone composition, specifically, for example,
(A) an organopolysiloxane containing at least two alkenyl groups bonded to silicon atoms,
(B) Organohydrogenpolysiloxane containing at least two hydrogen atoms bonded to silicon atoms (ie, SiH groups) The silicon atoms in component (b) per mole of alkenyl groups in the total curable silicone composition And an amount of hydrogen atoms bonded to the amount of 0.1 to 5.0 mol, and (c) an addition-curable silicone composition containing an effective amount of a platinum group metal catalyst.

-Component (a) The organopolysiloxane of component (a) is a base polymer of an addition-curable silicone composition and contains at least two alkenyl groups bonded to silicon atoms. As the component (a), a known organopolysiloxane can be used. The weight average molecular weight of the organopolysiloxane of component (a) measured by gel permeation chromatography is preferably about 3,000 to 300,000 in terms of polystyrene. Furthermore, the viscosity of the organopolysiloxane of component (a) at 25 ° C. is preferably 100 to 1,000,000 mPa · s, particularly preferably about 200 to 100,000 mPa · s. The organopolysiloxane as component (a) is basically composed of repeating diorganosiloxane units ((R ¹ ) ₂ SiO _2/2 units) in the molecular chain (main chain), and both ends of the molecular chain are triorgano. It has a non-branched linear structure blocked with a siloxy group ((R ¹ ) ₃ SiO _1/2 ), or a molecular structure in which the molecular chain is composed of repeating diorganosiloxane units, and has a non-branched cyclic structure. , R ¹ SiO _3/2 unit or a branched structure containing SiO _4/2 unit may be partially contained (where R ¹ is the same or different unsubstituted or substituted carbon atom number) Is preferably a monovalent hydrocarbon group of 1 to 10, more preferably 1 to 8.).

As the component (a), for example, the following average composition formula (1):
R ¹ _a SiO _{(4-a) / 2} (1)
Wherein R ¹ is as described above, and a is preferably in the range of 1.5 to 2.8, more preferably 1.8 to 2.5, and even more preferably 1.95 to 2.05. There is a positive number.)
And an organopolysiloxane having at least two alkenyl groups in one molecule is used.

Examples of the monovalent hydrocarbon group represented by R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. Alkyl groups such as octyl group, nonyl group and decyl group; aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group; aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group; vinyl group and allyl group , Alkenyl groups such as propenyl group, isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group, octenyl group; some or all of the hydrogen atoms of these hydrocarbon groups are halogen atoms such as fluorine, bromine, chlorine, cyano Groups substituted with groups such as chloromethyl, chloropropyl, bromoethyl, tri Ruoropuropiru group, cyanoethyl group and the like.

In this case, at least two of R ¹ are alkenyl groups (in particular, alkenyl groups having preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms). The content of the alkenyl group is within the total organic group bonded to the silicon atom (that is, within the unsubstituted or substituted all monovalent hydrocarbon group represented by R ¹ in the average composition formula (1)), preferably 0.01 to 20 mol%, particularly preferably 0.1 to 10 mol%. When the organopolysiloxane of component (a) has a linear structure, the alkenyl group is bonded to a silicon atom only in one of the molecular chain terminal and the non-molecular chain terminal, and both of them are silicon. Although it may be bonded to an atom, it is preferable that at least one alkenyl group is bonded to the silicon atom at the end of the molecular chain in view of the curing speed of the composition, the physical properties of the cured product, and the like.

R ¹ may be basically any of the above, but the alkenyl group is preferably a vinyl group, and the monovalent hydrocarbon group other than the alkenyl group is preferably a methyl group or a phenyl group. .

  Specific examples of the component (a) include compounds represented by the following general formula.

R in the above general formula is the same as R ¹ except that it does not represent an alkenyl group. m and n are integers satisfying m ≧ 1 and n ≧ 0, and m + n is a number at which the molecular weight and viscosity of the organopolysiloxane are the above values.

-Component (b) The organohydrogenpolysiloxane of component (b) has at least 2 (usually 2 to 200) hydrogen atoms (SiH groups) bonded to silicon atoms, preferably 3 or more (usually 3 or more). ~ 100). The component (b) reacts with the component (a) and acts as a crosslinking agent. The molecular structure of the component (b) is not particularly limited. For example, any conventionally produced organohydrogenpolysiloxane such as linear, cyclic, branched, and three-dimensional network (resinous) can be used as the component (b). Can be used as In the case where the component (b) has a linear structure, the SiH group is bonded to the silicon atom only in one of the molecular chain terminal and the non-molecular chain terminal, or both. Also good. The number (or degree of polymerization) of silicon atoms in one molecule is usually 2 to 300, preferably about 4 to 150, and the organohydrogenpolysiloxane that is liquid at 25 ° C. is component (b). Can be preferably used.

As the component (b), for example, the following average composition formula (2):
R ² _b H _c SiO _{(4-bc) / 2} (2)
(Wherein R ² is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and b and c are preferably 0.7 ≦ b ≦ 2.1, 0.001 ≦ c ≦ 1.0 and 0.8 ≦ b + c ≦ 3.0, more preferably 1.0 ≦ b ≦ 2.0, 0.01 ≦ c ≦ 1.0, and 1.5 ≦ b + c (It is a positive number satisfying ≦ 2.5.)
The organohydrogenpolysiloxane shown by these is used. Examples of R ² include the same groups as R ¹ in the average composition formula (1) (excluding alkenyl groups).

Specific examples of the organohydrogenpolysiloxane represented by the above average composition formula (2) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (Hydrogendimethylsiloxy) methylsilane, tris (hydrogendimethylsiloxy) phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane-dimethylsiloxane cyclic copolymer, both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both Terminal trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, both ends dimethylhydrogensiloxy group-blocked dimethyl Loxane / methylhydrogensiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, both-end trimethyl Siloxy group-blocked methylhydrogensiloxane / methylphenylsiloxane / dimethylsiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methylhydrogensiloxane / dimethylsiloxane / diphenylsiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methylhydro siloxane-dimethylsiloxane-methylphenylsiloxane copolymers, (CH _{3) 2} HSiO _1/2 units and (CH _{3) 3} S Copolymers consisting of O _1/2 units and SiO _4/2 units, copolymers comprising (CH _{3) 2} HSiO _1/2 units and SiO _4/2 units, (CH _{3) 2} HSiO _{1/2 Examples} thereof include copolymers comprising units, SiO _4/2 units, and (C ₆ H ₅ ) ₃ SiO _1/2 units.

  Component (b) is added in an amount of 0.1 to 5.0 moles, preferably 0, per mole of alkenyl groups bonded to silicon atoms in component (a). .5 to 3.0 mol, more preferably 0.8 to 2.0 mol. When the added amount is such that the amount of the SiH group is less than 0.1 mol, the crosslinking density of the cured product obtained from the composition of the present invention becomes too low, and the heat resistance of the cured product is adversely affected. . Further, when the added amount is such that the amount of the SiH group is more than 5.0 mol, foaming due to a dehydrogenation reaction occurs in the cured product, and the heat resistance of the cured product is further adversely affected. .

-Component (c) The platinum group metal catalyst of component (c) is used as a catalyst for promoting the addition curing reaction (hydrosilylation) between component (a) and component (b). As the component (c), a known platinum group metal catalyst can be used, but it is preferable to use platinum or a platinum compound. Specific examples of the component (c) include platinum black, platinous chloride, chloroplatinic acid, alcohol-modified products of chloroplatinic acid, and complexes of chloroplatinic acid with olefins, aldehydes, vinyl siloxanes or acetylene alcohols. It is done.

  The addition amount of the component (c) is an effective amount as a catalyst, and may be appropriately increased or decreased depending on the desired curing rate. Preferably, the component (a) is converted to a platinum group metal with respect to the component on a mass basis. It is in the range of 0.1 to 1,000 ppm, more preferably 1 to 200 ppm.

<Ultraviolet curable silicone composition>
As an ultraviolet curable silicone composition, specifically, for example,
(D) UV-reactive organopolysiloxane, and (e) UV-curable silicone composition containing a photopolymerization initiator.

-Component (d) The UV-reactive organopolysiloxane of component (d) usually acts as a base polymer in the UV-curable silicone composition. The component (d) is not particularly limited, and is preferably an organopolysiloxane having at least 2, more preferably 2 to 20, particularly preferably 2 to 10 ultraviolet-reactive groups in one molecule. A plurality of the UV-reactive groups present in the organopolysiloxane may be the same or different.

The organopolysiloxane of component (d) is basically composed of repeating diorganosiloxane units, and both ends of the molecular chain are triorganosilyl-substituted alkyl groups such as triorganosiloxy groups or triorganosilylethyl groups. It is preferable to have a non-branched linear structure that is blocked with, or a molecular chain that is composed of repeating diorganosiloxane units, and that has a non-branched cyclic structure, but a trifunctional siloxane unit or SiO ₂ unit. A branched structure such as the above may be partially contained. When the organopolysiloxane of component (d) has a linear structure, it has an ultraviolet-reactive group only at one of the molecular chain terminal and the part that is not the molecular chain terminal. However, it is preferable to have UV reactive groups at least at both ends of the molecular chain.

  Examples of the ultraviolet reactive group include alkenyl groups such as vinyl group, allyl group and propenyl group; alkenyloxy groups such as vinyloxy group, allyloxy group, propenyloxy group and isopropenyloxy group; acryloyl group and methacryloyl group. Aliphatic unsaturated groups other than alkenyl groups; mercapto groups; epoxy groups; hydrosilyl groups and the like, preferably acryloyl groups, methacryloyl groups, mercapto groups, epoxy groups, and hydrosilyl groups, more preferably acryloyl groups and A methacryloyl group is mentioned.

  The ultraviolet-reactive group may be directly bonded to the silicon atom constituting the main chain in the organopolysiloxane of the component (d) depending on the type thereof, or silicon via a linking group such as an alkylene group. It may be bonded to an atom.

  The viscosity of the organopolysiloxane is not particularly limited, but is preferably 25 mPa · s or more, more preferably 100 to 10,000,000 mPa · s at 25 ° C., and more preferably 100 to 100,000 mPa · s. It is particularly preferred that

  As a preferable form of the component (d), for example, the following general formula (3a):

[Wherein R ³ is the same or different, unsubstituted or substituted monovalent hydrocarbon group having no UV-reactive group, and R ⁴ and R ⁵ are the same or different, UV-reactive group or UV A group having a reactive group, R ⁵ is the same or different group having an ultraviolet-reactive group, t is an integer of 5 to 1,000, u is an integer of 0 to 100, p Is an integer from 0 to 3, q is an integer from 0 to 3, provided that p + q + u ≧ 2. ]
Or the following general formula (3b):

[Wherein R ³ , R ⁴ , R ⁵ , t, u, p and q are as defined in the general formula (3a), k is an integer of 2 to 4, and r and s are each 1 It is an integer of -3, However, it is pr + qs + u> = 2. ]
And an organopolysiloxane having at least two ultraviolet-reactive groups represented by the formula:

In the above general formulas (3a) and (3b), R ³ is preferably the same or different, unsubstituted or substituted, carbon atoms having no UV-reactive group, preferably 1 to 20, more preferably 1 to 10. Even more preferably, it is a monovalent hydrocarbon group of 1 to 8. Examples of the monovalent hydrocarbon group represented by R ³ include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, and 2-ethylbutyl. Group, alkyl group such as octyl group; cycloalkyl group such as cyclohexyl group and cyclopentyl group; aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group and diphenyl group; aralkyl group such as benzyl group and phenylethyl group; Groups in which some or all of the hydrogen atoms bonded to the carbon atoms of these hydrocarbon groups are substituted with halogen atoms, cyano groups, amino groups, carboxyl groups, etc., such as chloromethyl groups, trifluoropropyl groups, 2-cyanoethyl group, 3-cyanopropyl group, etc. are mentioned, preferably methyl group and phenyl group are Gerare, more preferably methyl group. The monovalent hydrocarbon group represented by R ³ may have one or more sulfonyl groups, ether bonds (—O—), carbonyl groups and the like in its skeleton.

In the general formulas (3a) and (3b), the ultraviolet reactive groups represented by R ⁴ and R ⁵ are as described above. The group having an ultraviolet reactive group is a case where the ultraviolet reactive group is bonded to a silicon atom via a linking group. Specific examples thereof include a 3-glycidoxypropyl group, 2- (3, 4-epoxycyclohexyl) ethyl group, 3-methacryloyloxypropyl group, 3-acryloyloxypropyl group, 3-mercaptopropyl group, 2- {bis (2-methacryloyloxyethoxy) methylsilyl} ethyl group, 2-{(2- Methacryloyloxyethoxy) dimethylsilyl} ethyl group, 2- {bis (2-acryloyloxyethoxy) methylsilyl} ethyl group, 2-{(2-acryloyloxyethoxy) dimethylsilyl} ethyl group, 2- {bis (1,3 -Dimethacryloyloxy 2-propoxy) methylsilyl} ethyl group, 2-{(1,3-dimethacrylate) Royloxy-2-propoxy) dimethylsilyl} ethyl group, 2- {bis (1-acryloyloxy 3-methacryloyloxy 2-propoxy) methylsilyl} ethyl group, and 2-{(1-acryloyloxy 3-methacryloyloxy 2-propoxy) ) Dimethylsilyl} ethyl group, etc., preferably 3-methacryloyloxypropyl group, 3-acryloyloxypropyl group, 2- {bis (2-methacryloyloxyethoxy) methylsilyl} ethyl group, 2-{(2-methacryloyl) Oxyethoxy) dimethylsilyl} ethyl group, 2- {bis (2-acryloyloxyethoxy) methylsilyl} ethyl group, 2-{(2-acryloyloxyethoxy) dimethylsilyl} ethyl group, 2- {bis (1,3- Dimethacryloyloxy 2 Propoxy) methylsilyl} ethyl group, 2-{(1,3-dimethacryloyloxy 2-propoxy) dimethylsilyl} ethyl group, 2- {bis (1-acryloyloxy 3-methacryloyloxy 2-propoxy) methylsilyl} ethyl group, And 2-{(1-acryloyloxy 3-methacryloyloxy 2-propoxy) dimethylsilyl} ethyl group, more preferably 3-acryloyloxypropyl group, 2- {bis (2-methacryloyloxyethoxy) methylsilyl} ethyl. Group, 2-{(2-methacryloyloxyethoxy) dimethylsilyl} ethyl group, 2-{(2-acryloyloxyethoxy) dimethylsilyl} ethyl group, 2- {bis (1,3-dimethacryloyloxy-2-propoxy) Methylsilyl} ethyl group, 2- { Bis (1-acryloyloxy 3-methacryloyloxy 2-propoxy) methylsilyl} ethyl group may be mentioned.

In the general formulas (3a) and (3b), R ⁴ and R ⁵ may be the same or different, and R ⁴ and R ⁵ may be the same or different.

  In the general formulas (3a) and (3b), t is usually an integer of 5 to 1,000, preferably 10 to 800, and more preferably 50 to 500. u is usually an integer of 0 to 100, preferably 0 to 50, more preferably 0 to 20. p is usually an integer of 0 to 3, preferably 0 to 2, more preferably 1 or 2. q is preferably an integer of 0 to 2, more preferably 1 or 2. In said formula (3b), k is an integer of 2-4 normally, Preferably it is 2 or 3. r and s are each an integer of 1 to 3, preferably 1 or 2. Furthermore, since the organopolysiloxane represented by the general formulas (3a) and (3b) has at least two ultraviolet-reactive groups as described above, p + q + u ≧ 2 in the formula (3a), and the formula (3b ) Pr + qs + u ≧ 2.

  Specific examples of the organopolysiloxane represented by the above formula (3a) or (3b) include those shown below.

[Wherein R ⁶ is 90 mol% of a methyl group and 10 mol% of a phenyl group]
-(E) component The photoinitiator of (e) component has the effect | action which accelerates | stimulates photopolymerization of the ultraviolet-reactive group in the said (d) component. The component (e) is not particularly limited, and specific examples thereof include acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, 4-methylacetophenone, 3-pentylacetophenone, 4- Methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4-chloro-4′-benzylbenzophenone 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoin methyl ether, benzoin butyl ether, bis (4-dimethylamino) Phenyl) ketone, benzylmethoxyacetal, 2-chlorothioxanthone, diethylacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl- (4- (methylthio) phenyl) -2-morpholino-1-propane, 2,2-dimethoxy- 2-phenylacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one and the like are preferable, and benzophenone, 4-methoxyacetophenone, 4-methylbenzophenone, diethoxyacetophenone, 1 -Hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one, more preferably diethoxyacetophenone, 1-hydroxycyclohexylphenyl Ketones, and 2-hydroxy-2-methyl-1-phenylpropan-1-one. These photopolymerization initiators may be used alone or in combination of two or more.

  (E) Although the addition amount of a component is not specifically limited, Preferably it is 0.01-10 mass parts with respect to 100 mass parts of (d) component, More preferably, it is 0.1-3 mass parts, More preferably 0.5 to 3 parts by mass. When this addition amount is within this range, the cured rubber obtained by curing the composition of the present invention is excellent in physical properties such as strength and tensile strength.

<Condensation-curable silicone composition>
As the condensation curable silicone composition, specifically, for example,
(H) an organopolysiloxane containing at least two silicon atom-bonded hydroxyl groups or silicon atom-bonded hydrolyzable groups, preferably at both ends of the molecular chain;
(I) A hydrolyzable silane and / or a partially hydrolyzed condensate thereof as an optional component, and (j) a condensation curable silicone composition containing a condensation reaction catalyst as an optional component.

-Component (h) Component (h) is an organopolysiloxane containing at least two silicon atom-bonded hydroxyl groups or silicon atom-bonded hydrolyzable groups, and is a base polymer of a condensation-curable silicone composition. Component (h), the organopolysiloxane, basically has a linear or cyclic structure with no molecular branch consisting of repeating diorganosiloxane units, but has a partial branched structure. You may do it. In the present specification, the “hydrolyzable group” means a group capable of decomposing by the action of water to form a hydroxyl group.

  In the organopolysiloxane of component (h), examples of hydrolyzable groups include acyloxy groups such as acetoxy group, octanoyloxy group and benzoyloxy group; dimethyl ketoxime group, methyl ethyl ketoxime group, diethyl ketoxime group and the like. Ketoxime group (namely, iminoxy group); alkoxy group such as methoxy group, ethoxy group, propoxy group; alkoxyalkoxy group such as methoxyethoxy group, ethoxyethoxy group, methoxypropoxy group; vinyloxy group, isopropenyloxy group, 1-ethyl Alkenyloxy groups such as -2-methylvinyloxy group; amino groups such as dimethylamino group, diethylamino group, butylamino group and cyclohexylamino group; aminoxy groups such as dimethylaminoxy group and diethylaminoxy group; N-methylacetate Bromide group, N- ethyl acetamide group, and amide groups such as N- methylbenzamide group.

  These hydrolyzable groups include, for example, trialkoxysiloxy groups, dialkoxyorganosiloxy groups, triacyloxysiloxy groups, diacyloxyorganosiloxy groups, triiminoxysiloxy groups (ie, triketoxime siloxy groups), diiminoxy groups Siloxy groups containing 2 or 3 hydrolyzable groups, such as organosiloxy groups, trialkenoxysiloxy groups, dialkenoxyorganosiloxy groups, trialkoxysiloxyethyl groups, dialkoxyorganosiloxyethyl groups, or two Alternatively, it is preferably located at both ends of the molecular chain of the linear diorganopolysiloxane in the form of a siloxyalkyl group containing three hydrolyzable groups.

The other atom or group bonded to the silicon atom other than the hydroxyl group and the hydrolyzable group is a monovalent hydrocarbon group, and the monovalent hydrocarbon group is exemplified for R ¹ in the above average composition formula (1). And the same unsubstituted or substituted monovalent hydrocarbon group.

  As the component (h), for example, the following formula:

[In the above formula, Y is a hydrolyzable group, x is 1, 2 or 3, y and z are each an integer of 1-1000]
An organopolysiloxane having a hydroxyl group bonded to a silicon atom or a hydrolyzable group bonded to a silicon atom at both ends of the molecular chain represented by

  Specific examples of those having hydrolyzable groups Y at both ends among the organopolysiloxanes represented by the above chemical formula include molecular chain both ends trimethoxysiloxy group-blocked dimethylpolysiloxane, molecular chain both ends trimethoxysiloxy group Capped dimethylsiloxane / methylphenylsiloxane copolymer, molecular chain both ends trimethoxysiloxy group blocked dimethylsiloxane / diphenylsiloxane copolymer, molecular chain both ends methyldimethoxysiloxy group blocked dimethylpolysiloxane, molecular chain both ends triethoxysiloxy group Examples thereof include blocked dimethylpolysiloxane and molecular chain both ends 2- (trimethoxysiloxy) ethyl group-blocked dimethylpolysiloxane. These can be used singly or in combination of two or more.

-(I) component The hydrolyzable silane of component (i) and / or its partial hydrolysis condensate is an optional component and acts as a curing agent. When the component (h) which is the base polymer is an organopolysiloxane containing at least two silicon atom-bonded hydrolyzable groups other than silanol groups in one molecule, the component (i) is a condensation-curable silicone composition. It can be omitted. As component (i), a silane containing at least three silicon atom-bonded hydrolyzable groups in one molecule and / or a partial hydrolysis condensate thereof (that is, at least one, preferably two or more hydrolysis products) An organopolysiloxane in which a functional group remains is preferably used.

Examples of the hydrolyzable silane include formula (4):
R ⁷ _e SiX _4-e (4)
(Wherein R ⁷ is an unsubstituted or substituted monovalent hydrocarbon group, X is a hydrolyzable group, and e is 0 or 1) is preferably used. R ⁷ is particularly preferably an alkyl group such as a methyl group or an ethyl group; an alkenyl group such as a vinyl group, an allyl group or a propenyl group; and an aryl group such as a phenyl group. Examples of X include all of those exemplified as the silicon atom-bonded hydrolyzable group Y in the component (h).

  Specific examples of the hydrolyzable silane include, for example, methyltriethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, ethyl orthosilicate and the like, and partial hydrolysis condensates thereof. These can be used singly or in combination of two or more.

  When the component (i) hydrolyzable silane and / or partial hydrolysis condensate thereof is used, the amount added is preferably 0.01 to 20 parts by mass, particularly preferably 100 parts by mass of the component (h). 0.1 to 10 parts by mass. When the component (i) is used, if the addition amount is within the above range, the storage stability, adhesiveness and curing rate of the composition of the present invention are particularly good.

-Component (j) The condensation reaction catalyst of component (j) is an optional component, and the hydrolyzable silane and / or partially hydrolyzed condensate thereof of component (i) is, for example, an aminoxy group, amino group, ketoxime group Etc., it may not be used. Examples of the condensation reaction catalyst of component (j) include organic titanates such as tetrabutyl titanate and tetraisopropyl titanate; diisopropoxybis (acetylacetonato) titanium, diisopropoxybis (ethylacetoacetate) titanium and the like. Organic titanium chelate compounds; organoaluminum compounds such as aluminum tris (acetylacetonate) and aluminum tris (ethylacetoacetate); organozirconium compounds such as zirconium tetra (acetylacetonate) and zirconium tetrabutyrate; dibutyltin dioctoate and dibutyltin Organotin compounds such as dilaurate and dibutyltin di (2-ethylhexanoate); tin naphthenate, tin oleate, tin butyrate, cobalt naphthenate, stearic acid Metal salts of organic carboxylic acids such as: amine compounds such as hexylamine and dodecylamine phosphate, and salts thereof; quaternary ammonium salts such as benzyltriethylammonium acetate; lower fatty acid salts of alkali metals such as potassium acetate; dimethylhydroxylamine; Examples thereof include dialkylhydroxylamine such as diethylhydroxylamine; guanidyl group-containing organosilicon compound and the like. These can be used singly or in combination of two or more.

  (J) When using the condensation reaction catalyst of a component, the addition amount in particular is not restrict | limited, Although an effective amount as a catalyst may be sufficient, Preferably it is 0.01-20 mass parts with respect to 100 mass parts of (h) component. Especially preferably, it is 0.1-10 mass parts. When the component (j) is used, if the addition amount is within the above range, the curability and storage stability of the composition of the present invention are particularly good.

<Inorganic filler>
An inorganic filler is blended as an essential component in any of the above curable silicone compositions. As the inorganic filler, a functional filler is preferable. Examples of the functional filler include silica, alumina, zirconia, silicon nitride, aluminum, titanium oxide, barium oxide, zinc oxide, bismuth oxide, ferric oxide, carbon black, silver, gold, palladium-silver mixture, ruthenium oxide. And boron nitride. These are known to be selected and used in a timely manner according to the application. For example, carbon black, silver, gold, palladium-silver mixture, ruthenium oxide, etc. are used to impart conductivity, and titanium oxide, barium oxide, zinc oxide, bismuth oxide are used to impart dielectric performance. Etc. are used.

  When powder or granular material is used as the inorganic filler, its shape may be irregular, regular such as spherical, or any shape, but those having an average particle diameter of 0.1 to 100 μm are preferred. If the average particle size is less than 0.1 μm, the fluidity of the silicone composition as the raw material of the inorganic molded body may be lost and the processability may be poor, and if it exceeds 100 μm, the uniformity of the silicone composition will be poor.

  The compounding quantity of the said inorganic filler shall be 1-60 volume% of the whole silicone composition, Preferably it is 2-45 volume%, More preferably, it is 5-30 volume%. If the blending amount is less than 1% by volume, the required functionality cannot be obtained, and if it exceeds 60% by volume, the fluidity is lost and the processability is poor.

  In addition, when mixing the composition sufficiently uniformly by a mixer or the like, it is preferable to perform surface treatment or the like in advance with an inorganic filler as a wetter with a silane coupling agent or the like in order to improve the storage stability of the resulting composition.

  Here, as the silane coupling agent, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, γ- Methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, N-β (aminoethyl) ) Γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropylto Methoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, bis (triethoxypropyl) tetrasulfide, γ- An isocyanate propyl triethoxysilane etc. are mentioned. Here, the amount of the silane coupling agent used for the surface treatment and the surface treatment method are not particularly limited.

  Content of the said organosilane shall be 0.1-10 mass% in the silicone composition used as the raw material of an inorganic molded object. If the content is less than 0.1% by mass, the effect of improving the wettability of the surface of the inorganic filler cannot be obtained, and if it exceeds 10% by mass, the effect is saturated and uneconomical.

<Molding / Curing>
When the curable silicone composition is molded into a required shape and cured, the shape is arbitrary and is selected according to the purpose. When forming an inorganic molded object on a base material, the kind of curable silicone composition can be selected suitably according to the material, dimension, etc. of a base material. The molding method of the silicone composition can also be selected as appropriate, and can be molded by methods such as injection molding, transfer molding, injection molding, and coating. The curing conditions of a typical curable silicone composition will be described.

・ In the case of heat curable type, especially addition curable type silicone composition:
In the case of a thermosetting silicone composition, the curing is performed by heating. In particular, the temperature condition for curing the addition-curable silicone composition is preferably 60 ° C to 180 ° C, more preferably 80 ° C to 160 ° C. The curing time is 1 minute to 3 hours, and even more preferably 3 minutes to 2 hours. Moreover, you may perform a secondary cure as needed, As temperature conditions in that case, Preferably it is 120 degreeC or more, More preferably, it is 150 to 250 degreeC. The curing time at this time is preferably 10 minutes to 48 hours, more preferably 30 minutes to 24 hours.

・ In the case of UV curable silicone composition:
The ultraviolet irradiation conditions for curing the ultraviolet curable silicone composition are, for example, an ultraviolet light emitting diode having an emission wavelength of 365 nm, an illuminance of 5 to 500 mW / cm ² , preferably 10 to 200 mW / cm ² , and a light amount of 0.5 to 100 J / cm. ² , preferably 10 to 50 J / cm ² can be cured by irradiating with ultraviolet rays. Moreover, you may perform a secondary cure as needed, As temperature conditions in that case, Preferably it is 120 degreeC or more, More preferably, it is 150 to 250 degreeC. The curing time at this time is preferably 10 minutes to 48 hours, more preferably 30 minutes to 24 hours.

In the case of a condensation curable silicone composition:
The curable silicone composition is cured by leaving it in air at room temperature to 200 ° C. Specifically, usually, when the composition is left in an atmosphere containing moisture (for example, 25 to 90% RH, preferably 50 to 85% RH), the composition is cured by moisture in the atmosphere. You may heat in order to accelerate hardening. Moreover, you may perform secondary hardening as needed. The temperature condition at that time is preferably 120 ° C or higher, more preferably 150 ° C to 250 ° C. The curing time at this time is preferably 10 minutes to 48 hours, more preferably 30 minutes to 24 hours.

-Formation of patterned curable silicone composition layer-
In one embodiment of the present invention, the inorganic molded body is formed in a patterned form on a substrate.

  In this embodiment, the silicone-based molded product is formed by applying a liquid curable silicone composition containing an inorganic filler onto a substrate in a required pattern by printing to form a patterned curable silicone composition layer. The patterned curable silicone composition layer is cured to form a patterned cured silicone layer. By patterning the patterned cured silicone layer thus obtained into an inorganic ceramic, a patterned inorganic molded body is formed on the substrate.

  In this embodiment, since it is necessary to apply the curable silicone composition to the substrate in a certain pattern by printing, the curable silicone composition needs to be liquid at room temperature. The viscosity is preferably 1,000,000 mPa · s or less, more preferably 100,000 mPa · s or less at room temperature. The lower limit of the viscosity is preferably 100 mPa · s or more, more preferably 200 mPa · s or more at room temperature.

  Coating by the printing method is advantageous in terms of cost as well as being simple in the process because it does not require the coating and peeling of the photoresist necessary for lithography. The printing method that can be used is not particularly limited, and examples thereof include an imprint method, an offset printing method, an ink jet printing method, and a relief printing method. Among these, the imprint method and the ink jet method are preferable.

  Examples of the substrate to which the curable silicone composition is applied include a semiconductor substrate such as a silicon substrate. Patterning can be performed in various ways according to the purpose of forming the inorganic molded body, and is not particularly limited. If the purpose is to form a circuit or a wiring, it may be applied on the substrate in a pattern that has a required circuit shape or wiring shape.

[Heating in non-oxidizing atmosphere]
In the method of the present invention, the silicone-based molded product obtained as described above is heated at 400 to 1500 ° C. in a non-oxidizing atmosphere. As a result, the matrix portion of the silicone-based molded product (that is, the portion other than the inorganic filler of the cured silicone) becomes an inorganic ceramic. When the silicone-based molded product is a patterned cured silicone layer, a patterned inorganic molded product is obtained.

  The heating temperature is preferably 600 ° C. or higher, and more preferably 800 ° C. or higher. The heating temperature is preferably 1300 ° C. or lower, and more preferably 1100 ° C. or lower. Therefore, typically, 600 to 1300 ° C is preferable, and 800 to 1100 ° C is more preferable. By this heat treatment, cleavage of carbon-hydrogen bonds existing in silicone and elimination of hydrogen occur, and inorganic ceramicization proceeds. However, almost no elimination of silicon and carbon in the silicone molded product occurs and the silicon molded product is retained in the product.

  The above reaction proceeds satisfactorily when a trace amount of Group 8 elements such as platinum, palladium, rhodium and the like are present. The Group 8 element is preferably present in the silicone-based molded product in an amount of 0.1 to 5,000 ppm, more preferably 10 to 2,000 ppm, and even more preferably 50 to 1,000 ppm. In this case, for example, a required amount of Group 8 element is added to the curable silicone composition that is the starting material. Addition-curable silicone compositions usually contain a platinum group metal as a catalyst. In the absence of a Group 8 element, heating at 600 ° C. or higher is desirable.

Heating is performed in a non-oxidizing atmosphere, preferably in an inert gas atmosphere. Examples of the inert gas include nitrogen gas, argon gas, helium gas, and practically, nitrogen gas is preferable. The completion point of the heat treatment is, for example, when the weight loss is less than 1% by weight even when the heated product is heated at 600 ° C. for 1 hour.
[Inorganic molded body]
As described above, the inorganic molded body of the present invention obtained by heating a silicone-based molded article to 400 to 1500 ° C. in a non-oxidizing atmosphere is composed of a matrix made of inorganic ceramics and an inorganic filler dispersed in the matrix. Become. The matrix portion typically comprises, for example, silicon, carbon and oxygen, and the average elemental ratio of silicon, carbon and oxygen is the following composition formula (5):
SiC _V O _W (5)
(In the formula, v is a number that satisfies 0.5 ≦ v ≦ 3.0, and w is a number that satisfies 1.0 ≦ w ≦ 4.0.)
It is considered that it is made of an amorphous inorganic ceramic material having a siloxane skeleton composed of Si—O—Si bonds and having a mass fraction of hydrogen of 0 to 1 mass%.

  The present invention will be specifically described below with reference to examples. In the following description, Me is a methyl group and Vi is a vinyl group. The experiments in the following examples were performed at room temperature. The viscosity is a measured value at 25 ° C. unless otherwise specified.

[Example 1]
(A) Diorganopolysiloxane of the following formula containing a vinyl group in one molecule:

(Wherein h is a number such that the viscosity of the siloxane at 25 ° C. is 600 mPa · s.) 90 parts by mass,
(B-1) Organohydrogenpolysiloxane represented by the following formula:

10 parts by mass,
(B-2) platinum-divinyltetrameryldisiloxane complex / toluene solution (platinum element content 0.5 mass%; hydrosilylation catalyst) 0.15 parts by mass, and (C) fumed silica (manufactured by Shin-Etsu Chemical Co., Ltd., average) In preparing an addition-curable silicone rubber composition having an amount of 15% by volume in the total composition, first of the above (A), (B-1) and (C) Each component was put into a planetary mixer (registered trademark of a mixer manufactured by Inoue Seisakusho Co., Ltd.) and stirred at room temperature for 1 hour, and then component (B-2) was added and stirred at room temperature for 30 minutes.

  The obtained silicone rubber composition was poured into a 10 mm deep mold having a surface with irregularities of 100 μm in width, and cured by heating in air at 125 ° C. for 1 hour. As a result, a sheet-like silicone molded product having a thickness of 10 mm with a surface roughness of 100 μm was obtained.

  Next, the silicone rubber molded product was placed in an alumina boat and heated in a horizontal tubular furnace to 1000 ° C. over 10 hours while raising the temperature at a rate of 100 ° C./h in a nitrogen gas atmosphere. And then cooled to room temperature. A black inorganic molded body was thus obtained. The mass lost by this heat treatment was 20.6%, and the atomic composition ratio was silicon / carbon / oxygen = 1.0 / 1.2 / 1.6. Moreover, when the surface was observed with SEM (scanning electron microscope), the shape and dimension before heat processing were maintained.

[Example 2]
In Example 1, (C ′) acetylene black (trade name: Denka Black, manufactured by Denki Kagaku Kogyo Co., Ltd.) was used instead of (C) fumed silica in an amount of 15% by volume in the total composition. Was prepared in the same manner as in Example 1 to prepare an addition-curable silicone rubber composition.

  The obtained composition was poured into a 1 mm thick screen mask having an opening of 1 cm square, and transferred onto an alumina substrate with a squeegee. Then, it heated in air at 125 degreeC for 1 hour, and obtained the sheet-like silicone rubber molding of thickness 1mm on a 1 cm square on an alumina substrate. When the electrical resistance of this silicone rubber molded product was measured, it was 1 kΩ / □. Further, the alumina substrate on which the silicone rubber molding was formed was placed in an alumina boat, and heated in a horizontal tubular furnace at a heating rate of 100 ° C./h for 10 hours in a nitrogen gas atmosphere to raise the temperature to 1000 ° C. After holding at 1000 ° C. for 1 hour, it was cooled to room temperature. Thus, a black inorganic molded body was obtained. The mass lost by this heat treatment was 15.6%. The composition of the constituent elements of the inorganic molded body was carbon / silicon / oxygen = 2.1 / 1.0 / 1.0. The inorganic molded body retained a 1 cm square shape and dimensions. Further, when the resistance of the inorganic molded body was measured, it was 200Ω / □.

[Example 3]
A black inorganic molded body was obtained in the same manner as in Example 1 except that amorphous alumina (manufactured by Showa Denko KK, average particle size 1.7 μm) was used as the component (C) instead of fumed silica. The mass lost by the heat treatment was 19.8% by mass, and the atomic composition ratio was silicon / carbon / oxygen = 1.0 / 1.3 / 1.6. Moreover, when the surface was observed by SEM, the unevenness | corrugation with a surface width of 100 micrometers maintained the shape and dimension before heat processing.

[Comparative Example 1]
The silicone molded product was treated in the same manner as in Example 1 except that the atmosphere when heating in the horizontal tubular furnace was changed to an air atmosphere. As a result, a white inorganic substance was obtained. The mass lost by this heat treatment was 44.6% by mass, and the atomic composition ratio of the product was silicon / carbon / oxygen = 1.0 / 0 / 1.9. Moreover, although it tried trying to pinch the sample after heat processing with tweezers, it broke easily and it was not able to be pinched. Moreover, since it was very brittle, the sample for observation by SEM was not able to be created.

[Example 4]
(D) 100 parts by mass of a liquid organopolysiloxane represented by the following formula:

(E) 2 parts by mass of 2-hydroxy-2-methyl-1-phenylpropan-1-one,
(F-1) 1,4,6-Trimethylbenzoyldiphenylphosphine oxide 1 part by mass,
(F-2) 1 part by mass of a partially hydrolyzed condensate of tetramethoxysilane (methoxysiloxane oligomer),
(G) 0.1 part by mass of a titanium chelate compound represented by the following formula,

and,
The same fumed silica as that used as the component (C) in Example 1 was mixed in an amount of 15% by volume in the entire composition to obtain an ultraviolet curable reactive silicone rubber composition.

The composition thus prepared was poured into a mold having a depth of 10 μm and a surface having irregularities having a width of 100 μm. The composition was cured by irradiating ultraviolet rays with two metal halide mercury lamps (illuminance 80 W / cm ² , energy amount 400 mJ / s). As a result, a sheet-like silicone molded product having a thickness of 10 mm with a surface roughness of 100 μm was obtained.

  Next, the silicone molded product thus obtained was heat-treated in a nitrogen gas atmosphere in the same manner as in Example 1 to obtain a black inorganic molded body. The mass lost by the heat treatment was 22.2%, and the atomic composition ratio was silicon / charcoal / oxygen = 1.0 / 1.3 / 1.7. Moreover, when the surface was observed by SEM, the unevenness | corrugation of the surface width of 100 micrometers maintained the shape and dimension before heat processing.

[Example 5]
(H) The following formula:

100 parts by weight of both ends trimethoxysiloxy group-blocked dimethylpolysiloxane represented by the formula (I) 0.1 parts by weight of a titanium chelate catalyst, and (J) fumed silica used as the component (C) in Example 1 in the entire composition. By mixing in an amount of 15% by volume, a condensation curing reaction type silicone rubber composition was obtained.

  The composition thus prepared was poured into a mold having a depth of 10 μm and a surface having irregularities having a width of 100 μm. The composition was cured by heating at 180 ° C. for 1 hour. As a result, a sheet-like silicone molded product having a thickness of 10 mm with a surface roughness of 100 μm was obtained.

  Next, the silicone molded product thus obtained was heat-treated in a nitrogen gas atmosphere in the same manner as in Example 1 to obtain a black inorganic molded body. The mass lost by the heat treatment was 20.2%, and the atomic ratio of the composition was silicon / carbon / oxygen = 1.0 / 1.2 / 1.7. Moreover, when the surface was observed by SEM, the unevenness | corrugation of the surface width of 100 micrometers maintained the shape and dimension before heat processing.

  The method of the present invention can be used as a low-temperature sintering method capable of simultaneously firing conductors having high electrical conductivity, and can be used in electronics packaging technology. The patterned inorganic molded body formed by the method of the present invention can be formed as a resistor, a dielectric, or a conductor. Therefore, for example, it is useful for producing a conductor circuit, a resistor circuit, a dielectric circuit, and the like.

Claims (9)

  Heating the silicone-based molded article comprising a matrix made of solid silicone and an inorganic filler dispersed in the matrix at 400 to 1500 ° C. in a non-oxidizing atmosphere to convert the solid silicone into inorganic ceramics. A method for producing an inorganic molded body comprising a matrix made of inorganic ceramics and an inorganic filler dispersed in the matrix.   The method for producing an inorganic molded body according to claim 1, wherein the silicone-based molded article is obtained by curing a curable silicone composition containing an inorganic filler.   The method for producing an inorganic molded body according to claim 2, wherein the curable silicone composition is a heat-curable, photocurable, or condensation-curable silicone composition.   The method for producing an inorganic molded body according to claim 3, wherein the curable silicone composition is a heat-curable silicone composition, and the heat-curable silicone composition is an addition-curable silicone composition.   The manufacturing method of the inorganic molded object which concerns on any one of Claims 2-4 in which the said curable silicone composition contains the said inorganic filler 1-60 volume% of this whole composition.   The silicone-based molding forms a patterned curable silicone composition layer by applying a liquid curable silicone composition containing an inorganic filler on a substrate in a required pattern by printing, and then forming the patterned curable silicone composition layer. The manufacturing method of the inorganic molded object which concerns on any one of Claims 1-5 which is the pattern hardening silicone layer obtained by hardening a silicone composition layer.   The method for producing an inorganic molded body according to claim 6, wherein the application of the curable silicone composition on the substrate by printing is performed by an imprint method, an offset printing method, an ink jet printing method, or a relief printing method. .   The inorganic molded object which consists of the matrix which consists of inorganic ceramics obtained by the method of any one of Claims 1-7, and the inorganic filler disperse | distributed in this matrix.   The inorganic molded body according to claim 8, wherein the inorganic molded body is a patterned inorganic molded body formed on a substrate.