JP3499393B2 - Precured product containing silicon-based compound as main component and method for producing molded article using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a component which is cured by a hydrolysis / condensation reaction of an alkoxysilyl group and / or a condensation reaction of a silanol group containing a silsesquioxane ladder polymer as a main component, and a SiH group in the molecule. And / or a novel silicon-based interpenetrating structure (IPN) composed of a silicon compound having at least two vinyl groups and having a molecular weight of 1000 or less and a component which is hardened by a hydrosilylation reaction (addition reaction) and which comprises a hydrosilylation catalyst. The present invention relates to a pre-cured product that gives a molded product that is considered to have, and a method for obtaining a molded product having an arbitrary shape by compression-molding the pre-cured product.

[0002]

2. Description of the Related Art Proceedings of the 2nd Symposium on Research and Development of Industrial Science and Technology, 2nd Silicon-based Polymer Materials (published on December 5, 1994) show that condensation reaction and addition reaction are carried out simultaneously in one pot with good yield. , A silsesquioxane ladder polymer and a polycarbosilane are disclosed to provide a curable composition having a silicon-based interpenetrating structure (IPN). Among them, it has been clarified that a cured product having high transparency can be obtained when the gelation rates of both components in the initial stage of curing are close to each other.

However, since the method for producing a cured product is a solution casting method, it is difficult to produce a high-thickness sample. Therefore, it has been a problem that it is impossible to fabricate a test piece having an arbitrary shape in order to measure physical properties applicable as a heat resistant structural material.

[0004]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a component which is cured by a hydrolysis / condensation reaction of an alkoxysilyl group containing a silsesquioxane ladder polymer as a main component and / or a condensation reaction of a silanol group, and a molecule. A component which is cured by a hydrosilylation (addition) reaction consisting of a silicon compound having a molecular weight of 1000 or less having at least 2 SiH groups therein, a silicon compound having a molecular weight of 1000 or less having at least 2 vinyl groups in the molecule, and a hydrosilylation catalyst. To provide a pre-cured product which can be melt compression molded to give a molded product considered to have a novel silicon-based interpenetrating structure (IPN) composed of and a method for producing a molded product having an arbitrary shape. is there.

[0005]

The object of the present invention is to provide a component which is cured by a hydrolysis / condensation reaction of an alkoxysilyl group containing a silsesquioxane ladder polymer as a main component and / or a condensation reaction of a silanol group, and a molecular weight. A pre-cured product which is considered to have a novel silicon-based interpenetrating structure (IPN) composed of a 1000 or less silicon compound and a component which cures by a hydrosilylation (addition) reaction consisting of a hydrosilylation catalyst is compression molded, Achieved by curing. High heat resistance and high elastic modulus can be obtained by optimizing pre-curing conditions and molding conditions, and in some cases, by forming a curable composition in which a silanol condensation catalyst, a polyfunctional crosslinking agent, water, or a silica-based crosslinking agent is combined. It was possible to produce a molded body having. That is, the present invention is
It has the following configuration.

1. (A) Formula (1) (R ¹ and R ² represent a hydrogen atom or a substituted or unsubstituted monovalent organic group,
R ³ , which may be the same or different, each represents a hydrogen atom or a substituted or unsubstituted monovalent organic group, and l, m, n
Represents 0 or a positive integer satisfying 2 ≦ l + m + n. ) A silsesquioxane ladder polymer having a number average molecular weight of 500 or more represented by the general formula (1)

[0007]

[Chemical 2]

(B) a silicon compound having at least two SiH groups in the molecule and having a molecular weight of 1000 or less, (C)
A silicon compound having at least two vinylsilyl groups in the molecule and having a molecular weight of 1000 or less, (D) a neutral platinum catalyst as an essential component, and (A) to (D) components of 50 to 300.
A pre-cured product obtained by heating at 0 ° C. to simultaneously carry out hydrolysis / condensation reaction of alkoxysilyl group and / or condensation reaction of silanol group and hydrosilylation reaction,
Flowability measurement with a high-performance flow tester using a die with a hole diameter of 1 mm and a length of 10 mm was performed at 150 ° C for 30 seconds.
After preheating for 60 seconds, 100kgf / cm
^2. A pre-cured product that can be melt compression molded and has a fluidity of 10 ⁻¹ to 10 ⁻⁶ cm ³ / s at a certain point in 30 minutes after the start of measurement under the condition of 150 ° C.

2. In the fluidity measurement according to 1 above, the precured product according to 1 above, which has a maximum fluidity of 10 ^-1 to 10 ^-6 cm ³ / s in a time range of 0 to 30 minutes after the start of measurement. 3. 3. The pre-cured product as described in 1 or 2 above, which contains a silanol condensation catalyst as an essential component as the component (E). 4. 4. The pre-cured product as described in 3 above, wherein the silanol condensation catalyst of the component (E) is a neutral organometallic compound.

5. The precured product as described in 3 above, wherein the silanol condensation catalyst of the component (E) is a titanium compound. 6. As the component (F), at least one component selected from the group consisting of a polyfunctional silicon compound capable of undergoing a hydrolysis / condensation reaction, a silanol compound, water, and a silica-based crosslinking agent is contained as an essential component. The pre-cured product according to 1 or 2 above.

7. 6. The pre-cured product as described in 1, 2, 4 or 5 containing the component (E) described in 3 above and the component (F) described in 6 above as essential components. 8. The pre-cured product according to any one of 1 to 7 is 5
A method for producing a molded product, which comprises compression molding under conditions of 0 to 500 ° C. and 1 to 500 kgf / cm ² . 9. A method for curing a molded article, which comprises subjecting the molded article obtained by molding the pre-cured product according to any one of 1 to 7 to the method described in 8 above to a post-heat treatment at 50 to 500 ° C.

The present invention will be described in detail below. First, the pre-cured product that is the first invention of the present invention will be described. The silsesquioxane ladder polymer which is the component (A) of the present invention has a structure represented by the formula (1), and its number average molecular weight is 500 or more. The number average molecular weight is 500 or more because of its good meltability and solubility in solvents.
It is preferably 0000 or less, more preferably 500 or more and 5000 or less, and particularly preferably 500 or more and 200 or less.
It is preferably 0 or less.

In the formula, R ¹ and R ² are a hydrogen atom or a substituted or unsubstituted monovalent organic group, and they may be the same or different from each other, specifically, a methyl group, an ethyl group,
n-propyl group, i-propyl group, n-butyl group, n-
Alkyl groups such as pentyl group, n-hexyl group, n-octyl group; aryl groups such as phenyl group, tolyl group, xylyl group; alkenyl groups such as vinyl group, allyl group, butenyl group, hexenyl group; chloromethyl group, Examples thereof include halogen-substituted alkyl groups such as trichloroethyl group and chloropropyl group. R ¹ is preferably a methyl group and R ² is preferably a phenyl group. R ³ is a hydrogen atom or a substituted or unsubstituted monovalent organic group, and specifically, a hydrogen atom or an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group; a phenyl group, Examples thereof include aryl groups such as tolyl group and xylyl group; alkenyl groups such as vinyl group, allyl group, butenyl group and hexenyl group; and halogen-substituted alkyl groups such as chloromethyl group, trichloroethyl group and chloropropyl group. Also, R ³
The _{-COCH 3, -N = C (Me} ) (Et), -
Highly active hydrolyzable groups such as C (CH ₃ ) ═CH ₂ can also be suitably used. Here, it is preferably a hydrogen atom, a methyl group or an ethyl group.

L, m and n are 0 satisfying 2 ≦ l + m + n
Or it is a positive integer. In the formula (1), R in 1 repeating unit (hereinafter, this unit is referred to as 1 unit)
¹ and R ² may be the same or different for each l unit. The same applies to R ¹ of m repeating units (hereinafter, this unit will be referred to as m unit), and the same applies to R ² of n repeating units (hereinafter, this unit will be referred to as n unit). . Further, the l unit, the m unit, and the n unit may be blocks or may be random in which these are mixed.

The ladder structure of the silsesquioxane ladder polymer may contain an irregular structure other than the ladder structure therein. Examples of the irregular structure include a structure having a bond defect in two column portions forming a ladder, that is, a ladder structure, and a structure having a bond defect in a horizontal bar portion connecting the two columns, as shown below. The deficient portion has a form in which a silanol group and / or an alkoxy group is bound.

[0016]

[Chemical 3]

Further, the following structure in which an irregular branched structure is further developed from the defective portion can be given.

[0018]

[Chemical 4]

In the formula, R is a hydrogen atom or a substituted or unsubstituted monovalent organic group, which may be the same or different from each other, and specifically, a hydrogen atom or a methyl group, an ethyl group or an n-propyl group. , I-propyl group, n-butyl group,
Alkyl group such as n-pentyl group, n-hexyl group, n-octyl group; aryl group such as phenyl group, tolyl group, xylyl group; alkenyl group such as vinyl group, allyl group, butenyl group, hexenyl group; chloromethyl Groups, halogen-substituted alkyl groups such as trichloroethyl group, chloropropyl group and the like.

R ³ is a hydrogen atom or a substituted or unsubstituted monovalent organic group, specifically, a hydrogen atom or a methyl group, an ethyl group, an n-propyl group, an i-propyl group,
n-butyl group, n-pentyl group, n-hexyl group, n-
Alkyl group such as octyl group; aryl group such as phenyl group, tolyl group, xylyl group; alkenyl group such as vinyl group, allyl group, butenyl group, hexenyl group; halogen such as chloromethyl group, trichloroethyl group, chloropropyl group Substituted alkyl groups and the like are exemplified. Further, as R ³ , -COCH ₃ , -N = C (Me) (Et), -C (CH
Highly active hydrolyzable groups such as ₃ ) = CH ₂ can also be suitably used. Here, it is preferably a hydrogen atom, a methyl group or an ethyl group.

The disordered structure may be contained in the compound of the formula (1) (excluding the disordered structure) in an amount of 80% by weight or less. Also,
The compound of formula (1) may be a partially cured product. Here, the partial curing is a structure in which an irregular branched structure is developed from the defective portion in the ladder structure as described below, and for example, the gel fraction (measured by the method defined in Example 1) is 5% to 30% compound.

[0022]

[Chemical 5]

Next, the components (B), (C) and (D) which are used in the present invention and which are cured by the hydrosilylation reaction will be explained. The component (B) used in the present invention is
Molecular weight 1 with at least 2 SiH groups in the molecule
Any silicon compound of 000 or less can be used without particular limitation. Specifically, the _{formula: HSiR 2 -X-SiR 2 H} (2) HSiR 2 H (3) H a SiR (4-a) (4) H (a-1) SiR (4-a) - ( _{X) m (SiRH) n SiR} (4-a) H (a-1) (5) R '- (X) m (SiRH) (n + 2) -R' (6) [X-SiR (4- _a) H _(a-2) ] _{(n + 2)} (7) (In the formula, R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ′ represents hydrogen or a monovalent organic group. , X represents a divalent group, a is an integer of 3 or 4, and n is an integer of 0 to 30), or three or more hydrogens on the aromatic ring are SiR ₂ H, An aromatic ring substituted with SiRH ₂ and SiH ₃ (R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms) and hydrosilane composed of the substituent can be preferably used. These compounds may be used alone or in combination of two or more. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in the formulas (2) to (7) include methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, isoamyl and n-. Examples thereof include octyl, n-nonyl, phenyl group, chloro group, trimethylsiloxy group and the like, with a methyl group and a phenyl group being preferred. Formulas (2), (5),
Specific examples of the divalent group: X in (6) and (7) include the structures shown below.

[0024]

[Chemical 6]

(In the formula, n represents an integer of 1 to 4.) Of these,

[0026]

[Chemical 7]

(In the formula, Me represents a methyl group, and n is the same as the above). Moreover,

[0028]

[Chemical 8]

(Wherein n is as defined above) is particularly preferred. In the formula (6), hydrogen or a monovalent organic group: R ′ is specifically hydrogen, methyl, ethyl, phenyl, trimethylsiloxy group or the like, and hydrogen is particularly preferable. As a preferred specific example of the component B,

[0030]

[Chemical 9]

(Wherein Me is the same as above, Ph is a phenyl group, and n is an integer of 3 to 5). Component (C) used in the present invention can be used without particular limitation as long as it is a silicon compound having at least two vinylsilyl groups in the molecule and having a molecular weight of 1000 or less. Specifically, the _{formula: CH 2 = CR'-SiR 2} -X-SiR 2 -CR '= CH 2 (8) CH 2 = CR'-SiR 2 -CR' = CH 2 (9) (CH 2 = CH _{) a SiR (4-a)} (10) (CH 2 = CH) (a-2) SiR (4-a) - (X) m -SiR (4-a) (CH = CH 2) (a-1 ) (11) R '- ( X) m [SiR (CH = CH 2)] (n + 2) -R' (12) [X-SiR (4-a) (CH = CH 2) (a-2 ₎ ] _{(N + 2)} (13) (wherein R, X, a and R ′ are the same as R, X, a and R ′ in the formulas (2) to (7), and a preferable structure is also The same, m is an integer of 1 to 31 and n is an integer of 0 to 30), or 3 or more hydrogens on the aromatic ring are SiR ₂ (CH═CH ₂ ), SiR
_{(CH = CH 2) 2,} Si (CH = CH 2) 3 (R is a monovalent represents a hydrocarbon group. 1 to 20 carbon atoms) such as vinyl silane comprising an aromatic ring and the substituent substituted by It can be preferably used. These compounds may be used alone or in combination of two or more. As the component (C),

[0032]

[Chemical 10]

(In the formula, Me and Ph are the same as above, and n is 3
Represents an integer of 5; The structure shown by this is preferable. In the present invention, in addition to the components (B) and (C) that can be cured by an addition reaction, an organosilicon compound having a molecular weight of 1,000 or less, each having at least one SiH group and one vinylsilyl group in the molecule, depending on the purpose of use. Can be used. Specifically, the following compounds:

[0034]

[Chemical 11]

(In the formula, Me is the same as above). The neutral platinum catalyst which is the component (D) of the present invention is preferably one that allows the hydrosilylation reaction and the hydrolysis / condensation reaction of the alkoxysilane to proceed in a good yield in one pot without causing the formation of undesired by-products. As the neutral platinum catalyst, platinum-organic compound complex, platinum-organofunctional siloxane complex, platinum-diolefin compound complex and the like can be used. Preferred are platinum-vinylsiloxane complex, platinum-acetylacetonate complex, platinum-decadiene complex and the like. With particular preference, Karstedt US Pat. No. 3,715,334,3.
775452 and 3814730 are platinum-vinyl siloxane complexes. The amount of the catalyst is not particularly limited, but it is preferable to use it in the range of 10 ^-1 to 10 ^-8 mol with respect to 1 mol of the SiH group. Furthermore, it is preferable to use it in the range of 10 ⁻³ to 10 ⁻⁶ mol.

In addition to the neutral platinum catalyst which is the component (D),
In some cases, it is possible to control the reaction rate of the hydrosilylation reaction by combining with a curing inhibitor,
It is possible to simultaneously proceed with the hydrosilylation reaction and the hydrolysis / condensation reaction of the alkoxysilane. As the curing inhibitor, a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, an organic peroxide and the like can be used. Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohol, an ene-yne compound, and a maleic acid ester such as dimethyl maleate. Examples of the organic phosphorus compound include triorganophosphine, diorganophosphine, organophosphon, triorganophosphite, and the like. Examples of the organic sulfur compound include organomercaptan, diorganosulfide, hydrogen sulfide, benzothiazole, benzothiazole disulfite and the like. Examples of the nitrogen-containing compound include ammonia, primary to tertiary alkyl amines, aryl amines, urea, hydrazine and the like. Examples of the tin-based compound include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, t-butyl perbenzoate and the like.

The silanol condensation catalyst of the component (E) is used to accelerate the hydrolysis / condensation reaction of the terminal functional group SiOR ³ of the silsesquioxane ladder polymer of the component (A) represented by the formula (1). be able to. In the claim 3, the term "containing the component (E) as an essential component" means (A).
At least one or more time points selected from before the formation of the pre-cured product of (D), during the formation of the pre-cured product, and after the formation of the pre-cured product and before compression molding of the pre-cured product. It means to mix with these components and / or the pre-cured product.

As the component (E), various kinds of conventionally known acid catalysts, alkali catalysts, organic metal compounds and the like can be widely used and are not particularly limited. Specific examples thereof include acid catalysts. Examples thereof include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid, activated clay, iron chloride, boric acid, trifluoroacetic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid. Examples of the alkali catalyst include hydroxides of alkali metals or alkaline earth metals, alkoxides of alkali metals or alkaline earth metals, tetraalkylammonium hydroxides, tetraalkylphosphonium hydroxides, amine compounds and the like. As the amine compound,
For example, pyridine, picoline, lutidine, pyrazine, piperidone, piperidine, piperazine, pyrazole, pyridazine, pyrimidine, pyrrolidine, butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, Diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine,
2,4,6-Tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-
4-Methylimidazole, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), or salts of these amine compounds with carboxylic acid, etc., low molecular weight obtained from excess polyamine and polybasic acid Polyamide resin, reaction product of excess polyamine and epoxy compound, γ-aminopropyltrimethoxysilane, N- (β
Examples include silane coupling agents having an amino group such as -aminoethyl) aminopropylmethyldimethoxysilane. Further, a fluorinated compound such as tetrabutylammonium fluoride, potassium fluoride or sodium fluoride can be used. Organic metal compound catalysts include organic acid salts such as tin, lead, zinc, iron, cobalt, titanium, aluminum, zirconium and boron, alkoxides and chelates.

Specific examples of the tin-based catalyst used in the present invention include, for example, the general formula (14)

[0040]

[Chemical 12]

(R ⁵ represents a substituted or unsubstituted monovalent hydrocarbon group. For example, a substituted alkyl group such as an alkyl group and a chloromethyl group, an alkenyl group such as a vinyl group and an allyl group, and a phenyl group. Group, aryl group such as tolyl group, etc. Y ¹ and Y ² have 1 carbon atoms.
To 8 are alkyl groups, alkoxy groups, d is 0, 1 or 2). Alternatively, for example, the general formula (15)

[0042]

[Chemical 13]

(R ⁶ represents a substituted or unsubstituted monovalent hydrocarbon group. For example, a substituted alkyl group such as an alkyl group and a chloromethyl group, an alkenyl group such as a vinyl group and an allyl group, a phenyl group and a tolyl group. And aryl groups such as groups). For example, tin (II) methoxide, tin (II) ethoxide, tin (II) 2,4-pentanedionate, tin (II) octoate, tin acetate (II),
Examples thereof include dibutyltin dilaurate, dibutyltin malate, dibutyltin diacetate, tin naphthenate, a reaction product of dibutyltin oxide and a phthalic acid ester, and dibutyltin diacetylacetonate. Specific examples of the lead catalyst used in the present invention include, for example, general formula (16)

[0044]

[Chemical 14]

(Y ³ and Y ⁴ are a substituted or unsubstituted alkyl group or alkoxy group having 1 to 8 carbon atoms). For example, lead (II) hexafluoropentanedionate, lead (II) 2,4-pentanedionate, lead (II) 2,
2,6,6-tetramethyl-3,5-heptanedionate, lead octylate and the like can be mentioned. Specific examples of the zinc-based catalyst used in the present invention include the general formula (17)

[0046]

[Chemical 15]

(R ⁷ represents a substituted or unsubstituted monovalent hydrocarbon group. For example, a substituted alkyl group such as an alkyl group and a chloromethyl group, an alkenyl group such as a vinyl group and an allyl group, a phenyl group and a tolyl group. Examples thereof include aryl groups such as groups, etc. Y ⁵ and Y ⁶ are alkyl groups having 1 to 8 carbon atoms, alkoxy groups, and e is 0, 1 or 2). Alternatively, for example, the general formula (18)

[0048]

[Chemical 16]

(R ⁸ represents a substituted or unsubstituted monovalent hydrocarbon group. For example, a substituted alkyl group such as an alkyl group and a chloromethyl group, an alkenyl group such as a vinyl group and an allyl group, a phenyl group and a tolyl group. And aryl groups such as groups). For example, dimethoxyzinc, diethoxyzinc, zinc methoxyethoxide, zinc 2,4-pentanedionate, zinc acetate, zinc 2-ethylhexanoate, zinc formate, zinc methacrylate, zinc neodecanoate, zinc undecylenate, zinc octylate. And so on.

Specific examples of the iron catalyst used in the present invention include, for example, the general formula (19)

[0051]

[Chemical 17]

(R ⁹ represents a substituted or unsubstituted monovalent hydrocarbon group. For example, a substituted alkyl group such as an alkyl group and a chloromethyl group, an alkenyl group such as a vinyl group and an allyl group, a phenyl group and a tolyl group. And aryl groups such as groups, etc. Y ⁷ and Y ⁸ are substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms, alkoxy groups, f is 0,
1, 2, or 3). Examples thereof include iron (III) benzoylacetonate, iron (III) ethoxide, iron (III) 2,4-pentanedionate, iron (III) trifluoropentanedionate, and iron octylate.

Specific examples of the cobalt-based catalyst used in the present invention include the general formula (20)

[0054]

[Chemical 18]

(Y ⁹ and Y ¹⁰ are each a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an alkoxy group, and g is 2 or 3). Examples thereof include cobalt (II) 2,4-pentanedionate and cobalt (III) 2,4-pentanedionate. Specific examples of the titanium-based catalyst used in the present invention include tetraalkyl orthotitanate and titanium chelate. Tetraalkyl orthotitanate is represented by, for example, the general formula (21)

[0056]

[Chemical 19]

(In the formula, R ¹⁰ is a substituted or unsubstituted monovalent hydrocarbon group, preferably a hydrocarbon group having 1 to 4 carbon atoms). Examples of such a monovalent hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. The titanium chelate has, for example, the general formula (22):

[0058]

[Chemical 20]

(In the formula, R ¹¹ , R ¹² , and R ¹⁴ represent a monovalent hydrocarbon group, and R ¹³ represents a hydrogen atom or a monovalent hydrocarbon group). Examples of such titanium chelates include diisopropoxybis (ethyl acetoacetate).
Examples include titanium, diisopropoxybis (methylacetoacetate) titanium, diisopropoxybis (acetylacetone) titanium, dibutoxybis (ethylacetoacetate) titanium and the like. Specific examples of the aluminum alkoxide used as a catalyst in the present invention include, for example, the general formula (23)

[0060]

[Chemical 21]

(Wherein R ¹⁵ is a substituted or unsubstituted alkyl group, X is a monovalent negative group other than an alkoxy group, h is 0,
1, 2, or 3). The most preferable aluminum alkoxide is h in the general formula (23).
Is an aluminum trialkoxide where 3 is 3, but a compound in which a part of the alkoxy group is substituted with X or the like may be used. X is a halogen atom such as F ⁻ , Cl ⁻ or Br ⁻ , or a general formula (24)

[0062]

[Chemical formula 22]

A negative group represented by (Y ¹¹ and Y ¹² represent an alkyl group or an alkoxy group having 1 to 8 carbon atoms) is preferable. Specifically, aluminum triisopropoxide, aluminum trisecondary butoxide, aluminum diisopropoxy second butoxide, aluminum diisopropoxide acetylacetonate, aluminum disecondary butoxide acetylacetonate, aluminum diisopropoxide ethylacetate. Examples thereof include acetate and aluminum di (secondary butoxide) ethylacetoacetate. Specific examples of the zirconium alkoxide or chelate used as the catalyst in the present invention include, for example, the general formula (25).

[0064]

[Chemical formula 23]

(R ¹⁶ represents a substituted or unsubstituted monovalent hydrocarbon group. For example, a substituted alkyl group such as an alkyl group and a chloromethyl group, an alkenyl group such as a vinyl group and an allyl group, a phenyl group and a tolyl group. Examples thereof include aryl groups such as groups, etc. Y ¹³ and Y ¹⁴ are alkyl groups having 1 to 8 carbon atoms, alkoxy groups, and i is 0, 1, 2, 3, or 4). Specifically, zirconium tetrabutoxide, zirconium tetraisopropoxide, zirconium tetramethoxide, zirconium tributoxide monoacetylacetonate, zirconium dibutoxide bisacetylacetonate, zirconium monobutoxide trisacetylacetonate, zirconium tributoxide monoethylacetate. Examples thereof include acetate, zirconium dibutoxide bisethylacetoacetate, zirconium monobutoxide trisethylacetoacetate, zirconium tetraacetylacetonate, and zirconium tetraethylacetoacetate.

Specific examples of the boron alkoxide catalyst used in the present invention include the general formula (26)

[0067]

[Chemical formula 24]

(R ¹⁷ represents a substituted or unsubstituted monovalent hydrocarbon group. For example, a substituted alkyl group such as an alkyl group and a chloromethyl group, an alkenyl group such as a vinyl group and an allyl group, a phenyl group and a tolyl group. And aryl groups such as groups). Examples thereof include boron methoxide, boron ethoxide, boron n-butoxide and the like. These catalysts may be used alone or in combination of two or more if no problem.
Preferred catalysts are neutral organometallic compounds, more preferably titanium-based and aluminum-based catalysts, and particularly preferred catalysts are titanium-based catalysts. The amount of the catalyst used is 0.01 to 20 parts by weight, preferably 0.3 to 1 with respect to 100 parts by weight of the silsesquioxane ladder polymer.
0, most preferably 0.5 to 6 parts by weight.

Further, at least one selected from the group consisting of the polyfunctional silicon compound capable of undergoing a hydrolysis / condensation reaction which is the component (F) in the present invention, a silanol compound, water, and a silica-based crosslinking agent is used. In this case, the condensation reaction between the alkoxy group or silanol group contained therein or the silanol group produced by hydrolysis, or the functional group and the terminal of the silsesquioxane ladder polymer represented by the formula (1) It is possible to accelerate the condensation reaction of the functional group SiOR ³ .

In the sixth aspect, the inclusion of the component (F) as an essential component means that the precured products (A) to (D) are produced, during the formation of the precured products, and the formation of the precured products. It refers to the mixing with these components and / or the pre-cured product at a later time and at least one or more time points selected from before compression molding of the pre-cured product. Further, in claim 7, the fact that the component (E) and the component (F) are contained as essential components has the same meaning as described above.

As the polyfunctional silicon compound which is one of the component (F) in the present invention, the compound represented by the formula (27) can be preferably used.

[0072]

[Chemical 25]

(R¹⁸Is a substituted or unsubstituted monovalent hydrocarbon
Represents a base. For example, alkyl group and chloromethyl group
Alkanes such as substituted alkyl groups, vinyl groups and allyl groups
Aryl groups such as nyl, phenyl, tolyl, etc.
And so on). Preferably hydrogen source
Child, a methyl group, and k is a positive group satisfying 1 ≦ k ≦ 10
It is an integer, preferably 4 on average. For example, Si (OM
e)_Four , Si (OEt) _Four , Si (OAc)_Four , MeO
{Si (OMe)₂ O}_nMe (n = average 3 to 6), E
tO {Si (OEt)₂ O}_nEt (n = average 3 to 6)
Etc. can be mentioned. Other than that shown in equation (27)
As the compound, MeSi (OMe)₃ , MeSi (O
Et)₃ , MeSi (OAc)₃ , MeSi (OC (C
H₃ ) = CH₂ )₃ , MeSi (ON = CMeEt)
₃ , Me₂ Si (N (Et) CO (Me))₂ , Me₂ 
Si (N (Me) CO (Me))₃ Etc.
come. The amount of this polyfunctional crosslinking agent used is silsesquioxa
1 to 50 parts by weight based on 100 parts by weight of ladder polymer
And preferably 10 to 50 parts by weight.

As one of the components (F) of the present invention, sila
A nol compound can be used. Illustrate concretely
Then Ph₂ Si (OH)₂ , PhMe₂ SiOH,
Ph ₂ MeSiOH, PhSi (OH)₃ And its low
Examples include molecular weight oligomers. Also, HO
Si (Me)₂ -P-C₆ H_Four -Si (Me)₂ OH,
HOSi (Me)₂ -M-C₆ H_Four -Si (Me)₂ O
H, (HO)₂ SiMe-p-C₆ H_Four -SiMe (O
H)₂ , (HO)₂ SiMe-m-C₆ H_Four -SiMe
(OH)₂ Etc. are also illustrated.

The amount of the silanol compound used is 1 to 5 with respect to 100 parts by weight of the silsesquioxane ladder polymer.
It is 0 parts by weight, preferably 10 to 50 parts by weight.
Further, water can be added and used as one of the components (F) of the present invention. The amount of water added is arbitrary,
It is preferably 5 to 100 mol% with respect to the terminal alkoxy group of the silsesquioxane ladder polymer as the component (A). Further, it is more effective to use water in combination with the above-mentioned hydrolyzable / condensable polyfunctional silicon compound. Also in this case, the amount of water added is arbitrary, but it is preferably 5 to 100 mol% with respect to all the alkoxy groups of the component and the component (A).

Examples of the silica-based crosslinking agent as the component (F) that can be used in the present invention include finely powdered hydrous silica or anhydrous silica, and silica powder treated with various surface treatment agents. These silanol groups or adsorbed water participate in the condensation reaction of the terminal functional group SiOR ³ of the silsesquioxane ladder polymer represented by the formula (1), and the physical properties of the resulting cured product can be improved. The amount of the silica-based crosslinking agent used is preferably 5 to 30 parts by weight with respect to 100 parts by weight of the silsesquioxane ladder polymer. These silica-based crosslinking agents may be used in combination with the above-mentioned hydrolyzable / condensable polyfunctional silicon compound, silanol compound, and water.

Furthermore, an organic solvent can be used to uniformly mix the above components. For example, hydrocarbon solvents such as benzene, hexane, toluene and heptane, ether solvents such as tetrahydrofuran, 1,4-dioxane and diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, halogen solvents such as chloroform and methylene chloride. Can be preferably used. The solvent can also be used as a mixed solvent of two or more kinds. Tetrahydrofuran, toluene and chloroform are preferable as the solvent. Tetrahydrofuran is more preferred. The amount of the organic solvent used is 1 to 200 mL, preferably 50 to 150 mL, and more preferably 8 to 100 g of silsesquioxane.
It is 0 to 120 mL.

As described above, in the present invention, the silsesquioxane ladder polymer and its partially cured product, various catalysts, organic solvents, polyfunctional silicon compounds capable of undergoing hydrolysis / condensation reaction, silanol compounds, water, and silica-based crosslinking agents are used. Can be mixed and used. In the present invention, (A)-
In addition to the component (F), various components can be added depending on the purpose. For example, for the purpose of improving mechanical function, glass fiber, carbon fiber, silicone carbide fiber, silicone nitride fiber, organic fiber such as titanium fiber or aramid, potassium titanate whiskers, mica, glass flakes, graphite, molybdenum sulfide, etc. Can be added. Metal powder or metal coating filler can be used for the purpose of improving electrical performance. Aluminum hydroxide, magnesium hydroxide, antimony trioxide and the like can be used to improve the thermal characteristics.

The precured product of the present invention heats the components (A) to (D) or these components (E) and (F) to 50 to 300 ° C. to appropriately react the components. That is, the fluidity was measured by a high-performance flow tester using a die having a hole diameter of 1 mm and a length of 10 mm.
100 kgf / c after preheating for 60 seconds to 60 seconds
It may be carried out under conditions of m ² and 150 ° C. so that the fluidity at a certain point in 30 minutes after the start of the measurement is 10 ⁻¹ to 10 ⁻⁶ cm ³ / s. Here, the reaction means that the hydrolysis / condensation reaction of the alkoxysilyl group and / or the silanol group in the component and the hydrosilylation reaction are simultaneously carried out.

At a certain point within 30 minutes after the start of the measurement of the fluidity in the present invention, the pre-cured product outside the scope of the present invention causes the following disadvantages. If pre-curing is insufficient, the fluidity within the measurement time will be 10 ^-1 cm ³ / s.
The workability is impaired, for example, it will flow out of the mold and overflow from the formwork due to too much flow. If pre-cured too much, the maximum fluidity does not reach 10 ^-6 cm ³ / s, and a uniform melt compression molded product cannot be obtained (see FIG. 1).

As a specific method for obtaining the pre-cured product of the present invention, the above components are directly placed in a mold such as metal or glass, or a polyimide film or aluminum foil is laid and placed in an oven. Heat to ~ 300 ° C. Alternatively, a heatable kneading device such as a hot roll or a kneader is used. It is also possible to use a high frequency heating device. The temperature may be kept constant or may be raised stepwise or continuously. By heating, the reaction of the condensation component and the addition component is allowed to proceed in a well-balanced manner, curing is promoted, and a pre-cured product having fluidity during molding can be obtained. Although the heating temperature and the heating time depend on the kind of the material, it is preferable that the heating temperature and the heating time are approximately 50 to 200 ° C. and several minutes to 5 hours. An organic solvent may be used to ensure reliable and rapid mixing / dispersion. The amount of the organic solvent used is 1 to 200 mL, preferably 50 to 150 mL, and more preferably 80 per 100 g of silsesquioxane.
~ 120 mL. In addition, a mortar, a freeze pulverizer, various mills, kneaders, rolls, homogenizers, stirring devices, etc. can be used to mix the components (A) to (F) with various fibers, metal powders, and fillers. It is more effective to mix in a molten state while heating. Samples pre-cured in this way are powdered, granular, flaky,
It can be made into pellets or tablets.

The fluidity of the pre-cured product was evaluated by the Koka type flow test.
-A tester is used, but one made by Shimadzu
You can The high-performance flow tester is placed in the cylinder.
The entered resin is heated to a certain temperature to melt it, and the piston
Apply a constant pressure P to the die hole N (diameter D, length
L) is used to flow out the resin, and the resin flow-out amount Q and its time variation
The fluidity and curing behavior of the resin can be known by
It is a device. The pre-cured product of the present invention has a hole diameter of 1 mm,
With an advanced flow tester that uses a die with a length of 10 mm
The fluidity measurement is performed at 150 ° C for 30 to 60 seconds.
After heating, 100kgf / cm² , 150 ℃ condition
Flow at a certain point in 30 minutes after starting measurement
Sex is 10^-1-10^-6cm³ / S, preferably 10^-2~
10^-Fivecm ³ / S, most preferably 10^-3-10^-Fourcm
³ / S is a pre-cured product, the preferred embodiment is the same
The maximum fluidity is 0 to 30 minutes after the start of measurement.
Liquidity is 10^-1-10^-6cm³ / S, preferably 10
^-2-10^-Fivecm³ / S, most preferably 10^-3-10^-Four
cm³ It is a pre-cured product showing / s. Maximum liquidity is 10
^-1cm³ The pre-cured product of over s / s is not sufficiently pre-cured.
And work such as flowing out of the form due to too much flow
Sex is impaired. Also, the maximum liquidity is 10^-6cm³ / S
The pre-cured product that does not exceed the maximum
There is a problem that a melt compression molded product cannot be obtained.

A method for producing a molded article, which is the second aspect of the present invention, will be described. In the molding method of the present invention, a pre-cured product is compression-molded under the conditions of 50 to 500 ° C. and 1 to 500 kgf / cm ² , but in the point that a condensation component is generated at the time of curing, it is the same curing type phenol. Examination was performed according to the resin molding method (preliminary curing → crushing → powdering → melt compression molding), and a shape-retained test piece was obtained. The method will be specifically described below.

The pre-cured product of the first invention of the present invention, which is in the form of powder, granules, flakes, pellets, tablets, etc., is placed in a mold and heated to 50 to 500 ° C.
Molding is performed by applying a pressure of 500 kgf / cm ² . By preheating the molding material using a heating device such as an oven or high-frequency preheater before pressurizing, shortening the molding time,
The efficiency can be improved. Preheating temperature is 50 ~
It is preferable that the temperature is 200 ° C. and the time is several seconds to 10 minutes. The compression molding temperature is preferably such that the pre-cured sample melts. Molding pressure is in the range of 1~500kgf / cm ^2, preferably 50~300kgf / cm ^2, 10
-200 kgf / cm ² is more preferable. The molding time needs to be optimized according to the sample amount, the degree of pre-curing, the shape of the mold, etc. However, in the standard prescription, when a sample with a projected area of 1 × 10 cm ² is used, About 1 minute to 10 hours is preferable per 4 mm of the thickness of the molded body. Furthermore, about 10 minutes to 1 hour is preferable.

The molded body after compression molding is kept at 50 to 500 ° C. for a certain time, usually 1 hour to 24 hours, preferably 5 hours to.
The post-heat treatment for 10 hours can reduce internal stress and improve heat resistance. Such after-curing conditions depend on the shape of the molded body material and the molding conditions, but in general, a method of heating from a temperature slightly lower than the molding temperature and gradually raising the temperature is preferable. It is possible to prevent the deterioration of the material by performing the after-cure in an inert gas atmosphere or in a vacuum degassing condition. In this way, a molded body of any shape can be produced.

The precured product of the present invention and its molded product can be used as a paint / protective coating material.
Further, the pre-cured product of the present invention and the molded article thereof are adhesives,
It can be used as an adhesive and a contact adhesive. Further, it can be used as various thermosetting resins or as a modifier of thermosetting resins. The pre-cured product and the molded product thereof of the present invention can be used as an electronic / electrical material. Specifically, a rigid wiring board for semiconductor mounting,
Flexible printed wiring board, adhesive material for semiconductor mounting,
Adhesives for flexible printed wiring boards, resins for semiconductor encapsulation, encapsulants around electrical and electronic parts, insulating films for semiconductors, cover lay films for protecting flexible printed circuits, resin modifiers, wiring coating coating agents, etc. Can be used for. The pre-cured product and its molded product can be used as a civil engineering / building material. Specifically, it is a sealing agent, a vibration-damping / vibration-proof material, a paint, an adhesive, a coating agent spraying agent, a waterproofing agent, a structural member and the like. It can also be used as a material for automobiles and aircraft. Specifically, it is a sealant, a sliding member, a coating agent, a structural member, an adhesive, a molding material, or the like. Examples of the optical material include a core material and a clad material for an optical fiber, and an abrasion resistant coating agent for plastic lenses. As a medical material, artificial bone or the like can be used. The fields of application and uses of the pre-cured product and the molded product of the present invention are not limited to the fields described above.

[0087]

EXAMPLES The present invention will be specifically described below with reference to examples, but the scope of the present invention is not limited thereto. As the silsesquioxane ladder polymer, glass resin (trade name) manufactured by Showa Denko KK, GR-10 in which the ratio of substituents on silicon is methyl group / phenyl group = 2/1
0 (Mw / Mn = 7210/1260) and methyl group /
GR-950 (Mw / Mn = 10) of phenyl group = 0/1
80/690). The catalyst, diisopropoxybis (acetylacetone) titanium, is T-50 (isopropyl alcohol solution (75%)) manufactured by Nippon Jita Co., Ltd.
It was used. (Example 1) In a 100 mL glass sample bottle, G
32.5 g of R100 was weighed and added. After adding 33 mL of tetrahydrofuran (THF) as a solvent thereto, the glass resin was completely dissolved using an ultrasonic cleaner. After the glass resin was completely dissolved, the condensation catalyst Ti (Oi-Pr) ₂ (acac) ₂ (iP
r: isopropyl, acac; acetylacetonate) (974 mg) and water (1.24 g) were added. In another 30 mL sample tube, 5.25 g (21.3 mmol) of 1,4-bis (dimethylvinylsilyl) benzene, 1,3,5,5.
2.56 g of 7-tetramethylcyclotetrasiloxane
(10.7 mmol) is weighed, and 61 mg of a 1 wt% THF solution of dimethylmalate as a curing inhibitor is weighed therein.
(10 equivalents to platinum catalyst) was added, and the mixture was shaken lightly to mix. The carbosilane solution and the silsesquioxane polymer solution are mixed (silsesquioxane polymer component /
Carbosilane component = 8/2 (weight ratio), Pt-vinylsiloxane complex (H ₂ PtCl ₆ .6H ₂ O / [Me ₂
(CH ₂ ═CH) Si] ₂ O / synthesized from NaHCO ₃ / toluene, 9.71 × 10 ⁻⁶ mmol / mg) 64 m
g (1 × 10 ⁻⁵ relative to Si-vinyl group).

A polyimide film having a thickness of 25 μm was previously spread with a double-sided tape so that the bottom surface was 13 × 17c.
The metal container of m was prepared. The solution prepared in the above procedure was gently poured into this. The container was covered with an aluminum foil, and then left still in a hot air dryer adjusted to 50 ° C. so as to be horizontal. Then, it preheated by heating at 50 degreeC for 12 hours. After cooling the obtained yellow transparent rubber-like solid with dry ice,
Grind using a mortar and use a vacuum pump to bring it to room temperature at 3.5.
It dried over time. The obtained pre-cured product was in the form of a yellow powder, and its gel fraction was 54%. The fluidity of the obtained pre-cured product was evaluated using a Koka type flow tester. For the measurement, a die with a diameter of 1 mm and a height of 10 mm is used.
After preheating at 50 ℃ for 60 seconds, 150 ℃, 100k
It was evaluated under the condition of gf / cm ² . The results are shown in Fig. 1. In FIG. 1, the horizontal axis represents the elapsed time including preheating (60 sec), and the vertical axis represents the fluidity (cm) of the pre-cured product (resin).
³ / s).

The gel fraction was determined by the following (same below). The gel fraction was measured by the following procedure. Put about 100 mg of resin in the wire net, 50 mL of tetrahydrofuran
Soaked it for 12 hours. Take out the net 90 ° C
And dried for 2 hours. The gel fraction was calculated by the following formula. Gel fraction (%) = (total weight after extraction−net weight) /
(Total weight before extraction-net weight) × 100 (Example 2) G in a 200 mL glass sample bottle
74.8 g of R100 was weighed and added. After adding 75 mL of tetrahydrofuran (THF) as a solvent thereto, the glass resin was completely dissolved using an ultrasonic cleaner. After the glass resin was completely dissolved, the condensation catalyst Ti (Oi-Pr) ₂ (acac) ₂ was added to 2.37.
g and 2.84 g of water were added. Add 1,4-bis (dimethylvinylsilyl) benzene 1 to another 50 mL sample tube.
2.07 g (50.0 mmol), 1,3,5,7-tetramethylcyclotetrasiloxane 5.89 g (24.
(5 mmol) was weighed, 141 mg (10 equivalents to the platinum catalyst) of a 1 wt% THF solution of dimethylmalate, which is a curing inhibitor, was added thereto, and shaken gently to mix. The carbosilane solution and the silsesquioxane polymer solution were mixed (silsesquioxane polymer component / carbosilane component = 8/2 (weight ratio)), and the Pt-vinylsiloxane complex (H ₂ PtCl ₆ .6H ₂ O / [ Me ₂ (CH ₂
= CH) Si] ₂ O / synthesized from NaHCO ₃ / toluene, 110 mg of 9.71 × 10 ⁻⁶ mmol / mg) was added (1 × 10 ^{−5 with} respect to the Si-vinyl group).

A polyimide film having a thickness of 25 μm was previously prepared.
The bottom of the film laid with double-sided tape is 19 x 27c
The metal container of m was prepared. In this, above
The solution prepared in the procedure was gently poured. This container
After covering with Lumi foil, adjust the temperature to 50 ° C in advance.
It was left to stand horizontally in a prepared hot air dryer. That
After that, preheating was performed by heating at 50 ° C. for 12 hours. Obtained
After cooling the yellow transparent rubbery solid with dry ice,
Grind in a mortar and use a vacuum pump at room temperature for 6 hours
It dried over. The obtained pre-cured product is a yellow powder.
The gel fraction was 57%. Obtained pre-cure
The fluidity of the product was evaluated using a Koka type flow tester.
The conditions are the same as those described in Example 1. as a result
Is shown in FIG. 2 as in FIG. (Example 3) About 5 g of the pre-cured product obtained in Example 1 was added.
Enter the mold (1 x 10 cm) heated to 150 ℃
After preheating for 1 minute in a hot air dryer at 150 ° C,
150 ° C / 50kgf / cm² Primary under the condition of / 1 min
Pressurization was applied. After that, degassing is performed once and 150 ° C
/ 100kgf / cm² Secondary pressure under the condition of / 60min
I went. 150 ℃ / after removing the molded body from the mold
4h / normal pressure → 180 ° C / 5h / post-heating under vacuum
went. Yellow transparent rod-shaped molded product (3.5 × 9.8 × 97.
2 mm) was obtained. Measured according to JIS-K7203
Mechanical properties: flexural modulus 1.92 GPa, maximum strength 4
The maximum elongation was 1.9 MPa and the maximum elongation was 2.7%. 5% weight
The weight reduction rate is 545 ℃ and 500 ℃.
It was 3.4%. (Example 4) About 5 g of the pre-cured product obtained in Example 1 was added.
Enter the mold (1 x 10 cm) heated to 150 ℃
After preheating for 1 minute in a hot air dryer at 150 ° C,
150 ° C / 50kgf / cm² Primary under the condition of / 1 min
Pressurization was applied. After that, degassing is performed once and 150 ° C
/ 100kgf / cm² Secondary pressure under the condition of / 60min
I went. 150 ℃ / after removing the molded body from the mold
4h / normal pressure → 180 ° C / 5h / post-heating under vacuum
went. Yellow transparent rod-shaped molded product (3.1 × 9.7 × 97.
2 mm) was obtained. In accordance with JIS-K7110
The impact resistance was evaluated. Izod impact value 2.7 kJ / m² 
Met. 5% weight loss temperature is 560 ℃, 500 ℃
The weight loss rate was 2.9%. The specific gravity is 1.
2299 g / cm³ Met. (Example 5) About 6 g of the pre-cured product obtained in Example 2 was added.
Enter the mold (1 x 12 cm) heated to 150 ℃
After preheating for 1 minute in a hot air dryer at 150 ° C,
150 ° C / 50kgf / cm² Primary under the condition of / 1 min
Pressurization was applied. After that, degassing is performed once and 150 ° C
/ 100kgf / cm² Secondary pressure under the condition of / 15min
I went. 150 ℃ / after removing the molded body from the mold
After post-heating at 16h / normal pressure, the temperature shoe shown in Fig. 3
After that, post-heating was performed. In FIG. 3, the horizontal axis represents elapsed time and the vertical axis represents
The temperature was indicated. Also, in the initial 30 minutes, nitrogen is 50 L / min,
Nitrogen can be heated up to 10 L / min for 9 hours after that in a dryer
It was carried out by circulating and supplying to the molded body which was left still.
Yellow transparent rod-shaped body (4.2 x 9.7 x 116.9 m
m) was obtained. Deflection temperature under load according to JIS-K7207
Degree (HDT) was measured (load: 18.5 kgf / cm
² ). HDT> 280 ° C. or higher. (Example 6) About 2.5 g of the pre-cured product obtained in Example 2
The mold (0.65 × 10
cm) and preheat for 1 minute in a hot air dryer at 150 ° C.
After heating, 150 ℃ / 50kgf / cm² / 1 min
Primary pressurization was performed under the conditions. After that, degas once
150 ℃ / 100kgf / cm² / 15min Article
Secondary pressurization was performed in some cases. The molded body was taken out of the mold
After that, after post-heating at 150 ° C./16 h / normal pressure, FIG.
Post-heating was performed with the temperature history shown in. Yellow transparent rod molding
A body (2.8 × 6.5 × 97.8 mm) was obtained. JIS-
Oxygen index measured according to K7201 is 51.5-5
A value of 3.5 was shown. Example 7 In a 200 mL glass sample bottle, G
50.0 g of R100 was weighed and added. There solvent
50 mL of tetrahydrofuran (THF) was added as
After that, completely dissolve the glass resin using an ultrasonic cleaner.
Let After the glass resin has completely dissolved, use a condensation catalyst.
Ti (O-i-Pr)₂ (Acac)₂ To 1.50
g and 1.89 g of water were added. Another 50 mL sample tube
1,4-bis (dimethylvinylsilyl) benzene 3
1.23 g (127 mmol), 1,3,5,7-teto
Lamethylcyclotetrasiloxane 15.27 g (63.
5 mmol) was weighed, and there was a curing inhibitor, Dimethy.
183 mg of lumarate (500 equivalent to platinum catalyst)
Amount) and shaken lightly to mix. This carbosilane solution
And the silsesquioxane polymer solution (silse
Squioxane polymer component / carbosilane component = 5/5
(Weight ratio)), Pt-vinyl siloxane complex (H₂ Pt
Cl ₆ ・ 6H₂ O / [Me₂ (CH₂ = CH) Si]₂ 
O / NaHCO₃ / Synthesized from toluene, 9.71 × 10
^-6260 mg of (mmol / mg) was added (Si-vinyl
1 x 10 for the group^-Five).

A polyimide film having a thickness of 25 μm was previously spread with double-sided tape so that the bottom surface was 16 × 23c.
The metal container of m was prepared. The solution prepared in the above procedure was gently poured into this. The container was covered with an aluminum foil, and then left still in a hot air dryer adjusted to 50 ° C. so as to be horizontal. Then, it heated at 50 degreeC for 13 hours, and pre-cured. The obtained yellow transparent jelly-like solid was cooled with dry ice, pulverized with a mortar, and dried at room temperature for 7.5 hours using a vacuum pump. The obtained pre-cured product was a yellow solid, and its gel fraction was 61%. The fluidity of the obtained pre-cured product was evaluated using a Koka type flow tester. The conditions are the same as those described in Example 1.
The results are shown in FIG. 4 as in FIG. (Example 8) About 2.5 g of the pre-cured product obtained in Example 7
The mold (0.65 × 10
placed in cm), was preheated for 1 minute in a 0.99 ° C. in a hot air dryer, was primary pressure under the conditions of ^{150 ℃ / 50kgf / cm 2 /} 1min. After that, degassing was performed once. Gradually 100 kgf / cm for 2 minutes at 150 ° C
^The pressure was increased to ² , and then the secondary pressure was applied for 30 minutes while maintaining the pressure. After removing the molded body from the mold, 150
After the post-heating at ℃ / 16h / normal pressure, the post-heating was performed with the temperature history shown in FIG. Yellow transparent rod-shaped body (3.2
X 6.5 x 97.5 mm) was obtained. JIS-K7201
The oxygen index measured according to the above method was 36.1 to 36.4. (Example 9) A kneader obtained by heating 150 g of GR100 to 100 ° C. (a tabletop kneader manufactured by Irie Shokai, PBV-0.
(Type 3) and kneaded for 14 minutes to melt. 1,4-
Bis (dimethylvinylsilyl) benzene 24.14g
(100 mmol), 11.3,5,7-tetramethylcyclotetrasiloxane 11.78 g (49.0 mmo)
l) was mixed to give a carbosilane solution. The carbosilane solution was added 14 minutes after the start of kneading (silsesquioxane polymer component / carbosilane component = 8/2 (weight ratio)). Ti (Oi-Pr) ₂ (ac
ac) ₂ 4.74 g, water 5.68 g, Pt-vinyl siloxane complex (H ₂ PtCl ₆ .6H ₂ O / [Me ₂
220 (CH ₂ = CH) Si] ₂ O / NaHCO ₃ / toluene, 9.71 × 10 ⁻⁶ mmol / mg)
mg (1 × 10 ^{−5 with} respect to the Si-vinyl group), 28 wt% of a 1 wt% THF solution of dimethylmalate as a curing inhibitor.
2 mg were mixed to obtain a catalyst solution. 18 minutes after the kneading was started, the catalyst solution was added together with the carbosilane solution. The addition of the carbosilane solution was completed after 40 minutes, and the addition of the catalyst solution was completed after 45 minutes. The pre-cured product obtained after 5 minutes was taken out.

The obtained pre-cured product was crushed using a mortar
It was The gel fraction was 58%. Obtained pre-cure
The fluidity of the product was evaluated using a Koka type flow tester.
The conditions are the same as those described in Example 1. Start measurement
Maximum fluidity in the next 0 to 30 minutes is 4 × 10^-3cm³ 
Was / s. (Example 10) Approximately 2.5 pre-cured product obtained in Example 9
Mold preheated to 150 ° C (0.65 x 1
0 cm) and prepare for 1 minute in a hot air dryer at 150 ° C
After heating, 150 ℃ / 50kgf / cm² / 1min
Primary pressurization was performed under the conditions of. After that, degas once
150 ℃ / 100kgf / cm² / 15min Article
Secondary pressurization was performed in some cases. The molded body was taken out of the mold
After that, after post-heating at 150 ° C./16 h / normal pressure, FIG.
Post-heating was performed with the temperature history shown in. Yellow translucent bar
A feature (2.7 x 6.4 x 97.6 mm) was obtained. JIS
-Oxygen index measured according to K7201 is 52.0-5
A value of 2.5 was shown. Also, the 5% weight loss temperature is 555
The weight loss rate at 1.5 ° C and 500 ° C was 1.5%. (Example 11) In a 50 mL glass sample bottle, G
16.3 g of R950 was weighed in. There solvent
16mL of tetrahydrofuran (THF) was added as
After that, completely dissolve the glass resin using an ultrasonic cleaner.
Let After the glass resin has completely dissolved, use a condensation catalyst.
Ti (O-i-Pr)₂ (Acac)₂ To 487 m
g and 0.62 g of water were added. Another 10 mL sample tube
And 1,4-bis (dimethylvinylsilyl) benzene
2.63 g (10.7 mmol), 1,3,5,7-te
1.28 g of tramethylcyclotetrasiloxane (5.4
mmol) is weighed, and dimethyl, which is a curing inhibitor, is added thereto.
30 mg of 1 wt% THF solution of malate (for platinum catalyst
(10 equivalents) were added and shaken lightly to mix. This cal
Mix the bosilane solution and the silsesquioxane polymer solution.
Compound (silsesquioxane polymer component / carbosilane
Component = 8/2 (weight ratio)), Pt-vinyl siloxane complex
Body (H ₂ PtCl₆ ・ 6H₂ O / [Me₂ (CH₂ = C
H) Si]₂ O / NaHCO₃/ Synthesized from toluene,
9.71 x 10^-632 mg of (mmol / mg) was added.
(1 x 10 relative to Si-vinyl group^-Five).

A metal container having a bottom surface of 7 × 8 cm, in which a 25 μm-thick polyimide film was laid with a double-sided tape, was prepared in advance. The solution prepared in the above procedure was gently poured into this. The container was covered with an aluminum foil, and then left still in a hot air dryer adjusted to 50 ° C. so as to be horizontal. Then 5
Pre-curing was performed by heating at 0 ° C. for 12 hours. The obtained yellow transparent rubber-like solid was cooled with dry ice, crushed with a mortar, and dried at room temperature for 3.5 hours using a vacuum pump. The obtained pre-cured product was in the form of a yellow powder, and its gel fraction was 58%. The fluidity of the obtained pre-cured product was evaluated using a Koka type flow tester.
The conditions are the same as those described in Example 1. Maximum fluidity is 8 × 10 ⁻³ cm ^{3 for} 0 to 30 minutes after the start of measurement.
Was / s. (Example 12) About 5 g of the pre-cured product obtained in Example 11
Mold (1 x 10 cm) heated in advance to 150 ° C
Put, after preheating for 1 minute in a 0.99 ° C. in a hot air dryer, it was primary pressure under the conditions of ^{150 ℃ / 50kgf / cm 2 /} 1min. After that, degas once and
0 was secondary pressurization at conditions ^{℃ / 100kgf / cm 2 / 60min} . After removing the molded body from the mold, 150
Post-heating was performed under the conditions of ° C / 4h / normal pressure → 180 ° C / 5h / vacuum. Yellow transparent rod-shaped body (3.2 x 9.8 x 9
7.3 mm) was obtained. Mechanical properties measured according to JIS-K7203 were a flexural modulus of 2.30 GPa, a maximum strength of 30.9 MPa, and a maximum elongation of 1.8%. 5% again
The weight loss temperature was 535 ° C., and the weight loss rate at 500 ° C. was 3.1%. (Example 13) In a 100 mL glass sample bottle,
20.0 g of GR100 was weighed and added. After adding 20 mL of tetrahydrofuran (THF) as a solvent thereto, the glass resin was completely dissolved using an ultrasonic cleaner. After the glass resin was completely dissolved, Ti (Oi-Pr) ₂ (acac) ₂ as a condensation catalyst was added to 0.6
0 g and 0.71 g of water were added. In another 100 mL sample tube, 49.6 g (201 mmol) of 1,4-bis (dimethylvinylsilyl) benzene and 24.4 g (101 of 1,3,5,7-tetramethylcyclotetrasiloxane).
mmol) and weighed 296 mg of dimethylmalate, which is a curing inhibitor (500 equivalents to the platinum catalyst).
In addition, it was shaken lightly to mix. The carbosilane solution and the silsesquioxane polymer solution were mixed (silsesquioxane polymer component / carbosilane component = 2/8 (weight ratio)) to obtain a Pt-vinylsiloxane complex (H ₂ PtCl).
_{6 · 6H 2 O / [Me} 2 (CH 2 = CH) Si] 2 O /
Synthesized from NaHCO ₃ / toluene, 9.71 × 10 ^-6 m
mol / mg) was added (1 × 10 ^{−5 with} respect to the Si-vinyl group).

A 25 μm-thick polyimide film was previously laid with double-sided tape so that the bottom surface was 16 × 23 c.
The metal container of m was prepared. The solution prepared by the above procedure was gently poured into this. The container was covered with an aluminum foil, and then left still in a hot air dryer adjusted to 50 ° C. so as to be horizontal. Then, it heated at 50 degreeC for 13 hours, and pre-cured. The obtained yellow transparent jelly-like solid was cooled with dry ice, pulverized with a mortar, and dried at room temperature for 7.5 hours using a vacuum pump. The obtained pre-cured product was a yellow solid, and its gel fraction was 53%. The fluidity of the obtained pre-cured product was evaluated using a Koka type flow tester. The conditions are the same as those described in Example 1.
Maximum fluidity is 2 × 10 for 0 to 30 minutes after the start of measurement.
^{It was −3} cm ³ / s. (Comparative Example) GR1 is placed in a 30 mL glass sample bottle.
00 was weighed and put into 5.0 g. After adding 5 mL of tetrahydrofuran (THF) as a solvent thereto, the glass resin was completely dissolved using an ultrasonic cleaner. After the glass resin is completely dissolved, the condensation catalyst Ti
151 mg of (Oi-Pr) ₂ (acac) ₂ and 191 mg of water were added. In another 10 mL sample tube,
4-bis (dimethylvinylsilyl) benzene 807 mg
(3.3 mmol) and 397 mg (1.6 mmol) of 1,3,5,7-tetramethylcyclotetrasiloxane were weighed, and 1 g of dimethylmalate as a curing inhibitor was added thereto.
A 9% wt% THF solution (10 equivalents to the platinum catalyst) was added and shaken gently to mix. This carbosilane solution was mixed with a silsesquioxane polymer solution (silsesquioxane polymer component / carbosilane component = 8/2
(Weight ratio)), Pt-vinyl siloxane complex (H ₂ Pt
Cl ₆ .6H ₂ O / [Me ₂ (CH ₂ = CH) Si] ₂
Synthesized from O / NaHCO ₃ / toluene, 9.71 × 10
^-7 mmol / mg) was added (1 × 10 ^{-5 with} respect to the Si-vinyl group).

In advance, a φ6.7 cm ointment can in which a 25 μm-thick polyimide film was laid with double-sided tape was prepared. The solution prepared by the above procedure was gently poured into this. This ointment can was placed horizontally in a hot air drier, then covered with a lid and allowed to stand. After that, 50 ° C /
18h → 80 ° C / 9h → 100 ° C / 14h → 150 ° C /
It was cured by heating for 22 hours. A brown transparent solid having a thickness of 3 mm was obtained, but the curvature was large, and voids were generated inside the cured product, which was unsuitable for physical property measurement.

[0096]

Industrial Applicability According to the present invention, it is considered that a novel silicon-based interpenetrating structure (IPN) having a high heat resistance and a high elastic modulus, which is composed of a silsesquioxane component and a carbosilane component, is conventionally used. It is possible to easily manufacture a molded product having a difficult arbitrary shape.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the fluidity of a pre-cured product and compression moldability in the present invention.

FIG. 2 is a graph showing the results of fluidity measurement by a high performance type flow tester of the pre-cured product obtained in Example 1.

FIG. 3 is a graph showing the results of fluidity measurement by a Koka type flow tester of the pre-cured product obtained in Example 2.

FIG. 4 is a graph showing a temperature history of post heat treatment in Example 5.

FIG. 5 is a graph showing the results of fluidity measurement by a Koka type flow tester of the pre-cured product obtained in Example 7.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI // C08G 77/44 C08K 5/54 (56) References JP-A-6-256518 (JP, A) JP-A-8-225647 (JP, A) JP-A-8-319422 (JP, A) JP-A-9-278901 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 83/00 -83 / 16 C08G 77/00-77/62

Claims (9)

(57) [Claims] 1. (A) Formula (1) (R ¹ and R ² represent a hydrogen atom or a substituted or unsubstituted monovalent organic group, which may be the same or different, R ³ is a hydrogen atom or a substituted group. Alternatively, it represents an unsubstituted monovalent organic group, and l, m, and n are 2
Represents 0 or a positive integer satisfying ≦ l + m + n. ) A silsesquioxane ladder polymer having a number average molecular weight of 500 or more represented by the general formula (1): (B) a silicon compound having at least two SiH groups in the molecule and having a molecular weight of 1000 or less; and (C) having at least two vinylsilyl groups in the molecule, having a molecular weight of 1000.
The following silicon compounds, (D) neutral platinum catalyst as an essential component, (A) ~ (D) component is a pre-cured product obtained by heating to 50 ~ 300 ℃, the diameter of the hole 1mm, length 10mm With the fluidity measurement by the advanced flow tester using the die of
After preheating at 150 ° C for 30 to 60 seconds, 1
Under the conditions of 00 kgf / cm ² and 150 ° C., the fluidity at a certain point in the 30 minutes after the start of measurement is 10 ⁻¹ to 10
^-6 cm ³ / s, a melt-compression moldable pre-cured product. 2. The preliminary curing according to claim 1, wherein in the fluidity measurement according to claim 1, the maximum fluidity in the time range of 0 to 30 minutes after the start of measurement is 10 ^-1 to 10 ^-6 cm ³ / s. object. 3. The silanol condensation catalyst as the component (E) is contained as an essential component.
Precured product described. 4. The precured product according to claim 3, wherein the silanol condensation catalyst of the component (E) is a neutral organometallic compound. 5. The pre-cured product according to claim 3, wherein the silanol condensation catalyst as the component (E) is a titanium compound. 6. As the component (F), a polyfunctional silicon compound capable of undergoing a hydrolysis / condensation reaction, a silanol compound, water,
The precured product according to claim 1 or 2, further comprising at least one component selected from the group consisting of and a silica-based crosslinking agent as an essential component. 7. The pre-cured product according to claim 1, which comprises the component (E) according to claim 3 and the component (F) according to claim 6 as essential components. 8. The pre-cured product according to claim 1, which is 50 to 500 ° C. and 1 to 500 kgf / cm ^2.
A method for producing a molded article, which comprises performing compression molding under the conditions of. 9. A molded body obtained by molding the precured product according to claim 1 by the method according to claim 8.
A method for curing a molded article, which comprises post-heating treatment at 0 to 500 ° C.