JP2001089662A - Curable composition and method of producing molding using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cured product that has higher mechanical characteristics by subjecting a curable composition to hydrosilylation curing. SOLUTION: This curable composition comprises a silsesquioxane oligomer obtained by cohydrolysis of vinyltrichlorosilane with a monosubstituted trichlorosilane, a silicon compound having an SiH group and a hydrosilylation catalyst, and a method of producing the curable composition is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable composition which is cured by a hydrolysis / condensation reaction of a silsesquioxane oligomer having a vinyl group in a side chain and a hydrosilylation reaction with a silicon compound having a SiH group in the molecule. And a method for producing a molded article using the same. As used herein, the term "silsesquioxane" refers to a siloxane having a ratio of 1.5 oxygen atoms to 1.5 silicon atoms.

[0002]

2. Description of the Related Art Silsesquioxane oligomers having a reactive substituent on the side chain are disclosed in JP-A-56-15173.
1. A vinyl group or a (meth) acryloxyalkyl group has been studied as a reactive substituent, and styrene-grafted silsesquioxane has been synthesized by anionic polymerization of styrene. However, there is no report on the production of a cured product using a hydrosilylation reaction between a vinyl group of a silsesquioxane oligomer side chain and a compound having a SiH group, and it has mechanical properties applicable as a heat-resistant structural material. There was no teaching about the method of producing a thick molded body.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel silicon-based curable composition applicable as a heat-resistant structural material and a method for producing a molded article using the same.

[0004]

According to the present invention, there is provided (A) CH ₂
ＣＨCHSiCl ₃ (vinyltrichlorosilane) and RS
iCl ₃ (wherein, R is a group having 1 to 1 carbon atoms which may have a substituent)
20 alkyl groups or aryl groups. A) a silsesquioxane oligomer obtained by co-hydrolyzing one or more trichlorosilanes represented by
The present invention relates to a curable composition containing (B) a silicon compound having at least two SiH groups in a molecule, and (C) a hydrosilylation catalyst.

Further, the present invention relates to (A) CH ₂ ＣＨCHSi
(OR ′) ₃ (wherein R ′ is an alkyl group having 1 to 4 carbon atoms);
1 represented by i (OR ′) ₃ (wherein R ′ is an alkyl group having 1 to 4 carbon atoms, and R is an alkyl group or an aryl group having 1 to 20 carbon atoms which may have a substituent). A silsesquioxane oligomer obtained by co-hydrolyzing one or more trialkoxysilanes, (B) a silicon compound having at least two SiH groups in a molecule, and (C) a hydrosilylation catalyst. Curable composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) of the present invention, which has been made to achieve the above object, comprises CH ₂ ＣＨCHSiCl ₃ (vinyltrichlorosilane) and RSiCl ₃ (where R represents a substituent. Or a silsesquioxane oligomer obtained by co-hydrolyzing one or two or more kinds of trichlorosilane represented by the following formula: CH ₂ =
A vinyl trialkoxysilane represented by CHSi (OR ′) ₃ (wherein R ′ is an alkyl group having 1 to 4 carbon atoms); and RSi (OR ′) ₃ (where R ′ represents 1 to 4 carbon atoms). An alkyl group of 4. R represents an optionally substituted carbon number of 1 to 20 carbon atoms
An alkyl group or an aryl group. ) Is a silsesquioxane oligomer obtained by co-hydrolyzing one or two or more trialkoxysilanes.

In the above formula, R represents an alkyl group such as methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, isoamyl, n-octyl, n-nonyl, and phenyl. And aryl groups such as tolyl, mesityl and naphthyl, and a methyl group or a phenyl group is preferred. The methyl group / phenyl group (molar ratio) is preferably 5 or less, more preferably 3 or less, and most preferably 1 or 2, from the viewpoint of curability and mechanical properties. In the silsesquioxane oligomer, the vinyl group content of all side chains is 5 to 90 mol%, preferably 10 to 70 mol%, and more preferably 20 to 50 mol%. The range of the molecular weight of the obtained silsesquioxane oligomer is not particularly limited.
It is preferably at most 10,000, more preferably at most 50,000, most preferably at most 10,000.

[0008] As a solvent used in the co-hydrolysis,
Diethyl ether, tetrahydrofuran, ethers such as dioxane, ketones such as methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, aromatics such as benzene, toluene, xylene, methanol,
Alcohols such as ethanol and halogens such as chloroform, methylene chloride and carbon tetrachloride are suitable. The solvent is used in an amount of about 0.5 to 20 per 1 part by volume of silanes.
It can be selected from a capacity part and a wide range. The water used for co-hydrolysis can be used in a wide range of 1 to 10 mol per 1 mol of silanes. The reaction temperature can be selected from the range of -78 ° C to the reflux temperature of the solvent used. When chlorosilanes are used, the reaction temperature is preferably 10 ° C. or lower to suppress gelation. Examples of the catalyst during the condensation include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide, amines such as triethylamine, diethylenetriamine, n-butylamine, p-dimethylaminoethanol and triethanolamine. And quaternary ammonium salts such as tetramethylammonium hydroxide.

As the silicon compound having at least two SiH groups in the molecule, which is the component (B) of the present invention, the following compounds can be used without particular limitation. _{HSiR 2 -X-SiR 2 H (} 1) HSiR 2 H (2) H a SiR (4-a) (3) H (a-1) SiR (4-a) - (X) m (SiRH) n SiR
_(4-a) H _(a-1) (4) R '-(X) _m (SiRH) _{(n + 2)} -R' (5) [X-SiR _(4-a) H _{(a-2) (N + 2)} (6) (wherein, R represents a monovalent organic group having 1 to 20 carbon atoms,
R ′ represents hydrogen or a monovalent organic group, X represents a divalent group, a is an integer of 3 or 4, n is an integer of 0 to 30, m is 1
Represents an integer of ~ 31. ) Or three or more hydrogens on the aromatic ring are SiR ₂ H, SiRH
₂ , an aromatic ring substituted with SiH ₃ (R represents a monovalent organic group having 1 to 20 carbon atoms) and a hydrosilane comprising the substituent can be preferably used. One or more of these compounds may be used. Formula (1)-
Examples of the monovalent organic group having 1 to 20 carbon atoms in (6) include methyl, ethyl, n-propyl, i-propyl, n
-Butyl, t-butyl, isoamyl, n-octyl, n
-Nonyl, phenyl, trimethylsiloxy and the like, and a methyl group and a phenyl group are preferred. Equation (1),
Specific examples of the divalent group X in (4), (5) and (6) include the structures shown below.

[0010]

Embedded image (In the formula, n represents an integer of 1 to 4.)

[0011]

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

[0012]

Embedded image (In the formula, n is the same as described above.) Equation (5)
Hydrogen or a monovalent organic group: R ′ is specifically hydrogen,
Examples thereof include a methyl, ethyl, phenyl, and trimethylsiloxy group, and hydrogen is particularly preferable. As preferred specific examples of the component (B),

[0013]

Embedded image (In the formula, Me represents the same as described above, and Ph represents a phenyl group.).

Further, a silicon-based polymer having a SiH group at the terminal can be used as the component (B) without any particular limitation. The ratio of all SiH / Si-vinyl groups involved in the addition reaction in the curable composition of the present invention is preferably 0.5 to 5, more preferably 0.6 to 3, and particularly preferably 0.8 to 2. .

The hydrosilylation catalyst, which is the component (C) of the present invention, is neutral in order to promote the hydrosilylation reaction and the hydrolysis / condensation reaction of the alkoxysilane in one pot with good yield without producing undesirable by-products. Platinum catalysts are preferred. As the neutral platinum catalyst, a platinum-organic compound complex, a platinum-organofunctional siloxane complex, a platinum-diolefin compound complex and the like can be used. Platinum-vinylsiloxane complex, platinum-acetylacetonate complex, platinum-
Decadiene complexes and the like are preferred. The amount of the catalyst is not particularly limited, but is 10 ^-1 to 10 ^-8 based on 1 mol of the SiH group.
mol is preferably used, and more preferably 10 mol.
^It is good to use in the range of ^-3 to 10 ^-6 mol.

In addition to the neutral platinum catalyst which is the component (C) of the present invention, the reaction rate of the hydrosilylation reaction can be controlled by a combination with a curing inhibitor in some cases. The hydrolysis / condensation reaction can proceed simultaneously. As such a curing inhibitor, a compound having 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 having an aliphatic unsaturated bond include propargyl alcohol, ene-yne compounds, and maleic esters such as dimethyl malate. Examples of the organic phosphorus compound include triorganophosphine, diorganophosphine, organophosphone, and triorganophosphite. 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 alkylamines, arylamines, urea, hydrazine and the like. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

Next, (E) which can be used in the present invention
The component and the component (F) will be described. The silanol condensation catalyst of the component (E) that can be used in the present invention includes various acid catalysts,
Conventionally known ones such as an alkali catalyst or an organometallic compound can be widely used, and are not particularly limited. Specific examples thereof include, for example, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid, and phosphate ester as an acid catalyst. , Activated clay,
Examples include iron chloride, boric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and the like. Examples of the alkali catalyst include a hydroxide of an alkali metal or an alkaline earth metal, an alkoxide of an alkali metal or an alkaline earth metal, a tetraalkylammonium hydroxide, a tetraalkylphosphonium hydroxide, and an amine compound. Examples of the amine compound include 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,
8-diazabicyclo [5,4,0] undecene-7 (D
BU) or salts of these amine compounds with carboxylic acids, etc., low molecular weight polyamide resins obtained from excess polyamines and polybasic acids, reaction products of excess polyamines with epoxy compounds, γ-aminopropyltrimethoxy Examples thereof include silane coupling agents having an amino group such as silane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane. Further, a fluorine-based compound such as tetrabutylammonium fluoride, potassium fluoride, and sodium fluoride can also be used. Organometallic 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 tin (II) methoxide, tin (II) ethoxide, tin (II) 2,4-pentanedionate, tin (II) octoate, tin (II) acetate, Examples thereof include dibutyltin dilaurate, dibutyltin malate, dibutyltin diacetate, tin naphthenate, a reaction product of dibutyltin oxide and a phthalate, and dibutyltin diacetylacetonate. Specific examples of the zinc-based catalyst used in the present invention include dimethoxy zinc, diethoxy zinc, zinc methoxy ethoxide, zinc 2,4-pentanedionate, zinc acetate, zinc 2-ethylhexanoate, zinc formate, and methacrylic acid. Examples include zinc, zinc neodecanoate, zinc undecylenate, and zinc octylate. Specific examples of the iron-based catalyst used in the present invention include iron (III) benzoylacetonate, iron (III) ethoxide, iron (III) 2,4-pentanedionate, and iron (II).
I) Trifluoropentanedionate, iron octylate and the like. Specific examples of the cobalt-based catalyst used in the present invention include, for example, cobalt (II) 2,4-pentanedionate and cobalt (III) 2,4-pentanedionate. Specific examples of the titanium-based catalyst used in the present invention include, for example, diisopropoxybis (ethyl acetoacetate) titanium, diisopropoxybis (methyl acetoacetate) titanium, diisopropoxybis (acetylacetone) titanium, dibutoxybis (acetoacetic acid) Ethyl) titanium and the like. Specific examples of the aluminum alkoxide used as a catalyst in the present invention include aluminum triisopropoxide, aluminum trisecond butoxide, aluminum diisopropoxy second butoxide, aluminum diisopropoxide acetylacetonate, and aluminum disecond butoxide acetyl. Examples include acetonate, aluminum diisopropoxide ethyl acetoacetate, and aluminum disecondary butoxide ethyl acetoacetate. Specific examples of the zirconium-based catalyst used as a catalyst in the present invention include, specifically, zirconium tetrabutoxide, zirconium tetraisopropoxide, zirconium tetramethoxide, zirconium tributoxide monoacetylacetonate, zirconium bisbutoxide monoacetylacetate. Examples include nato, zirconium monobutoxide trisacetylacetonate, zirconium tributoxide monoethylacetylacetate, zirconium dibutoxide bisethylacetoacetate, zirconium monobutoxide trisethylacetoacetate, zirconium tetraacetylacetonate, and zirconium tetraethylacetoacetate. Specific examples of the boron alkoxide catalyst used in the present invention include boron methoxide, boron ethoxide, boron n-butoxide and the like. One of these catalysts may be used alone, or two or more of them may be used in combination as long as there is no problem. Preferred catalysts are neutral organometallic compounds,
Specifically, titanium-based and aluminum-based catalysts are preferred, and among them, titanium-based catalyst is more preferred. Specifically, Ti (Oi-Pr) ₂ (acac) ₂ ,
Ti (On-Bu) ₄ , Ti (OMe) ₄ , Ti (O
—I-Pr) _{4 and the} like. The catalyst is used in an amount of 0.01 to 20 parts by weight, preferably 0.3 to 10 parts by weight, per 100 parts by weight of the silsesquioxane oligomer.
And most preferably 0.5 to 6 parts by weight.

The silanol condensation of the component (F) in the present invention
Use the compounds shown below as compatible polyfunctional crosslinking agents
I can do it. RO [Si (OR)_TwoO]_nR (7) (wherein, R is a monovalent organic group. N satisfies 1 ≦ k ≦ 7)
This is an integer. For example, Si (O
Et)_Four, MeSi (OMe)_Three , Si (OAc)_Four ,
MeO [Si (OMe)_Two O]_n Me (n = 3 on average)
6), EtO [Si (OEt)_TwoO]_nEt (n = average 3)
To 6) and the like. Expression other than equation (7)
Compounds include Ph_TwoSi (OH)_Two , PhMe_TwoS
iOH, Ph _TwoMeSiOH, PhSi (OH)_ThreeAnd
And its low molecular weight oligomer, Me_ThreeSiOH, MeS
i (OH)_ThreeAnd low molecular weight oligomers thereof
be able to. The amount of component (F) used is silsesquioxa.
5 to 50 parts by weight per 100 parts by weight of the oligomer
And preferably 10 to 50 parts by weight. This is fivefold
Less than 10 parts by weight has little effect, and exceeds 50 parts by weight
This is because the cured product becomes brittle.

In the present invention, various compounds having a vinyl group can be used in combination for the purpose of improving the mechanical properties of the cured product. Specific examples include the compounds shown below.

[0020]

Embedded image Further, a silica-based filler can be used for the purpose of improving the mechanical properties. Examples of the silica-based filler include fine powder of hydrated silica, anhydrous silica, and silica powder treated with various surface treatment agents. The amount of the silica-based filler to be used is preferably 5 to 30 parts by weight based on 100 parts by weight of the silsesquioxane oligomer.

Further, in the curable composition of the present invention,
An organic solvent can be used to uniformly mix the components constituting the composition. It is desirable that the organic solvent sufficiently dissolves the silsesquioxane ladder polymer and can dissolve water to some extent. As such organic solvents, benzene, hydrocarbon solvents such as toluene, tetrahydrofuran, 1,4-dioxane, ether solvents such as diethyl ether, acetone, ketone solvents such as methyl ethyl ketone, ester solvents such as ethyl acetate, Halogen solvents such as chloroform, methylene chloride, and 1,2-dichloroethane can be suitably used. These solvents can be used as a mixed solvent of two or more kinds. Tetrahydrofuran and chloroform are preferred as such solvents. The amount of the organic solvent used is 2 per 100 g of the silsesquioxane oligomer.
It is 0 to 200 ml, preferably 60 to 120 ml. This is because if it is less than 20 ml, it is difficult to dissolve the silsesquioxane oligomer, and if it is more than 200 ml, it becomes difficult to produce a cured product without bubbles and cracks.

Next, a method for producing a molded article will be described.
When heating and curing the curable composition of the present invention, by controlling the heating rate, the curing rate by condensation,
The rate of volatilization of volatiles from the system, the rate of diffusion of volatiles remaining in the system, and the like can be well balanced, and a molded article can be produced without generating significant cracks in the formed cured product. The method of raising the temperature of the curable composition is such that the temperature is maintained at a temperature of about 20 to 50 ° C. lower than the boiling point of the organic solvent used for 8 hours or more, and then at a temperature of 20 to 400 ° C., preferably 20 to 250 ° C. Raise the temperature stepwise or continuously. Thick molded body, for example, pour this curable composition into a mold with a polyimide film stuck with double-sided tape, cover and place it horizontally in a hot air drier, heat curing while gradually increasing the temperature It can be produced by performing The reason why the polyimide film is attached is that the cured product has good releasability, and even if the cured product shrinks during curing, the cured product easily comes off the mold and cracks are unlikely to occur. The temperature of the heat curing is preferably increased stepwise or continuously in the range of 20 to 400 ° C. When the temperature is continuously increased, it is preferable to gradually increase the temperature at a rate of 5 ° C./hr or less. Preferable stepwise temperature increasing conditions are, for example, 8 to 24 hours at 50 ° C, 8 to 24 hours at 80 ° C, 8 to 24 hours at 100 ° C, and 12 to 24 hours at 150 ° C.
Conditions for heating and curing in the order of 70 hours are listed.
After the heat curing, a heat treatment may be further performed according to the improvement of physical properties or the purpose of use. The conditions are 150-450 ° C
The reaction can be performed in air, in an inert gas such as nitrogen or argon, or under reduced pressure.

In the electric and electronic fields, the cured silicon-based polymer produced by the present technology can be used as a heat-resistant adhesive, a liquid crystal film, a polarizing film, a retardation film, a TAC film, a viewing angle improving film, a color filter, a transparent film. Conductive film, ACF, liquid crystal alignment film, plastic film substrate, liquid crystal spacer, liquid crystal photoresist, diffusion plate (film), prism sheet, reflector, AR film,
IDC connectors, thermal connectors, photosensitive interlayer insulating materials for printed circuit boards, thermosetting interlayer insulating materials, copper foil with resin, liquid solder resist, electrodeposition resist, DRF, FPC film, masking tape for PWB, photo for semiconductor Resist, interlayer insulating material, velcro, passivation film, back glide tape, dicing tape, sealing goods, TAB
Tape, LOC tape, camera integrated video drive mechanism,
DAT drive unit, stereo cassette drive unit, CD / LD deck mechanism, keyboard switch, printer, tractor parts, copier gear, IC card reader, FD shutter, washing machine gear, vacuum cleaner gear, kettle pot parts,
Microwave oven parts, nuclear mechanism parts, oilfield electronic parts,
It can be used for IC sockets, printer bearings, card holders, portable information terminal parts, polymer films for magnetic tapes, and the like.

In the field of optics, audio code, copier wiring, car navigation system wiring, medical lighting,
Plastic optical fiber for display, CD / L
It can be used as a disk substrate material for D / DVD / MO, a substrate material for solar cells, etc., a display material for ultra-thin monitors, small high-performance projectors, and ultra-large displays. Further, it can be used as a wear-resistant coating agent for various optical materials.

In the energy-related field, materials for new power storage systems such as superconducting storage systems, materials for secondary batteries such as lithium-ion batteries, lithium polymer batteries, nickel-metal hydride batteries, and zinc-air batteries; It can be used as a fuel cell member such as a salt type or a phosphoric acid type, an amorphous solar cell, a polycrystalline solar cell, a member for a single crystal solar cell, a cogeneration system, a high efficiency gas turbine, and other energy-related equipment materials.

In the construction and civil engineering related fields, particle board, aggregate, admixture, formwork / form sheet material, road marking paint, concrete protection paint, vibration damping paint, special waterproof paint, weather resistant paint, recursive paint Reflective paints, adhesives for stone, glass, and metal, sealing materials, high-performance thin fire-resistant coating materials, ceramic non-combustible paper, high-fire and fire-resistant materials for asbestos replacement, materials for waterproof panels and humidity control building materials, vinylidene chloride-based urethane Insulation, vibration insulation such as foamed insulation materials of composite type, phenolic type, polypropylene type, styrene type, silica type, etc., composite laminated rubber seismic isolation device, magnetic rubber composite seismic isolation plate, ultra-soft urethane rubber type vibration / shock absorber Material, flat type composite electromagnetic wave absorber, electromagnetic shielding glass, material for magnetic and electromagnetic wave shielding panels, water-permeable ceramic style, drainage pavement material, rolling compactor Ried paving, bridges material, can be used as one component of the soil improvement agent, soil stabilizer material. It can be used for aluminum sash fixing plate, toilet peripheral parts, water meter parts, gas box cock, gas hose joint, blind parts, etc.

In the transportation-related field, peripheral parts of engines for automobiles and aircraft, radiator tanks, electrical components, lamps, panels, tools, foils, radiator grills,
Exterior parts, gears, rotor arms, bearing retainers,
Wiper motor system gear, auto antenna system, door lock actuator, remote control door mirror,
It can be used for clips, carburetor gasoline float, regulator handle, outer door handle gear strut washer, jet engine parts, power control clutch, bearing connector for door hinge, bracket, etc.

In the machinery related fields, transport rollers, transport deceleration mechanisms, table top chains, pneumatic couplings, watch parts, micro printer parts, belt conveyor bearings,
It can be used for hydraulic pump sealing, piston ring, vane bearing retainer, semiconductor line manufacturing parts, oil field electric parts, pump parts valve seat, hydraulic seal backup ring, etc.

In the medical field, dialyzers, inhalers, medical containers, artificial dialysis membranes, syringes, dental equipment, syringe cylinders, contact lens sterilization containers, artificial joints, artificial bones, parts for home medical equipment, nursing equipment It can be used as one component of components, light-cured dental materials, antibacterial and antifungal materials, and the like. The fields of application and applications of the molded articles of this report are not limited to the above-mentioned fields.

Hereinafter, the present invention will be described specifically with reference to examples, but the contents of the present invention are not limited thereto.

[0031]

EXAMPLES Production Example 1 (Synthesis of (Ph / Me / Vi) -substituted silsesquioxane oligomer (1)) 500 mL of methyl isobutyl ketone was placed in a 1 L 4-neck flask.
And 90.7 g of ion-exchanged water, and cooled using an ice bath. Thereto, a mixed solution of 48.7 g of phenyltrichlorosilane, 34.4 g of methyltrichlorosilane, and 37.2 g of vinyltrichlorosilane was dropped over 2 hours. The dropping speed was controlled so that the maximum temperature during dropping was 10 ° C. or less. After completion of the dropwise addition, stirring was continued for 1.5 hours under ice cooling. After that, 36 mL of triethylamine was added to 3
It was added dropwise over 0 minutes. Thereafter, the ice bath was removed and stirring was continued for 3 hours. The obtained organic layer was washed with pure water until neutral, and dried overnight using anhydrous sodium sulfate. A white solid (1) is obtained by distilling off methyl isobutyl ketone under reduced pressure.
65.3 g (SiO based yield: 100%) were obtained. The obtained (1) was found to have a number average molecular weight _Mn = 1130 and a weight average molecular weight _Mw = 3150 by gel permeation chromatography analysis using polystyrene as a standard substance. The amount of the vinyl group was found to be 3.4 by the quantification of the vinyl group using dibromoethane as an internal standard.
It was found to be mmol / g.

A nuclear magnetic resonance spectrum (NMR) δ (p
pm) 1.61 (bs, 0.3H) 0.19 (bs, 3
H), 5.95 (bs, 3H), 7.25-7.70 (b
s, 5H). Production Example 2 [Synthesis of Vi-substituted silsesquioxane oligomer (2)]
0 mL and 48.0 g of ion-exchanged water were added and cooled using an ice bath. There, 60.0 g of vinyltrichlorosilane was dropped over 80 minutes. The dropping speed was controlled so that the maximum temperature during dropping was 10 ° C. or less. After completion of the dropwise addition, stirring was continued for 2 hours under ice cooling. Thereafter, 18 mL of triethylamine was added dropwise over 10 minutes. Thereafter, the ice bath was removed and stirring was continued for 3 hours. The obtained organic layer was washed with pure water until neutral, and dried overnight using anhydrous sodium sulfate. The methyl isobutyl ketone was distilled off under reduced pressure to give 28.68 g of a white solid (2) (SiO based yield:
98%). The obtained (2) was found to have a number average molecular weight _Mn = 1500 and a weight average molecular weight _Mw = 5120 by gel permeation chromatography analysis using polystyrene as a standard substance. In addition, quantification of the vinyl group using dibromoethane as an internal standard revealed that the amount of the vinyl group was 13 mmol / g. Example 1 In a 30 ml sample tube, (Ph /
Me / Vi) Substituted silsesquioxane oligomer (1)
3 g, 1,4-bis (dimethylsilyl) benzene 1.5
8 g (8.1 mmol) was weighed, and 23 mg of a 1 wt% THF solution of dimethyl malate as a storage stabilizer was added thereto.
The mixture was shaken lightly and mixed (10 equivalents with respect to the platinum catalyst). Then, Ti (Oi-Pr) ₂ which is a condensation catalyst
90 mg of (acac) ₂ and 114 mg of water were added. Finally, a Pt-vinylsiloxane complex (1.54 × 10 ⁻⁵ mm
ol / mg) was added (1 × to the SiH group).
10 ^-5 equivalents). An ointment can having a diameter of 6.7 cm, on which a polyimide film having a thickness of 25 μm was spread, was prepared in advance.
Into this, the solution prepared by the above procedure was gently poured. The ointment can was placed horizontally in a hot-air dryer, and then capped and allowed to stand. After that, 50 ° C / 16h, 8
Heat curing was performed at 0 ° C./8 h, 100 ° C./17 h, and 150 ° C./24 h to obtain a cured product (a). Gel fraction: 10
0%. The gel fraction was calculated by the following equation (the same applies hereinafter).

Gel fraction (%) = (total weight after extraction−
Net weight) / (total weight before extraction−net weight) × 10
0. Using a diamond cutter from the cured product, length about 40
A sample for bending test having a width of about 5 mm and a width of about 5 mm was cut out.
The bending properties of the obtained cured product were as follows: elastic modulus: 1.77 GP
a, strength: 52.8 MPa, maximum strain: 5.5%. -Method of bending test The test was performed using a Shimadzu precision universal testing machine. The measurement conditions are
The test was performed in accordance with the “Bending test method using a small test piece” specified in JIS (K7203). (Span: 15m
m, indenter: 5R, fulcrum: 2R, test speed: 0.
5 mm / min). Example 2 A cured product (b) was obtained in the same manner as in Example 1, except that 0.99 g (5.1 mmol) of 1,4-bis (dimethylsilyl) benzene was used. Gel fraction: 98
%. The bending characteristics of the obtained cured product were as follows: elastic modulus: 1.66 G
Pa, strength: 51.8 MPa, and maximum strain: 4.5%. Example 3 A cured product (c) was obtained in the same manner as in Example 1, except that 0.52 g (2.7 mmol) of 1,4-bis (dimethylsilyl) benzene was used. Gel fraction: 97
%. The bending properties of the obtained cured product were as follows: elastic modulus: 1.90 G
Pa, strength: 61.5 MPa, and maximum strain: 4.4%. Example 4 In Example 1, 2,6-dimethylsilylnaphthalene was used instead of 1,4-bis (dimethylsilyl) benzene.
The same procedure was carried out except that the amount was changed to 24 g (5.1 mmol) to obtain a cured product (d). Gel fraction: 98%. The bending properties of the obtained cured product were as follows: elastic modulus: 1.92 GPa, strength:
57.2 MPa, maximum strain: 3.3%. Example 5 The same procedure was followed as in Example 1, except that 1,4-bis (dimethylsilyl) benzene was replaced by 1.38 g (5.1 mmol) of 4,4′-bis (dimethylsilyl) biphenyl. A product (e) was obtained. Gel fraction: 98
%. The bending properties of the obtained cured product were as follows: elastic modulus: 1.68 G
Pa, strength: 46.8 MPa, and maximum strain: 3.3%. Example 6 In a 30 ml sample tube, 2 g of the Vi-substituted silsesquioxane oligomer (2) obtained in Production Example 2 and 4,4′-
3.51 g of bis (dimethylsilyl) biphenyl (13 m
mol), and 37 mg of a 1 wt% THF solution of dimethyl malate, which is a storage stabilizer, was added thereto, followed by gentle shaking and mixing (10 equivalents with respect to the platinum catalyst). Thereafter, Ti (Oi-Pr) ₂ (acac) ₂ 60 m, which is a condensation catalyst, is used.
g and water (76 mg) were added. Finally, 17 mg of Pt-vinylsiloxane complex (1.54 × 10 ⁻⁵ mmol / mg)
(1 × 10 ⁻⁵ equivalents based on SiH groups). In advance,
Φ6.7 with 25 μm thick polyimide film
cm ointment cans were prepared. Into this, the solution prepared by the above procedure was gently poured. The ointment can was placed horizontally in a hot-air dryer, and then capped and allowed to stand. Then, 50 ° C / 16h, 80 ° C / 9h, 100 ° C
/ 22 h, 150 ° C./24 h for heat curing to obtain a cured product (f). Gel fraction: 100%. The bending properties of the obtained cured product were as follows: elastic modulus: 2.53 GPa, strength: 29.
7 MPa, maximum strain: 1.2%. Comparative Example 1 In a 30 ml sample tube, a cured product was produced under the same conditions as in Example 1 using 3 g of the (Ph / Me) -substituted silsesquioxane oligomer (Ph / Me = 1/2). The obtained cured product was brittle and it was impossible to cut out a test piece for a bending test, and the gel fraction was as low as 65%.

[0034]

The cured product provided by the present invention can be used to produce a silicon-based cured product having a high elastic modulus and a high strength.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4F071 AA67 AH03 AH07 AH12 AH17 BA02 BB01 BC01 BC07 4J002 CL003 CP042 CP141 DD028 DD038 DE178 DF038 DG048 DH028 DK008 EC078 ED048 EE047 EE048 EF038 EG008 EN008 EX138 008 FD149 FD153 FD158 GB00 GL00 GM00 GN00 GP00 GQ00 4J035 BA12 CA02U CA022 CA14U CA141 FB03 LA03 LA04 LB01 LB02 LB03 LB16 LB17

Claims (9)

[Claims] (A) CH ₂ ＣＨCHSiCl ₃ (vinyltrichlorosilane) and RSiCl ₃ (where R is an alkyl group or an aryl group having 1 to 20 carbon atoms which may have a substituent). A silsesquioxane oligomer obtained by co-hydrolyzing one or more trichlorosilanes represented by the formula, (B) a silicon compound having at least two SiH groups in a molecule, and (C) hydrosilylation. A curable composition containing a catalyst. 2. A vinyltrialkoxysilane represented by (A) CH ₂ ＣＨCHSi (OR ′) ₃ (wherein R ′ is an alkyl group having 1 to 4 carbon atoms), and RSi (OR ′) ₃ (In the formula, R ′ is an alkyl group having 1 to 4 carbon atoms. R is an alkyl group or an aryl group having 1 to 20 carbon atoms which may have a substituent.) A silsesquioxane oligomer obtained by co-hydrolyzing a trialkoxysilane, (B) at least 2
A curable composition containing a silicon compound having two SiH groups and (C) a hydrosilylation catalyst. 3. (A) CH ₂ ＣＨCHSiCl ₃ (vinyltrichlorosilane) and RSiCl ₃ (R is 1 to 20 carbon atoms)
An alkyl group or an aryl group. A) a silsesquioxane oligomer obtained by co-hydrolyzing one or more trichlorosilanes represented by
A curable composition containing (B) a silicon compound having at least two SiH groups in a molecule, and (C) a hydrosilylation catalyst. 4. A vinyltrialkoxysilane represented by (A) CH ₂ ＣＨCHSi (OR ′) ₃ (wherein R ′ is an alkyl group having 1 to 4 carbon atoms), and RSi (OR ′) ₃ (Wherein, R ′ is an alkyl group having 1 to 4 carbon atoms.
20 alkyl groups or aryl groups. ), A silsesquioxane oligomer obtained by co-hydrolyzing one or more trialkoxysilanes, (B) a silicon compound having at least two SiH groups in the molecule, (C A) curable composition containing a hydrosilylation catalyst. (A) a silsesquioxane oligomer obtained by hydrolyzing CH ₂ ＣＨCHSiCl ₃ (vinyltrichlorosilane); (B) a silicon compound having at least two SiH groups in a molecule; (C) A curable composition containing a hydrosilylation catalyst. 6. A compound obtained by hydrolyzing a vinyl trialkoxysilanesilane represented by (A) CH ₂ ＣＨCHSi (OR ′) ₃ (wherein R ′ is an alkyl group having 1 to 4 carbon atoms). Silsesquioxane oligomer, (B)
A curable composition containing a silicon compound having at least two SiH groups in a molecule, and (C) a hydrosilylation catalyst. 7. The curable composition according to claim 1, further comprising (E) a silanol condensation catalyst in addition to the components (A) to (C). 8. The composition according to claim 1, further comprising (F) a polyfunctional crosslinking agent capable of condensing silanol, in addition to the components (A) to (C).
5. The curable composition according to any one of 4. 9. The method according to claim 1, wherein the silsesquioxane oligomer (A) is uniformly dissolved or dispersed in 20 to 200 parts by volume of an organic solvent with respect to 100 parts by weight of the oligomer. Is maintained at a temperature lower than the boiling point of the organic solvent used for 8 hours or more, and then 20 to 4
By increasing the temperature stepwise or continuously in the range of 00 ° C., the hydrolysis / condensation reaction of the silanol group and / or the alkoxysilyl group and the hydrosilylation (addition) reaction are carried out simultaneously. Of a molded article to be formed.