JP2002327077A - Polycarbosilane prepreg and laminated sheet using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a prepreg, having a polycarbosilane as a main component, and composed of this polycarbosilane and a reinforcing fiber, and to provide a high-strength and high heat-resistive laminated sheet obtained from the above prepreg. SOLUTION: The prepreg is composed of (A) a silicon compound having at least two SiH groups in a molecule, (B) a silicon compound having at least two silylvinyl groups, (C) a hydrosilylation catalyst, and a reinforcing fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a prepreg comprising polycarbosilane as a main component and a reinforcing fiber, and a high-strength and high heat-resistant laminate obtained from the prepreg.

[0002]

2. Description of the Related Art Conventionally, techniques relating to a laminate of a silicone resin have been disclosed (JP-B-52-36904, JP-B-59-17669, and JP-B-59-17670). For example, Japanese Patent Publication No. 59-17669 relates to a laminated board using hydrosilylation, but all components are limited to polysiloxane, and various resin skeletons could not be adopted. No prepreg containing polycarbosilane obtained by hydrosilylation of a monomer component as a main component and a laminate using the same have been found.

Until now, the Company has disclosed a technology relating to a prepreg comprising silsesquioxane and reinforcing fibers and a laminate using the same (Japanese Patent Laid-Open No. 10-154).
9). However, in this case, the main component is limited to siloxane, and the choice of the component that improves the adhesion to the reinforcing fiber is narrow. There was no knowledge about a prepreg containing a polycarbosilane component capable of easily changing the molecular structure and a laminate using the same.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a prepreg composed mainly of a polycarbosilane obtained by hydrosilylation of a hydrosilane compound and a silylvinyl compound, and a prepreg composed of reinforcing fibers, and a high-strength obtained from the prepreg. -To provide a high heat resistant laminate.

[0005]

According to the present invention, there is provided a prepreg composed mainly of a polycarbosilane obtained by hydrosilylation of a hydrosilane compound and a silylvinyl compound, and a prepreg comprising the reinforced fiber and the prepreg, and laminating the prepreg and heating and pressing the prepreg. This was achieved by making a laminate. That is, the present invention has the following configurations. (A) Silicon compound having at least two SiH groups in the molecule (B) Silicon compound having at least two silylvinyl groups in the molecule (C) Hydrosilylation catalyst These components (A) to (C) and reinforcing fibers The prepreg according to claim 1, wherein the (A) silicon compound having at least two SiH groups in the molecule has a molecular weight of 1,000 or less (claim 2). The prepreg according to claim 1 or 2, wherein (B) the silicon compound having at least two SiH groups in the molecule has a molecular weight of 1,000 or less. The prepreg according to any one of claims 1 to 3, wherein the silicon compound as a component has at least four silylvinyl groups in the molecule, and the reinforcing fiber is used. Claim 1 is a glass fiber
4. The prepreg according to claim 4, wherein the reinforcing fibers are carbon fibers, the prepreg according to claims 1 to 4 (claim 6), and a laminate obtained from the prepreg according to claims 1 to 6. Item 7). Hereinafter, the present invention will be described in detail.

The component (A) and the component (B) in the present invention form a polycarbosilane component using the hydrosilylation catalyst of the component (C). The silicon compound having at least two SiH groups in a molecule, which is the component (A) in the present invention, is not particularly limited as long as it has at least two SiH groups. Here, when two hydrogen atoms are bonded to one silicon atom, two SiH groups are counted. Such a compound may be used alone or in combination of two or more.

Specifically, the following equations (1) to (6) are used.
Hydrosilane or three or more hydrogens on the aromatic ring
R¹ ₂H, SiR¹H_Two And / or SiH₃Is replaced by
And the like. HSiR¹ ₂-Z-SiR¹ ₂H (1) HSiR¹ ₂H (2) H_aSiR¹ _(4-a) (3) H_(A-1)SiR¹ _(4-a)-(Z)_m(SiR¹H)_n SiR¹ _{(4-a )} H_(A-1) (4) R²-(Z)_m(SiRH)_{(N + 2)}-R² (5) [Z-SiR¹ _(4-a)H_(A-2)]_{(N + 2)} (6) In each formula, R¹Are the same or different and have 1 to 20 carbon atoms
Represents a monovalent organic group. R ²Is a hydrogen atom or carbon number 1
It represents 20 monovalent organic groups. Z represents a divalent group. a is
Represents an integer of 3 or 4; n represents an integer of 0 to 30;
Represents an integer of 1 to 31.

[0008] R ¹ or R ^{2 in} each formula has 1 carbon atom.
As the monovalent organic group having 20 to 20, a hydrocarbon group having 1 to 20 carbon atoms and a trialkylsiloxy group are preferable. Specifically, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, isoamyl,
n-octyl group, n-nonyl group, phenyl group, trimethylsiloxy group, triethylsiloxy and the like. R
¹ is preferably a methyl group or a phenyl group. On the other hand, R ² is preferably a hydrogen atom.

In formulas (1) and (4) to (6), Z represented by 2
The valent group is not particularly limited as long as it is a group capable of stably bonding to a silicon atom. Specifically, the following equations (7) to (2)
And the divalent group shown in 2).

[0010]

Embedded image

In the above formula (7), n represents an integer of 1 to 4. Among these, the above equations (7), (11), (1)
The groups 2), (13), (15) and (20) are preferred. Further, the above equations (11), (13) and (15)
Is more preferred.

As the component (A), the following formulas (23) to (23)
Compounds represented by (29) and S in the formulas (23) to (29)
A methyl or phenyl group on i is a hydrogen atom (SiH
Is preferred.

[0013]

Embedded image

In the above formulas (23) to (29), Me represents a methyl group and Ph represents a phenyl group. As the component (A), a silicon compound having a molecular weight of 1,000 or less is preferable from the viewpoint of handling and hydrosilylation reactivity.
The component (A) preferably does not contain a polysiloxane structure in order to improve the adhesion to the reinforcing fibers.

The silicon compound having at least two silylvinyl groups in the molecule as the component (B) in the present invention is not limited as long as it has at least two silylvinyl groups. In the present invention, a silylvinyl group refers to a structure in which a vinyl group is directly bonded to a silicon atom (Si-CH =
CH ₂ ).

The component (B) is preferably a compound having a molecular weight of 1,000 or less, more preferably a compound having a molecular weight of 700 or less, from the viewpoint of handling and hydrosilylation reactivity.

The component (B) is a compound containing preferably 2 to 6, more preferably 2 to 4, silylvinyl groups in one molecule in view of the balance between the reactivity and the storage stability. The component (B) is a compound having a viscosity of less than 1000 poise, preferably less than 300 poise, from the viewpoint of handleability and processability.

The component (B) preferably has a cyclic structure. Examples of the cyclic structure include a saturated alicyclic hydrocarbon structure, an unsaturated alicyclic hydrocarbon structure, an aromatic ring structure, a heterocyclic structure, and a cyclic polysiloxane. The cyclic structure is 4-
Those having an eight-membered ring are preferred. The component (B) preferably has 1 to 3 cyclic structures.

As the preferred component (B), X _{a-
Si (R 3-a) -R'} -Si (R 3-a) -X a compound represented by (wherein, X is .R representing a vinyl group, 1 to 20 carbon atoms, preferably 1 R ′ represents a divalent cyclic structure, and examples of the divalent cyclic structure representing R ′ include a phenylene group, a naphthalene group, and a biphenylene group. Represents 1, 2 or 3.) and a compound in which at least two vinyl groups are bonded to a silicon atom of a 4- to 12-membered cyclic polysiloxane.

The component (B) in the present invention is preferably a compound represented by the following formulas (30) to (37).

[0021]

Embedded image

The ratio of (A) and (B) used in the prepreg of the present invention is such that the ratio of all SiH / Si-vinyl groups involved in the addition reaction (hydrosilylation) is 0.5 to 5
A value that gives 0.6 to 3 are more preferable, and 0.8 to 2 are particularly preferable.

Next, the hydrosilylation catalyst as the component (C) will be described. The hydrosilylation catalyst is not particularly limited as long as it has the catalytic activity of the hydrosilylation reaction, and examples thereof include simple platinum, alumina, silica, and solid black supported on a carrier such as carbon black, chloroplatinic acid, and platinum chloride. Complexes of acids with alcohols, aldehydes, ketones, etc., platinum-olefin complexes (for example, Pt
_{(CH 2 = CH 2) 2} (PPh 3) 2, Pt (CH 2 =
CH ₂ ) ₂ Cl ₂ ), a platinum-vinylsiloxane complex (for example, Pt (ViMe ₂ SiOSiMe ₂ Vi) _n , P
t [(MeViSiO) ₄ ] _m ), a platinum-phosphine complex (for example, Pt (PPh ₃ ) ₄ , Pt (PB
u ₃ ) ₄ ), a platinum-phosphite complex (for example, Pt
[P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ )
(In the formula, Me is a methyl group, Bu is a butyl group, Vi is a vinyl group, Ph is a phenyl group, n and m are integers.), Dicarbonyldichloroplatinum, Karstedt's catalyst, Ashby (Ash
by) US Patents 3,159,601 and 31,596
No. 62, as well as the platinum-hydrocarbon complex described in Lamoreaux.
Platinum alcoholate catalysts described in U.S. Pat. No. 2,209,72. In addition, Modic
Platinum chloride-olefin complexes described in U.S. Pat. No. 3,516,946 are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , and RhAl ₂ O.
₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlC
l ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiC
l _4, and the like.

Of these, chloroplatinic acid, a platinum-olefin complex, a platinum-vinylsiloxane complex and the like are preferred from the viewpoint of catalytic activity. These catalysts may be used alone or in combination of two or more.

The amount of the catalyst to be added is not particularly limited. However, in order to have sufficient curability and keep the cost of the prepreg relatively low, 10 ^-1 to 1 ^-1 to 1 mol of the SiH group are used.
It is preferably in the range of ^0-8 mol, more preferably 10 mol.
The range is from ^-3 to ^10-6 mol.

The prepreg of the present invention may contain a hydrosilylation inhibitor (D). By combining the hydrosilylation catalyst (C) and the hydrosilylation inhibitor (D), the reaction rate of the hydrosilylation reaction can be controlled, and the viscosity of the resin can be adjusted during prepreg production.

As the hydrosilylation inhibitor of the component (D), dimethylmalate, benzothiazole, acetylene alcohol and the like can be mentioned. The amount of the component (D) is not particularly limited, but may be 0.01 to 1 equivalent of the component (C).
１０００1000 equivalents are preferred, more preferably 1-10
It is 0 equivalent.

For the purpose of increasing the adhesiveness between the resin and the reinforcing fibers, a silane coupling agent or an adhesion-imparting agent other than the silane coupling agent can be added to the prepreg of the present invention. Specific examples of the silane coupling agent include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane,
γ-isocyanatopropylmethyldiethoxysilane,
isocyanate group-containing silanes such as γ-isocyanatopropylmethyldimethoxysilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane,
γ-aminopropylmethyldiethoxysilane, γ- (2
-Aminoethyl) aminopropyltrimethoxysilane,
γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane , N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-
Amino group-containing silanes such as aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane;
Mercapto group-containing silanes such as γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxy Silane,
γ-glycidoxypropylmethyldimethoxysilane, β
-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl)
Epoxy group-containing silanes such as ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy)
Silane, N-β- (carboxymethyl) aminoethyl-
Carboxysilanes such as γ-aminopropyltrimethoxysilane; vinyl-containing unsaturated groups such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-acroyloxypropylmethyltriethoxysilane Silanes; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; and isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate. Amino-modified silyl polymers, silylated amino polymers, unsaturated amino silane complexes, phenylamino long-chain alkyl silanes, amino silylated silicones, silylated polyesters, and the like, which are derivatives thereof, can also be used as the silane coupling agent. .

The silane coupling agent used in the present invention is
Usually, based on 100 parts by weight of the total of the components (A) to (C),
It is used in the range of 0.01 to 20 parts by weight. In particular, 0.
It is preferable to use in the range of 1 to 10 parts by weight.

Specific examples other than the silane coupling agent are not particularly limited, and include, for example, epoxy resins, phenolic resins, sulfur, alkyl titanates, aromatic polyisocyanates and the like.

The above-mentioned adhesiveness-imparting agents may be used alone or in combination of two or more. The addition of these adhesion-imparting agents can improve the adhesion to the adherend.

The reinforcing fibers used in the present invention are made of long fibers, and are generally used as advanced composite materials and have good heat resistance and tensile strength. The reinforcing fibers include PA
N-based carbon fibers (Toray made by Toray, Vesfight made by Toho rayon, etc.), pitch-based carbon fibers (Kureka made by Kureha Chemical Industry, Dialead made by Mitsubishi Chemical, etc.), silicon carbide fibers (Nicalon made by Nippon Carbon, etc.), silicon nitride fibers , Alumina fiber (ALTEX manufactured by Sumitomo Chemical Industries, NEX manufactured by 3M)
TEL), boron fiber, tungsten carbide fiber, aramid fiber (Kevlar manufactured by DuPont, T
echnora), tyrano fiber, glass fiber and the like. Glass fiber or the like that has been surface-treated with a silane coupling agent or the like can be used to improve the adhesiveness with the resin. In the present invention, a long fiber-shaped reinforcing fiber is used, but the shape and arrangement thereof are not particularly limited. For example, a unidirectional, randomly oriented sheet, mat, fabric, braid, and the like can be used.

[0034] The prepreg of the present invention comprises the above (A) to
It is obtained by applying or impregnating a composition obtained by mixing the component (C) with a reinforcing fiber base material such as a glass cloth by an appropriate means. As a specific example, for example, (A)
~ (C) Each component was uniformly mixed via an organic solvent, diluted to a viscosity suitable for use to prepare a resin solution, and this was applied or impregnated on a reinforcing fiber substrate such as a glass cloth. Thereafter, a method of heating and drying at an appropriate temperature to remove the solvent and to preliminarily cure the resin is used.

Examples of the organic solvent used for preparing the resin solution include hydrocarbon solvents such as benzene, hexane, toluene and heptane, ether solvents such as tetrahydrofuran, 1,4-dioxane and diethyl ether, acetone and methyl ethyl ketone. Halogen solvents such as ketone solvents, chloroform and methylene chloride can be suitably used. The solvent can be used as a mixed solvent of two or more kinds. As the solvent, tetrahydrofuran, toluene and chloroform are preferred. More preferably, it is tetrahydrofuran. The viscosity of the resin solution and the amount of the resin attached to the prepreg can be adjusted by the amount of the organic solvent used. The viscosity of the solution is preferably such that the resin can be impregnated between the single fibers, and the amount of the solvent used is 1 to 200 g, preferably 5 to 100 g, based on 100 g of the polycarbosilane component in total.

The heating and drying conditions are from room temperature to 100.degree.
20 hours. In order to sufficiently remove the solvent, 40 to 6
After heating at 0 ° C for 3 to 18 hours,
Heating may be performed in stages, such as heating for 5 to 60 minutes. 1 to 60 ° C / h, preferably 5 to 40 ° C
The temperature may be continuously increased at a rate of / h. The cooling conditions after the heating and drying may be rapid cooling, or stepwise and continuous cooling. The state of the pre-cured product after the heating and drying is such that the resin applied or impregnated to the extent that a good laminate is obtained in the subsequent heating and pressurizing step for producing a laminate retains the melt fluidity. And there is no particular limitation. The resin adhesion after drying is 1% of the prepreg weight.
It is 0 to 80 wt%, preferably 15 to 50 wt%.

In order to produce a laminate, a plurality of prepregs may be overlaid and heated and pressed by an autoclave or a press. Although the manufacturing conditions vary depending on the shape such as the thickness and size of the laminate, the heating temperature is generally 100 to 200 ° C., preferably 130 to 170 ° C., and the pressure is 5 to 150 k.
g / cm ² , preferably 10 to 100 kg / cm ² , and the heating and pressurizing time is 15 minutes to 8 hours, preferably 1 hour to 5 hours.

Between 30 and 120 seconds after the start of heating and pressurizing,
Degas. The degassing is performed by releasing the pressure once to remove volatile components such as air mixed into the resin and condensation products generated by curing from the molded body.
Although it is not always necessary to perform the step depending on the desired thickness and size of the laminated plate, it is preferable to perform degassing in order to reduce voids generated in the laminated plate.

After the production of the laminate, post-curing is performed. The post-curing is carried out by heating the laminate to 50 to 500 ° C. in order to complete the curing, reduce the internal stress, and improve the heat resistance of the laminate. The post-curing conditions depend on the shape of the laminate and the production conditions, but are generally heated from a temperature slightly lower than the production temperature to 50 to 300 ° C./h.
Is preferable. Temperature drop is 10 ~ 100 ℃
/ H is preferable. In order to prevent the deterioration of the resin, it is preferable to perform the post-curing in an inert gas such as nitrogen or argon or under vacuum.

The use of the laminate thus produced is not particularly limited. For example, an insulating cylinder, an insulating lever, an arc extinguishing plate, a generator, a transformer, a rectifier, a circuit breaker, a controller, etc. Operating rods, insulating spacers, cases, wind tunnels, end bells, wind seals, switch boxes for standard electrical products, cases, crossbars, insulating shafts, fan blades, mechanical components, speaker diaphragms, eta diaphragms,
Television screens, fluorescent light covers, antennas for communications equipment and aerospace, horn covers, radomes, cases, mechanical components, wiring boards, aircraft, rockets, satellite electronic components, railway components, marine components, bathtubs , Septic tanks, corrosion-resistant equipment, chairs, safety hats, pipes, tank trucks, cooling towers, floating breakwaters, underground buried tanks, containers and the like.

[0041]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the scope of the present invention is not limited thereto. As the hydrosilylation catalyst (C), platinum vinyl siloxane (3 wt% xylene solution manufactured by Degassa) was used, and as the hydrosilylation inhibitor (D), dimethyl malate was used. As the reinforcing fiber, a satin weave cloth (Glaslon cloth SLS213B) was used as the glass fiber.

Example 1 2,6-bis (trivinylsilyl) naphthalene (34.5 g) and 4,4′-bis (dimethylsilyl) biphenyl (81.2 g) were added to THF (4
0g), a mixture of a solution of a platinum vinyl siloxane catalyst (3.9 mg) in THF (3.9 g) and dimethyl malate (86.5 mg) was added to prepare a varnish.

Pour the above varnish into a vat and add 20
12 pieces of about 200 μm thick satin-woven glass cloth cut to × 15 cm were immersed, sufficiently impregnated with the resin solution, hung one by one, dried and pre-cured at 50 ° C. for 17 hours in a hot air drier. A prepreg was prepared. (Amount of resin)
= 100 × [(prepreg weight) − (glass fiber weight)] / (prepreg weight) The resin amount of this prepreg was 19%.

The 12 prepregs thus obtained are overlaid,
The plate was compression-molded with a press at a hot platen temperature of 80 ° C. for 30 minutes and at 150 ° C. for 2 hours to form a laminate of about 20 cm × 15 cm × 0.22 cm. The bending strength of the obtained laminate was 23 ° C.
At 487 MPa and 119 MPa at 250 ° C.

[0045]

According to the present invention, a prepreg comprising polycarbosilane as a main component and a reinforcing fiber, and a high-strength and high-heat-resistant laminate obtained from the prepreg can be easily produced.

 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 4F072 AA04 AA07 AB06 AB08 AB09 AB10 AB22 AB24 AB27 AB28 AB29 AC06 AD47 AE02 AG03 AG16 AH02 AH25 AH26 AH31 AK03 AL02 AL03 AL07 AL11 AL12 AL13 AL14 AL16

Claims (7)

[Claims] (A) at least two SiHs in a molecule
Silicon compound having a group (B) Silicon compound having at least two silylvinyl groups in a molecule (C) Hydrosilylation catalyst A prepreg comprising these components (A) to (C) and reinforcing fibers. (A) at least two SiHs in a molecule;
2. The prepreg according to claim 1, wherein the silicon compound having a group has a molecular weight of 1,000 or less. (B) at least two SiHs in a molecule;
The prepreg according to claim 1 or 2, wherein the silicon compound having a group has a molecular weight of 1,000 or less. 4. The prepreg according to claim 1, wherein the silicon compound as the component (B) has at least four silylvinyl groups in the molecule. 5. The reinforcing fiber is a glass fiber.
4. The prepreg according to 4. 6. The reinforcing fiber is a carbon fiber.
The prepreg described. 7. A laminate obtained from the prepreg according to claim 1.