JP2902525B2 - Composite composition excellent in transparency and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for manufacturing
The present invention relates to a composite composition having toughness and heat resistance.

[0002]

2. Description of the Related Art Generally, organic polymers have low rigidity, hardness and heat resistance. As one of the attempts to overcome this point,
Many attempts have been made to combine with inorganic substances. For example, many methods have been proposed in which a silica-based compound or colloidal silica obtained by polycondensation of an alkoxysilane is dispersed in an acrylic resin solution as a coating film for surface hardening (Japanese Patent Application Laid-Open No. 53-53). 11952, JP-A-53-11989, etc.).

However, when such a coating is applied to a general-purpose plastic substrate, a coating film having high hardness and high wear resistance can be obtained, but improvement in rigidity is hardly expected.
Further, if the coating film thickness is about several tens of μ, the transparency is good, but if the coating film thickness is more than that, the transparency becomes extremely poor.

On the other hand, J. A. Mater. Res. , Vo
l. 4, p. 1018 (1989) describes that a silica gel-polymethyl methacrylate composite having excellent transparency can be obtained by impregnating a methyl methacrylate monomer into porous silica gel having a controlled pore size and then polymerizing the same. However, this method has a problem that the steps are complicated, unsuitable for an industrial production method, and that post-processing is difficult.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide excellent transparency, toughness, low specific gravity, and the like inherent in acrylic resins.
An object is to obtain a composite composition having high rigidity and heat resistance without impairing good processability.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to achieve the above object, and as a result, hydrolyzed and polycondensed a radically polymerizable vinyl compound and a specific silane alkoxide in the presence of colloidal silica. The present inventors have found that the intended purpose can be achieved by polymerizing the obtained silica-based polycondensate to form a composite composition, and have reached the present invention.

That is, according to the present invention, a radical polymerizable vinyl compound (A) is prepared by dispersing a radical polymerizable vinyl compound (A) in a colloidal silica dispersion represented by the following general formula (1): SiR ¹ _a R ² _b (OR ³ ) _c (1) ¹ , R ² has 1 to 1 carbon atoms which may have an ether bond, an ester bond or a carbon-carbon double bond.
0 hydrocarbon residue, R ³ is a hydrogen atom or an ether bond,
A hydrocarbon residue having 1 to 10 carbon atoms which may have an ester bond or a carbon-carbon double bond;
And c is 4-ab, and represents an integer of 1 to 4. (B) a silica-based condensation polymer obtained by hydrolyzing and condensation-polymerizing at least one silane compound represented by the formula (B):
Silica A composite composition obtained by polymerizing in the presence of
Silica skeleton of polycondensation polymer (B) and radical polymerizable vinyl
To form a semi-IPN structure with the polymer of compound (A)
A composite composition comprising:

[0008]

In the composite composition of the present invention, a silica skeleton of a silica-based condensation polymer comprising colloidal silica and at least one silane compound which hydrolyzes and condensation-polymerizes on the surface thereof, and a radical polymerizable vinyl compound Since the polymer forms a semi-IPN (Interpenetrating Network) structure, very good rigidity, toughness and heat resistance are exhibited. Further, according to the present invention, since the colloidal silica particles are incorporated into the silica skeleton and are uniformly dispersed, extremely excellent transparency is exhibited.

As the radically polymerizable vinyl compound (A) used in the present invention, known radically polymerizable monomers are used. For example, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate; acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; acrylic acid, methacrylic acid, maleic acid, and itaconic acid Unsaturated carboxylic acids such as maleic anhydride and itaconic anhydride; N-phenylmaleimide;
Maleimide derivatives such as -cyclohexylmaleimide and Nt-butylmaleimide; hydroxy group-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; acrylamide, methacryl Nitrogen-containing monomers such as amide, acrylonitrile, methacrylonitrile, diacetone acrylamide, and dimethylaminoethyl methacrylate; epoxy group-containing monomers such as allyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate; styrene such as styrene and α-methylstyrene -Based monomers: ethylene glycol diacrylate, ethylene glycol dimethacrylate, allyl acrylate, allyl methacrylate, divinyl Zen, crosslinking agents such as trimethylol propane triacrylate, and the like. Of these, methacrylates and acrylates are preferred. At least one monomer selected from methacrylates and acrylates accounts for 50% by weight of the radically polymerizable vinyl compound (A).
It is preferably at least 70% by weight, more preferably at least 70% by weight. Particularly preferred radically polymerizable vinyl compound (A) is methacrylic acid ester.

Further, a group capable of reacting with a silanol group in the silica-based condensation polymer (B), for example, at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a silyl halide group and an alkoxysilyl group. Is used as a part of the radically polymerizable vinyl compound (A) component since the vinyl compound having in the molecule functions to further improve physical properties such as rigidity, toughness, and heat resistance of the composite composition. It is an aspect.

Examples of the vinyl compound containing such a reactive group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, vinyltrichlorosilane, vinyl Trimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and the like.
Hydroxyethyl methacrylate, methacrylic acid, vinyltrichlorosilane, vinyltrimethoxysilane, γ-
Methacryloyloxypropyltrimethoxysilane is particularly preferred.

The silica-based polycondensate (B) used in the present invention is represented by the following general formula (1) SiR ¹ _a R ² _b (OR ³ ) _c (1) in a colloidal silica dispersion. ¹ , R ² has 1 to 1 carbon atoms which may have an ether bond, an ester bond or a carbon-carbon double bond.
0 hydrocarbon residue, R ³ is a hydrogen atom or an ether bond,
A hydrocarbon residue having 1 to 10 carbon atoms which may have an ester bond or a carbon-carbon double bond;
And c is 4-ab, and represents an integer of 1 to 4. )) At least one of the silane compounds represented by O
It is a condensation polymer obtained by hydrolyzing and condensation-polymerizing most of the R ³ groups, and has OR ³ groups or OR ³ groups and OH groups on its outer surface. Therefore, it dissolves in the radically polymerizable vinyl compound (A).

The silica-based polycondensate (B) is free from radical polymerization even at a silica concentration that would cause gelation when only colloidal silica was dispersed in the radically polymerizable vinyl compound (A). It is possible to disperse uniformly in the functional vinyl compound (A). That is, according to the present invention, it is possible to uniformly disperse silica at a high concentration in a composite composition, and to impart desired physical properties to the composite composition.

As the colloidal silica dispersion used in the present invention, various commercial products can be used. The particle size of the colloidal silica is usually 1 nm to 1 μm,
There is no particular limitation. However, the preferred particle size is between 5 nm and 500 nm. The dispersion medium of the colloidal silica is not particularly limited, but usually, water; alcohols such as methanol and isopropyl alcohol; cellosolves; dimethylacetamide and the like are used. Particularly preferred dispersion media are alcohols, cellosolves and water.

[0015] Among the silane compounds represented by the general formula (1) used in the present invention, the following general formula (2) to (7)
The silane compound represented by the following can be mentioned as a preferable example.

SiR ⁴ _a R ⁵ _b (OR ⁶ ) _c (2) SiR ⁴ _n (O—CH ₂ CH ₂ —O—CO— (R ⁷ ) C = CH ₂ ) _4-n (3) CH ₂ = C (R ⁷ ) COO (CH ₂ ) _p SiR ⁸ _n (OR ⁶ ) _3-n (4) CH ₂ = CHSiR ⁸ _n (OR ⁶ ) _3-n (5) HS (CH ₂ ) _p -SiR ⁸ _n (OR ⁶ ) _3-n (6)

[0017]

Embedded image (Wherein, R ⁴ and R ⁵ are a hydrocarbon residue having 1 to 10 carbon atoms which may have an ether bond or an ester bond; R ⁶ is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms; ⁷ is a hydrogen atom or a methyl group, R ^{8 is} an alkyl group having 1 to 3 carbon atoms or a phenyl group, a and b are integers of 0 to 3, c is 4-
ab, an integer of 1-4, n is an integer of 0-2, p
Represents an integer of 1 to 6. As the silane compound represented by the general formula (2),
For example, tetramethoxysilane, tetraethoxysilane,
Tetrapropoxysilane, tetrabutoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, methylethyldiethoxysilane, methylphenyldimethoxysilane Silane, trimethylethoxysilane, methoxyethyltriethoxysilane, acetoxyethyltriethoxysilane, diethoxyethyldiethoxysilane, tetraacetoxysilane, methyltriacetoxysilane, tetrakis (2-methoxyethoxy) silane and their partially hydrolyzed products No.

Examples of the silane compound represented by the general formula (3) include tetrakis (acryloyloxyethoxy) silane, tetrakis (methacryloyloxyethoxy) silane, methyltris (acryloyloxyethoxy) silane and methyltris (methacryloyloxyethoxy) silane. Among them, tetrakis (acryloyloxyethoxy) silane and tetrakis (methacryloyloxyethoxy) silane are preferable,
These are synthesized, for example, from tetrachlorosilane and 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate.

Examples of the silane compound represented by the general formula (4) include β-acryloyloxyethyldimethoxymethylsilane, γ-acryloyloxypropylmethoxydimethylsilane, γ-acryloyloxypropyltrimethoxysilane, β-methacryloyloxyethyl Dimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and the like.
As the silane compound represented by the general formula (5),
For example, vinyl methyl dimethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane can be mentioned.
Examples of the compound represented by the general formula (6) include γ-mercaptopropyldimethoxymethylsilane and γ-mercaptopropyldimethoxymethylsilane.
And mercaptopropyltrimethoxysilane.
Examples of the compound represented by the general formula (7) include p-vinylphenylmethyldimethoxysilane and p-vinylphenyltrimethoxysilane.

In the present invention, the above general formulas (2) to (7)
The following five embodiments are exemplified as preferred uses of the silane compound represented by

The first embodiment is an embodiment in which one or more silane compounds represented by the general formula (2) are used. In the general formula (2), R ⁴ , R ⁵ and R ⁶ each have 1 carbon atom.
It is preferable to use a silane compound that is a hydrocarbon residue of 4 to 4. When R ⁴ , R ⁵ , and R ⁶ are hydrocarbon residues having 4 or less carbon atoms, steric hindrance is small, so that hydrolysis,
The polycondensation rate is increased, and the colloidal silica particles are easily bonded to each other to form a silica skeleton. Particularly preferred silane compounds are tetraalkoxysilanes in which c is 4 in the above general formula (2). The tetraalkoxysilane is used alone, or a trialkoxysilane or tetraalkoxysilane is used in consideration of stability before polymerization. It is preferable to use a mixture of dialkoxysilane.

The second embodiment is an embodiment in which one or more silane compounds represented by the general formula (3) are used. When the silane compound represented by the general formula (3) is hydrolyzed and polycondensed, the acryloyloxyethoxy group or methacryloyloxyethoxy group remaining in the silica-based polycondensate (B) without being hydrolyzed becomes a radical during polymerization. It copolymerizes with the polymerizable vinyl compound (A) and chemically bonds. For this reason, it contributes to reinforcement of the interface between the polymer of the radically polymerizable vinyl compound (A) and the silica-based condensation polymer (B).

Further, even if the acryloyloxyethoxy group or methacryloyloxyethoxy group remaining without hydrolysis is eliminated due to further condensation polymerization during polymerization with the radically polymerizable vinyl compound (A), Since the leaving group is copolymerized with the radically polymerizable vinyl compound (A), it does not become a volatile component, and the resulting composite composition does not cause foaming, cracking, or cracking. In a third embodiment, one or more silane compounds represented by the general formula (2) and one or more silane compounds represented by the general formula (3) are used in combination. When these two types of silane compounds are used in combination, in addition to the effects obtained when each of the above-mentioned silane compounds is used alone, the silane compound represented by the general formula (3) has a three-dimensional structure around its silicon atom. Therefore, the silica-based condensation polymer (B) is stably maintained until the polymerization operation described below.

In a fourth embodiment, the above general formulas (4) to (7)
This is an embodiment in which one or more silane compounds represented by the following formulas are used. These silane compounds and their hydrolysis products are:
Since it also acts as a copolymerizable monomer or a chain transfer agent during the polymerization of the radically polymerizable vinyl compound (A), the interface between the polymer of the radically polymerizable vinyl compound (A) and the silica-based condensation polymer (B) It contributes to reinforcement and improves the physical properties of the composite composition of the present invention.

In a fifth aspect, one or more of the silane compounds represented by the general formula (2) and the silane compounds represented by the general formulas (4) to (4) are used.
This is an embodiment in which one or more silane compounds represented by (7) are used in combination. When these two silane compounds are used in combination, the silica skeletons formed from the silane compounds represented by the general formula (2) described in the first embodiment are represented by the general formulas (4) to (7). Radical polymerizable vinyl compound (A)
And a silica-based condensation polymer (B) to form a stronger bond, thereby improving the physical properties of the resulting composite composition.

In order to induce a silica-based condensed polymer (B) obtained by hydrolyzing and condensing a silane compound in a dispersion of colloidal silica, the above-mentioned silane compound alone may be used. Co-condensable components may be used in combination.
Examples of the component capable of co-condensing with the silane compound include metal alkoxides, organic metal salts, and metal chelates. The use ratio of the co-condensable component is preferably 0 to 100 parts by weight with respect to 100 parts by weight of the silane compound.
-50 parts by weight is more preferred.

Examples of metal alkoxides, organic metal salts and metal chelates which can be co-condensed include titanium tetraethoxide, titanium tetraisopropoxide, zirconium tetraethoxide, zirconium tetra-n-butoxide, aluminum triisopropoxide, and the like. Examples include zinc acetylacetonate, lead acetate, and barium oxalate.

In the hydrolysis and polycondensation reaction of the silane compound, water must be present in the reaction system.
In general, the effect of the proportion of water in the reaction system on the reaction rate is not particularly significant. However, when the proportion is extremely small, hydrolysis is too slow to obtain a condensation polymer.

As a catalyst for performing the hydrolysis reaction of the silane compound, an inorganic acid or an organic acid can be used. As the inorganic acid, for example, hydrohalic acid such as hydrochloric acid, hydrofluoric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid and the like are used. Organic acids include formic acid, acetic acid, oxalic acid,
Examples include acrylic acid and methacrylic acid.

In the hydrolysis reaction system of the silane compound, a solvent can be used to carry out the reaction mildly and uniformly. As the solvent, a solvent capable of dissolving the reactant silane alkoxide, water and a catalyst is desirable. Examples of such a solvent include water; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; ketones such as acetone and methyl isobutyl ketone; and ethers such as tetrahydrofuran and dioxane. As the solvent, the above-described dispersion medium of colloidal silica may be used as it is, or a new necessary amount may be added. The amount of the solvent to be used is not particularly limited as long as the reactant can be uniformly dissolved, but if the concentration of the reactant is too low, the reaction rate may be significantly reduced. The hydrolysis and polycondensation reaction of the silane compound is carried out at a temperature of about room temperature to about 120 ° C. for about 30 minutes to about 24 hours, preferably at about room temperature to about the boiling point of the solvent for about 1 to about 10 hours. Done.

The amounts of the colloidal silica in the silica-based condensation polymer (B) and the silane compound represented by the general formula (1) are not particularly limited.
The silane compound is preferably used in an amount of 0.1 to 2,000 parts by weight, more preferably 1 to 1,000 parts by weight, based on 0 parts by weight.

When one or more of the compounds represented by the general formula (2) is used as the silane compound, the silane compound is used in an amount of 5 to 20 based on 100 parts by weight of the solid content of the colloidal silica.
00 parts by weight is preferable, and 10 to 1000 parts by weight is more preferable.

When one or more of the compounds represented by the general formula (3) is used as the silane compound, the silane compounds 1 to 20 are added to 100 parts by weight of the solid content of the colloidal silica.
00 parts by weight is preferable, and 5 to 1000 parts by weight is more preferable.

When one or more of the compounds represented by the general formula (2) and one or more of the compounds represented by the general formula (3) are used in combination as the silane compound, based on 100 parts by weight of the solid content of the colloidal silica, The silane compound represented by the general formula (2) is preferably 5 to 2,000 parts by weight,
1000 parts by weight is more preferable, and the silane compound represented by the general formula (3) is preferably 0.1 to 2000 parts by weight, more preferably 1 to 1000 parts by weight.

The silane compounds represented by the general formulas (4) to (7)
When one or more of the compounds represented by formula (1) is used, the silane compound is preferably used in an amount of 1 to 2,000 parts by weight, more preferably 5 to 1,000 parts by weight, based on 100 parts by weight of the solid content of colloidal silica.

When one or more of the compounds represented by the general formula (2) and one or more of the compounds represented by the general formulas (4) to (7) are used in combination, the solid content of colloidal silica is 100% by weight. Parts by weight, the silane compound represented by the general formula (2) is preferably 5 to 2,000 parts by weight, more preferably 10 to 1000 parts by weight, and the silane compound represented by the general formulas (4) to (7) is 0.1 to 0.1 parts by weight. ~ 2
000 parts by weight is preferable, and 1 to 1000 parts by weight is more preferable.

The composite composition of the present invention comprises a silica-based condensed polymer (B) obtained by hydrolyzing and condensing a silane compound in a colloidal silica dispersion, and a radically polymerizable vinyl compound (A). ). The content ratio of the radical polymerizable vinyl compound (A) and the silica-based condensation polymer (B) is selected so as to be contained in the range of (A) 1 to 99% by weight and (B) 99 to 1% by weight. (A) 10 to 90% by weight, (B) 90 to 10% by weight
Is more preferably used, and more preferably (A) 20 to 80% by weight, and (B) 80 to 20% by weight. When the silica-based condensed polymer (B) is 80 to 20% by weight, the physical properties aimed at by the present invention are particularly sufficiently exhibited.

The composite composition of the present invention is preferably formed by mixing the radically polymerizable vinyl compound (A) and the silica-based condensed polymer (B) in a desired state and simultaneously polymerizing them. In addition, 1-20% by weight of monomer
The composition may be a composition obtained by mixing and polymerizing a radically polymerizable vinyl compound (A) containing a polymer partially polymerized and a silica-based condensation polymer (B).

The composite composition of the present invention has a haze value of 5% or less at a plate thickness of 3 mm even when the SiO ₂ content is 15% by weight or more. Electron micrographs show that the colloidal silica particles are very uniformly dispersed without agglomeration. This indicates that the colloidal silica particles in the composite composition of the present invention are incorporated into a silica skeleton obtained by hydrolyzing and polycondensing a silane compound, and the polymer and molecule of the radically polymerizable vinyl compound (A) It means that they are compatibilized at a level, and enables the expression of excellent transparency. In the case where silica fine particles are simply dispersed in an acrylic resin, when the SiO ₂ content is 15% by weight or more, the haze value at a plate thickness of 3 mm exceeds 20%, and the transparency is greatly reduced.

The method for obtaining the composite composition of the present invention is not particularly limited, but it is preferable to produce the composite composition by a conventionally known casting polymerization method. As an example of the casting polymerization method, first, a radical polymerizable vinyl compound (A) as a monomer or a partial polymer is mixed with a silica-based polycondensate (B), and a solvent remaining in the mixed solution or After distilling off water to prepare a mixed solution in which the component (B) is dissolved in the component (A), a radical polymerization initiator is added, and this is used as a casting raw material. As a specific method of mixing both components, a method in which the component (A) is directly mixed with a solution in which the silica-based condensation polymer (B) is dissolved in a solvent, and then the solvent and water of the component (B) are removed, or It is carried out by a method of adding the component (A) while removing the solvent of the component (B) and water from the solution of the silica-based condensation polymer (B). That is, it is important to prepare a mixed solution of both components in a state where the component (B) is not precipitated as a solid. It should be noted that the viscosity of the mixed solution used here is not a problem as long as the component (B) is uniformly dissolved in the component (A), and the mixed solution defines a gel-like state. It may be.

The radical polymerization initiator used here includes 2,2'-azobis (isobutyronitrile),
Azo compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), and organic compounds such as benzoyl peroxide and lauroyl peroxide Peroxides and redox-based polymerization initiators can be mentioned.

The casting material is injected between two opposed surface-treated inorganic glass plates or metal plates whose periphery is sealed with a gasket and heated (cell casting method) or proceeds at the same speed in the same direction. Casting polymerization is carried out by a method of continuously injecting the above-mentioned casting raw material from the upstream of a space sealed by two stainless steel endless belts polished to one side mirror surface and a gasket and heating (continuous casting method) or the like. be able to.

The polymerization curing temperature for producing the composite composition of the present invention is generally from 10 to 150 ° C.,
It is preferable that the polymerization is performed by simultaneously proceeding the polymerization of the radically polymerizable vinyl compound (A) and the further polycondensation of the silica-based polycondensate (B) at a temperature of 150 ° C. or higher at ordinary temperature.

Further, in any of the convenient steps of the present invention, it is possible to use a mixture of additives such as a coloring agent, an ultraviolet absorber, a heat stabilizer and a release agent as long as the effects of the present invention are not impaired. it can.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto. In the following examples, "parts" means "parts by weight" unless otherwise specified.

The transparency was measured using an integrating sphere haze meter (SEP-H-SS, manufactured by Nippon Seimitsu Kogaku).
Total light transmittance and haze were measured according to TMD1003. The heat resistance is determined by annealing a sample at 130 ° C. for 60 hours and then subjecting the sample to a heat distortion temperature (HDT) according to ASTM D648.
Was measured. As for the strength, after the sample was annealed at 130 ° C. for 60 hours, a bending test was performed according to ASTM D790, and the bending fracture strength and the flexural modulus were measured.

Example 1 In a glass flask equipped with stirring blades, 98.8 parts of tetraethoxysilane (hereinafter abbreviated as TES) and colloidal silica dispersed with isopropyl alcohol (silica content: 30% by weight, manufactured by Catalyst Chemical Industry Co., Ltd.) Brand name OSCAL-143
2, hereinafter abbreviated as S-1) 100 parts, and while stirring, 18 parts of deionized water and 0.5 part of 36% by weight hydrochloric acid were added, and
The temperature was raised to 0 ° C. After 2 hours, methyl methacrylate (hereinafter abbreviated as MMA) was added at the same rate as the evaporation of volatiles while removing the volatiles at 40 ° C. under reduced pressure using a rotary evaporator, and finally the solvent was completely replaced with MMA. And concentrated to a total of 150 parts. The solid content (SiO ₂ content) calculated from the ash content after baking this in a crucible was 40% by weight.

To 150 parts of this mixed solution, 2,2′-azobisisobutyronitrile (hereinafter referred to as AI) was used as a polymerization initiator.
After dissolving 0.15 parts (abbreviated as BN), dissolved air was removed by reducing the pressure, and the mixture was poured into a cell formed of a gasket and two stainless steel plates and set in advance to a thickness of 3 mm. . Thereafter, polymerization was carried out at 80 ° C. for 5 hours and at 130 ° C. for 2 hours to obtain a cast plate. Table 1 shows the evaluation results of the physical properties of the obtained cast plate.

Example 2 In a glass flask equipped with a stirring blade, 98.8 parts of TES,
3. Methyltriethoxysilane (hereinafter abbreviated as MTES)
5 parts, 100 parts of colloidal silica S-1 and 80 parts of ethanol were added, and while stirring, 18 parts of deionized water and 0.5 part of 36% hydrochloric acid were added, and the mixture was heated to 70 ° C. After 2 hours, use a rotary evaporator under reduced pressure at 40 ° C.
MMA was added at the same rate as the evaporation of the volatile components while distilling off the volatile components, and finally the solvent was completely replaced with MMA and concentrated to a total amount of 150 parts (SiO ₂ content 40% by weight).

AIBN was added to 150 parts of this mixed solution in 0.1 part.
Fifteen parts were added, and polymerization was performed in the same manner as in Example 1 to obtain a cast plate. Table 1 shows the evaluation results of the physical properties of the obtained cast plate.

Example 3 A glass flask equipped with a stirring blade was charged with 98.8 parts of TES,
4.5 parts of MTES and colloidal silica dispersed in methyl alcohol (silica content: 30% by weight, Catalyst Chemical Industry Co., Ltd.)
OSCAL-1132 (trade name, hereinafter abbreviated as S-2) 1
Add 00 parts and, with stirring, 36 parts of deionized water and 3 parts
0.5 parts of 6% by weight hydrochloric acid was added, and the mixture was heated under reflux. After 2 hours, the mixture was cooled, 100 parts of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA) was added, volatiles were distilled off at 40% under reduced pressure by a rotary evaporator, and the volatiles were completely removed by a vacuum pump. The solvent was distilled off to make the total amount 170 parts (SiO ₂ content 36% by weight).

AIBN was added to 150 parts of this mixed solution in 0.1 part.
Fifteen parts were added, and polymerization was performed in the same manner as in Example 1 to obtain a cast plate. Table 1 shows the evaluation results of the physical properties of the obtained cast plate.

Example 4 A glass flask equipped with stirring blades was charged with 22.3 parts of MTES and 200 parts of colloidal silica S-1, and 14 parts of deionized water and 0.5 part of 36% by weight hydrochloric acid were added with stirring. The temperature was raised to 70 ° C. Two hours later, 10 parts of HEMA was added, and MMA was added at 40 ° C. under reduced pressure at a reduced pressure using a rotary evaporator at the same rate as the evaporation of volatiles. Finally, the solvent was completely replaced with MMA and concentrated. The total amount was 135 parts (50% by weight of SiO ₂ ).

AIBN was added to 135 parts of this mixed solution in 0.1 part.
13 parts were added and polymerization was carried out in exactly the same manner as in Example 1 to obtain a cast plate. Table 1 shows the evaluation results of the physical properties of the obtained cast plate.

Example 5 98.8 parts of TES was placed in a glass flask equipped with stirring blades.
4.5 parts of MTES and colloidal silica S-1 10
0 parts, and with stirring, 18 parts of deionized water and 36 parts
0.5 parts by weight of hydrochloric acid was added, and the mixture was heated to 70 ° C. After 2 hours, the mixture is cooled to 0 ° C., and while stirring 5.0 parts of titanium tetraisopropoxide (hereinafter abbreviated as TTIP) previously cooled to 0 ° C. in 50 parts of isopropyl alcohol while stirring. Added slowly. Thereafter, MMA was added at the same rate as the evaporation of the volatile components while distilling off the volatile components at 40 ° C. under reduced pressure using a rotary evaporator.
Finally, the solvent was completely replaced with MMA and concentrated to a total volume of 1%.
50 parts (40% by weight of SiO ₂ ).

AIBN was added to 150 parts of the mixed solution in 0.1 part.
Fifteen parts were added, and polymerization was performed in the same manner as in Example 1 to obtain a cast plate. Table 1 shows the evaluation results of the physical properties of the obtained cast plate.

Example 6 In a glass flask equipped with stirring blades, 22.3 parts of MTES and water-dispersed colloidal silica (silica content: 20% by weight, manufactured by Nissan Chemical Industry Co., Ltd., trade name: Snowtex-
0, hereafter abbreviated as S-3) 300 parts were added, and 3
0.5 parts of 6% by weight hydrochloric acid was added, and the mixture was heated to 70 ° C. 2
After time, the mixture was cooled and 100 parts of HEMA was added.
In order to azeotrope water, 100 parts of ethyl cellosolve was added, and volatile components were completely distilled off by a rotary evaporator to make the total amount 170 parts (SiO ₂ content 40% by weight).

AIBN was added to 150 parts of this mixed solution in 0.1 part.
Fifteen parts were added, and polymerization was performed in the same manner as in Example 1 to obtain a cast plate. Table 1 shows the evaluation results of the physical properties of the obtained cast plate.

Examples 7 to 9 Cast plates were prepared in exactly the same manner as in Example 1 except that the types and amounts of the radically polymerizable vinyl compound, colloidal silica and silane compound were changed as shown in Table 1. Obtained.
Table 1 shows the evaluation results of the physical properties of the obtained cast plate.

Comparative Example 1 0.15 parts of AIBN was dissolved in 150 parts by weight of MMA.
Polymerization was carried out in the same manner as in Example 1 to obtain a cast plate. Table 1 shows the evaluation results of the physical properties of the obtained cast plate.

Comparative Example 2 100 parts of colloidal silica S-1 was subjected to MMA while removing volatile components at 40 ° C. under reduced pressure using a rotary evaporator.
Was added at the same rate as the evaporation of volatiles, and the solvent was completely replaced with MMA to obtain a solution having a solid content of 30% by weight.
Before completely replacing, the solution viscosity suddenly rises and gels,
The polymerization operation could not be performed.

[0062]

[Table 1] Synthesis Example 68 parts of tetrachlorosilane was added dropwise to 208 parts of HEMA at room temperature over 4 hours with stirring. After completion of the dropwise addition, stirring was continued for 0.5 hour, and then the temperature was raised to 50 ° C. One hour later, a volatile component was completely removed using a rotary evaporator to obtain tetrakis (methacryloyloxyethoxy) silane (hereinafter abbreviated as TMES).

Further, tetrakis (acryloyloxyethoxy) silane (hereinafter abbreviated as TAES) was obtained in the same manner except that 186 parts of 2-hydroxyethyl acrylate was used instead of 208 parts of HEMA.

Example 10 The TME obtained in Synthesis Example was placed in a glass flask equipped with stirring blades.
S32.6 parts and colloidal silica S-1 240 parts were added, and while stirring, 8.6 parts of deionized water and 0.1 part of 36% by weight hydrochloric acid were added, and the temperature was raised to 70 ° C. After 2 hours, MMA was added at the same rate as the evaporation of volatiles while removing the volatiles at 40 ° C. under reduced pressure using a rotary evaporator.
Finally, the solvent was completely replaced by MMA to make the total amount 150 parts (SiO ₂ content 50% by weight).

AIBN 0.15 was added to 150 parts of the mixture.
After dissolving the part, the pressure is reduced to remove the dissolved air, formed by a gasket and two stainless steel plates,
The mixture was poured into a cell which was previously set to have a thickness of 3 mm. Thereafter, polymerization was carried out at 80 ° C. for 2 hours and at 130 ° C. for 2 hours to obtain a cast plate. Table 2 shows the evaluation results of the physical properties of the obtained cast plate.

Example 11 A glass flask equipped with stirring blades was charged with 32.6 parts of TMES and 240 parts of colloidal silica S-1. While stirring, 4.3 parts of deionized water and 0.1% of 36% by weight hydrochloric acid were added.
Then, the temperature was raised to 70 ° C. After 2 hours, the mixture was cooled, 75 parts of HEMA was added, the volatiles were distilled off at 40 ° C. under reduced pressure by a rotary evaporator, and the volatiles were completely distilled off with a vacuum pump to make the total amount 150 parts (SiO 2).
50% by weight for ₂ minutes).

AIBN was added to 150 parts of this mixed solution in 0.1 part.
Fifteen parts were added, and polymerization was performed in the same manner as in Example 10 to obtain a cast plate. Table 2 shows the evaluation results of the physical properties of the obtained cast plate.

Example 12 A glass flask equipped with stirring blades was charged with 32.6 parts of TMES and 240 parts of colloidal silica S-2. While stirring, 4.3 parts of deionized water and 0.1 part of 36% by weight hydrochloric acid were added. In addition, the mixture was heated to reflux. After 2 hours, the MMA was distilled off at 40 ° C. under reduced pressure using a rotary evaporator.
At the same rate as the volatiles are distilled off.
And completely concentrated to 150 parts by weight (Si
O ₂ minute 50% by weight).

AIBN was added to 0.1 part of 150 parts of the mixed solution.
Fifteen parts were added, and polymerization was performed in the same manner as in Example 10 to obtain a cast plate. Table 2 shows the evaluation results of the physical properties of the obtained cast plate.

Example 13 27.2 parts of TMES and 300 parts of colloidal silica S-3 were placed in a glass flask equipped with stirring blades, and 0.5 part of 36% by weight hydrochloric acid was added with stirring, followed by heating to 70 ° C. . After 2 hours, the mixture was cooled and 95 parts of HEMA were added. Ethyl cellosolve 100 to azeotrope water
The volatile components were distilled off at 40 ° C. under reduced pressure by a rotary evaporator, and the volatile components were completely distilled off by a vacuum pump to make the total amount 157 parts (SiO ₂ content: 40% by weight).

AIBN was added to 150 parts of this mixed solution in 0.1 part.
Fifteen parts were added, and polymerization was performed in the same manner as in Example 10 to obtain a cast plate. Table 2 shows the evaluation results of the physical properties of the obtained cast plate.

Examples 14 to 16 Example 10 was repeated except that the types and amounts of the radically polymerizable vinyl compound, colloidal silica and silane compound and the solid content in the mixed solution were changed as shown in Table 2. A cast plate was obtained in exactly the same manner as described above. Table 2 shows the evaluation results of the physical properties of the obtained cast plate.

[0073]

[Table 2] Example 17 A glass flask with a stirring blade was charged with 41.6 parts of TES,
27.2 parts of TMES and colloidal silica S-12
Add 00 parts and, with stirring, 9 parts of deionized water and 36 parts.
0.2% by weight of hydrochloric acid was added, and the temperature was raised to 70 ° C.

After 2 hours, MMA was added at the same rate as the evaporation of volatiles while distilling off volatiles at 40 ° C. under reduced pressure using a rotary evaporator. Finally, the solvent was completely replaced with MMA and concentrated to obtain a total amount. Was 150 parts (50% by weight of SiO ₂ ).

In 150 parts of this mixed solution, 0.1 parts of AIBN were added.
After dissolving 5 parts, the dissolved air was removed under reduced pressure, and the mixture was poured into a cell formed of a gasket and two stainless steel plates and set in advance to a thickness of 3 mm. Thereafter, polymerization was carried out at 80 ° C. for 5 hours and at 130 ° C. for 2 hours to obtain a cast plate. Table 3 shows the evaluation results of the physical properties of the obtained cast plate.

Example 18 A glass flask equipped with a stirring blade was charged with 41.6 parts of TES,
27.2 parts of TMES and colloidal silica S-22
Add 00 parts and, with stirring, 36 parts of deionized water and 3 parts
0.5 parts of 6% by weight hydrochloric acid was added, and the mixture was heated under reflux.

After 2 hours, the mixture is cooled and HEMA 75
The volatile components were distilled off at 40 ° C. under reduced pressure by a rotary evaporator, and the volatile components were completely distilled off by a vacuum pump to make the total amount 150 parts (50% by weight of SiO ₂ ).

AIBN was added to 150 parts of this mixed solution in 0.1 part.
Fifteen parts were added, and polymerization was carried out in exactly the same manner as in Example 17 to obtain a cast plate. Table 3 shows the evaluation results of the physical properties of the obtained cast plate.

Example 19 MTES 26.7 was placed in a glass flask with stirring blades.
Parts, 27.2 parts of TMES and colloidal silica S-1
200 parts were added, and 14 parts of deionized water and 0.5 part of 36% by weight hydrochloric acid were added with stirring, and the temperature was raised to 70 ° C.

After 2 hours, MMA was added at the same rate as the evaporation of volatiles while distilling off volatiles at 40 ° C. under reduced pressure using a rotary evaporator. Finally, the solvent was completely replaced with MMA. (SiO ₂ content 50% by weight).

AIBN was added to 135 parts of this mixed solution in 0.1 part.
13 parts were added and polymerized in the same manner as in Example 17 to obtain a cast plate. Table 3 shows the evaluation results of the physical properties of the obtained cast plate.

Example 20 A glass flask equipped with a stirring blade was charged with 41.6 parts of TES,
27.2 parts of TMES and colloidal silica S-12
Add 00 parts and, with stirring, 18 parts of deionized water and 3 parts.
0.5 parts of 6% by weight hydrochloric acid was added, and the temperature was raised to 70 ° C.

After 2 hours, the mixture was cooled to 0 ° C. and 5.0 parts of TTIP, previously cooled to 0 ° C., were slowly added with stirring to a solution of 50 parts of isopropyl alcohol. Thereafter, MMA was added at the same rate as the evaporation of the volatile components while distilling off the volatile components at 40 ° C. under reduced pressure using a rotary evaporator. Finally, the solvent was completely replaced with MMA and concentrated to a total amount of 190 parts ( SiO ₂ content 40% by weight).

AIBN was added to 150 parts of the mixed solution in 0.1 part.
Fifteen parts were added, and polymerization was performed in the same manner as in Example 17 to obtain a cast plate. Table 3 shows the evaluation results of the physical properties of the obtained cast plate.

Example 21 A glass flask equipped with stirring blades was charged with MTES 26.7.
Parts, 27.2 parts of TMES and colloidal silica S-3
Add 300 parts and add 0.5% of 36% by weight hydrochloric acid while stirring.
And heated to 70 ° C.

After 2 hours, the mixture was cooled and HEMA 10
0 parts were added. To azeotrope water, add 100 parts of ethyl cellosolve and reduce the pressure by a rotary evaporator under reduced pressure.
Volatile components were distilled off at ℃, and the volatile components were further completely removed by a vacuum pump to make the total amount 180 parts (SiO ₂ content 40% by weight).

AIBN was added to 150 parts of this mixed solution in 0.1 part.
Fifteen parts were added, and polymerization was performed in the same manner as in Example 17 to obtain a cast plate. Table 3 shows the evaluation results of the physical properties of the obtained cast plate.

Examples 22 to 24 Except that the types and amounts of the radically polymerizable vinyl compound, colloidal silica, and silane compound were changed as shown in Table 3, a cast plate was prepared in the same manner as in Example 17. Obtained. Table 3 shows the evaluation results of the physical properties of the obtained cast plate.

[0089]

[Table 3] Example 25 A glass flask equipped with stirring blades was charged with γ-methacryloyloxypropyltrimethoxysilane (hereinafter referred to as MPTMS).
29.8 parts) and 6.5 parts of deionized water and 0.1 part of 36% by weight hydrochloric acid were added with stirring, and the temperature was raised to 70 ° C. After 2 hours, MMA was added at the same rate as the evaporation of volatiles while removing the volatiles at 40 ° C. under reduced pressure using a rotary evaporator.
Finally, the solvent was completely replaced with MMA and concentrated to a total volume of 1%.
58 parts (50% by weight of SiO ₂ ).

To 150 parts of this mixed solution was added 0.1 parts of AIBN.
After dissolving 5 parts, the dissolved air was removed under reduced pressure, and the mixture was poured into a cell formed of a gasket and two stainless steel plates and set in advance to a thickness of 3 mm. Thereafter, polymerization was carried out at 80 ° C. for 2 hours and at 130 ° C. for 2 hours to obtain a cast plate. Table 4 shows the evaluation results of the physical properties of the obtained cast plate.

Example 26 17.8 parts of vinyltrimethoxysilane (hereinafter abbreviated as VTMS) and 240 parts of colloidal silica S-1 were placed in a glass flask equipped with stirring blades, and 6.5 parts of deionized water was stirred. And 0.1 part of 36% by weight hydrochloric acid were added, and the mixture was heated to 70 ° C. After 2 hours, the mixture was cooled and H
10 parts of EMA was added, and MMA was added at the same rate as the evaporation of volatiles while removing volatiles at 40 ° C. under reduced pressure using a rotary evaporator. Finally, the solvent was completely replaced with MMA.
It was concentrated to a total amount of 158 parts (SiO ₂ content: 50% by weight).

To 150 parts of this mixed solution was added AIBN 0.1
Five parts were added and polymerization was carried out in exactly the same manner as in Example 25 to obtain a cast plate. Table 4 shows the evaluation results of the physical properties of the obtained cast plate.

Example 27 MPTMS 29.8 was added to a glass flask equipped with stirring blades.
Parts and 240 parts of colloidal silica S-2, 6.5 parts of deionized water and 0.1 part of 36% by weight hydrochloric acid were added with stirring, and the temperature was raised to 70 ° C. After 2 hours, the mixture was cooled, 75 parts of HEMA was added, the volatiles were distilled off at 40 ° C. under reduced pressure using a rotary evaporator, and the volatiles were completely distilled off with a vacuum pump to a total amount of 158 parts (S
iO ₂ 50% by weight).

AIBN was added to 0.1 part of the mixed solution in 150 parts.
Fifteen parts were added and polymerization was carried out in exactly the same manner as in Example 25 to obtain a cast plate. Table 4 shows the evaluation results of the physical properties of the obtained cast plate.

Examples 28-32 The radical polymerizable vinyl compound, colloidal silica, the type and amount of the silane compound, and the proportion of solids in the mixed solution were changed as shown in Table 4, except that: Example 2
A cast plate was obtained in exactly the same manner as in No. 5. Table 4 shows the evaluation results of the physical properties of the obtained cast plate.

[0096]

[Table 4] Abbreviations in the table are as follows. MCTMS: γ-mercaptopropyltrimethoxysilane MPDMS: γ-methacryloyloxypropyldimethoxymethylsilane VPTMS: p-vinylphenylmethyldimethoxysilane Example 33 98.8 parts of TES was placed in a glass flask with stirring blades.
6.2 parts of MPTMS, colloidal silica S-1 100
And 80 parts of ethanol, 18 parts of deionized water and 0.5 part of 36% by weight hydrochloric acid were added while stirring, and
The temperature was raised to 0 ° C.

After 2 hours, MMA was added at the same rate as the evaporation of volatiles while distilling off volatiles at 40 ° C. under reduced pressure using a rotary evaporator. Finally, the solvent was completely replaced with MMA and concentrated to obtain a total amount. Was set to 150 parts (SiO ₂ content: 40% by weight).

In 150 parts of this mixed solution, 0.1 parts of AIBN were added.
After dissolving 5 parts, the dissolved air was removed under reduced pressure, and the mixture was poured into a cell formed of a gasket and two stainless steel plates and set in advance to a thickness of 3 mm. Thereafter, polymerization was carried out at 80 ° C. for 2 hours and at 130 ° C. for 2 hours to obtain a cast plate. Table 5 shows the evaluation results of the physical properties of the obtained cast plate.

Example 34 A glass flask equipped with a stirring blade was charged with 98.8 parts of TES,
6.2 parts of MPTMS and colloidal silica S-21
Add 00 parts and, with stirring, 36 parts of deionized water and 3 parts
0.5 parts of 6% by weight hydrochloric acid was added, and the mixture was heated under reflux.

After 2 hours, the mixture was cooled and HEMA 10
0 parts were added and volatile components were distilled off at 40 ° C. under reduced pressure by a rotary evaporator, and then the volatile components were completely distilled off by a vacuum pump to make the total amount 170 parts (SiO ₂ content 36% by weight).

AIBN was added to 150 parts of this mixed solution in 0.1 part.
Fifteen parts were added, and polymerization was performed in the same manner as in Example 33 to obtain a cast plate. Table 5 shows the evaluation results of the physical properties of the obtained cast plate.

Example 35 A glass flask equipped with a stirring blade was charged with 22.9 parts of TES,
16.3 parts of VTMS and colloidal silica S-12
20 parts were added, and while stirring, 6 parts of deionized water and 0.1 part of 36% by weight hydrochloric acid were added, and the temperature was raised to 70 ° C.

Two hours later, 10 parts of HEMA was added, and MMA was added at the same rate as the evaporation of volatiles while removing volatiles at 40 ° C. under reduced pressure using a rotary evaporator. Finally, the solvent was completely replaced with MMA. And concentrated to a total amount of 160 parts (SiO ₂ content 50% by weight).

AIBN was added to 130 parts of this mixed solution in 0.1 part.
13 parts were added and polymerized in the same manner as in Example 33 to obtain a cast plate. Table 5 shows the evaluation results of the physical properties of the obtained cast plate.

Example 36 A glass flask equipped with a stirring blade was charged with 98.8 parts of TES,
6.2 parts of MPTMS and colloidal silica S-11
Add 00 parts and, with stirring, 18 parts of deionized water and 3 parts.
0.5 parts of 6% by weight hydrochloric acid was added, and the temperature was raised to 70 ° C.

After 2 hours, the mixture was cooled to 0 ° C. and slowly added with stirring to a solution of 5.0 parts of TTIP, previously cooled to 0 ° C., dissolved in 50 parts of isopropyl alcohol. Thereafter, MMA was added at the same rate as the evaporation of volatiles while distilling off volatiles at 40 ° C. under reduced pressure using a rotary evaporator. Finally, the solvent was completely replaced with MMA.
It was concentrated to a total amount of 150 parts (SiO ₂ content: 40% by weight).

AIBN was added to 150 parts of this mixed solution in 0.1 part.
Fifteen parts were added, and polymerization was performed in the same manner as in Example 33 to obtain a cast plate. Table 5 shows the evaluation results of the physical properties of the obtained cast plate.

Example 37 MTES 22.3 was placed in a glass flask with stirring blades.
Parts, 6.2 parts MPTMS and colloidal silica S-3
Add 300 parts and add 0.5% of 36% by weight hydrochloric acid while stirring.
And heated to 70 ° C.

After 2 hours, the mixture was cooled and HEMA 10
0 parts were added. To azeotrope water, add 100 parts of ethyl cellosolve and reduce the pressure by a rotary evaporator under reduced pressure.
Volatile components were distilled off at ℃, and the volatile components were further completely removed by a vacuum pump to make the total amount 172 parts (SiO ₂ content 40% by weight).

AIBN was added to 150 parts of this mixed solution in 0.1 part.
Fifteen parts were added, and polymerization was performed in the same manner as in Example 33 to obtain a cast plate. Table 5 shows the evaluation results of the physical properties of the obtained cast plate.

Examples 38 to 42 Cast plates were prepared in exactly the same manner as in Example 1 except that the types and amounts of the radically polymerizable vinyl compound, colloidal silica, and silane compound were changed as shown in Table 1. Obtained.
Table 5 shows the evaluation results of the physical properties of the obtained cast plate.

[0112]

[Table 5] Abbreviations in the table are as follows. VPDMS: p-vinylphenylmethyldimethoxysilane MCTMS: γ-mercaptopropyltrimethoxysilane

[0113]

According to the present invention, excellent transparency, heat resistance,
A composite composition having stiffness and toughness has been provided. The composite composition is useful for various applications in which inorganic glass has been used conventionally, that is, for various applications such as window glasses for houses and vehicles.

Continued on the front page (31) Priority claim number Japanese Patent Application No. 3-243402 (32) Priority date Heisei 3 (1991) September 24 (33) Priority claim country Japan (JP) (31) Priority claim number Special Ganpei 3-243403 (32) Priority Date Hei 3 (1991) September 24 (33) Priority Country Japan (JP) (72) Inventor Hiroyuki Watanabe 20-1 Miyukicho, Otake City, Hiroshima Prefecture Mitsubishi Rayon (56) References JP-A-63-312311 (JP, A) JP-A-4-270710 (JP, A) "Journal of Applied Polymer Science", Vol. 27, p2921-2931, 1989 (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 283/12 C08F 2/44 C08K 3/36 C08L 83/04-83/08 CA (STN)

Claims (13)

(57) [Claims] 1. A radically polymerizable vinyl compound (A),
In a colloidal silica dispersion, the following general formula (1): SiR ¹ _a R ² _b (OR ³ ) _c (1) (wherein R ¹ and R ² represent an ether bond, an ester bond or a carbon-carbon double bond) 1 to 1 carbon atoms that may be present
0 hydrocarbon residue, R ³ is a hydrogen atom or an ether bond,
A hydrocarbon residue having 1 to 10 carbon atoms which may have an ester bond or a carbon-carbon double bond;
And c is 4-ab, and represents an integer of 1 to 4. (B) a silica-based condensation polymer obtained by hydrolyzing and condensation-polymerizing at least one silane compound represented by the formula (B):
A complex composition obtained by polymerizing in the presence, Siri
The silica skeleton of the polycondensate (B) and the radical polymerizable polymer
Forms a semi-IPN structure with a polymer of the benzyl compound (A)
A composite composition comprising: 2. The radically polymerizable vinyl compound (A) is
The composite composition according to claim 1, which is a methacrylate ester. 3. The composite composition according to claim 1, wherein the content of SiO ₂ is 15% by weight or more, and the haze value measured at a plate thickness of 3 mm is 5% or less. 4. A silane compound represented by the following general formula (2): SiR ⁴ _a R ⁵ _b (OR ⁶ ) _c (2) wherein R ⁴ and R ⁵ may have an ether bond or an ester bond. A hydrocarbon residue having 1 to 10 carbon atoms, R ⁶ is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, a, b
Is an integer of 0 to 3, c is 4-ab, and represents an integer of 1 to 4. 3. The composite composition according to claim 1, which is one or more of the compounds represented by the formula (1). 5. A silane compound represented by the following general formula (3): SiR ⁴ _n (O—CH ₂ CH ₂ —O—CO— (R ⁷ ) C = CH ₂ ) _4-n (3) ⁴ is a hydrocarbon residue having 1 to 10 carbon atoms which may have an ether bond or an ester bond, R ⁷ is a hydrogen atom or a methyl group, and n is an integer of 0 to 2). The composite composition according to claim 1 or 2, wherein 6. The silane compound is at least one of those represented by the following general formula (2) and at least one of those represented by the following general formula (3): SiR ⁴ _a R ⁵ _b (OR ⁶ ) _c (2) SiR ⁴ _n (O—CH ₂ CH ₂ —O—CO— (R ⁷ ) C = CH ₂ ) _4-n (3) (wherein R ⁴ and R ⁵ are carbon atoms which may have an ether bond or an ester bond) A hydrocarbon residue of the number 1 to 10, R ⁶ is a hydrogen atom or a hydrocarbon residue of 1 to 10 carbon atoms, R ⁷ is a hydrogen atom or a methyl group, a and b are integers of 0 to 3, c is 4- a-b, wherein n is an integer of 1 to 4 and n is an integer of 0 to 2). 7. The silane compound represented by the following general formula (4)
(7) CH ₂ = C (R ⁷ ) COO (CH ₂ ) _p SiR ⁸ _n (OR ⁶ ) _3-n (4) CH ₂ = CHSiR ⁸ _n (OR ⁶ ) _3-n (5) HS (CH ₂ ) _p -SiR ⁸ _n (OR ⁶ ) _3-n (6) (Wherein, R ⁶ is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, R ⁷ is a hydrogen atom or a methyl group, R ⁸ carbon atoms 1
To 3 alkyl groups or phenyl groups, n represents an integer of 0 to 2, and p represents an integer of 1 to 6. 3. The composite composition according to claim 1, which is one or more of the compounds represented by the formula (1). 8. The silane compound is one or more of those represented by the following general formula (2) and one or more of those represented by the following general formulas (4) to (7): SiR ⁴ _a R ⁵ _b (OR ⁶ ) _c ( 2) CH ₂ = C (R ⁷ ) COO (CH ₂ ) _p SiR ⁸ _n (OR ⁶ ) _3-n (4) CH ₂ = CHSiR ⁸ _n (OR ⁶ ) _3-n (5) HS (CH ₂ ) _p- SiR ⁸ _n (OR ⁶ ) _3-n (6) (Wherein, R ⁴ and R ⁵ are a hydrocarbon residue having 1 to 10 carbon atoms which may have an ether bond or an ester bond; R ⁶ is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms; ⁷ is a hydrogen atom or a methyl group, R ^{8 is} an alkyl group having 1 to 3 carbon atoms or a phenyl group, a and b are integers of 0 to 3, c is 4-
ab, an integer of 1-4, n is an integer of 0-2, p
Represents an integer of 1 to 6. ).
Or the composite composition according to 2. 9. In a radically polymerizable vinyl compound (A) or a partial polymer thereof, in a colloidal silica dispersion, the following general formula (1): SiR ¹ _a R ² _b (OR ³ ) _c (1) Wherein R ¹ and R ² each have 1 to 1 carbon atoms which may have an ether bond, an ester bond or a carbon-carbon double bond.
0 hydrocarbon residue, R ³ is a hydrogen atom or an ether bond,
A hydrocarbon residue having 1 to 10 carbon atoms which may have an ester bond or a carbon-carbon double bond, a and b are integers of 0 to 3, c is 4-ab, Represents an integer of ４4. ), A step of preparing a mixed solution in which a silica-based condensed polymer (B) obtained by hydrolyzing and condensing a silane compound represented by formula (1) is dissolved, and then performing a radical polymerization of the mixed solution. Silica-based condensation polymer
(B) Silica skeleton and radically polymerizable vinyl compound
A method for producing a composite composition comprising the polymer (A) and a semi-IPN structure . 10. The method for producing a composite composition according to claim 9, wherein the radical polymerization of the mixed solution and the further polycondensation of the silica-based polycondensate (B) in the mixed solution are simultaneously carried out. 11. The radical polymerization of the mixed solution and the further condensation polymerization of the silica-based condensation polymer (B) are carried out at 40 to 150 ° C.
The method for producing a composite composition according to claim 10, which is carried out at a temperature of: 12. After the component (A) is mixed with a solution in which the silica-based condensation polymer (B) is dissolved in a solvent, the solvent and water of the component (B) are distilled off from the mixed solution to obtain the mixed solution. The method for producing the composite composition according to claim 9, which is prepared. 13. The composite composition according to claim 9, wherein the mixed solution is prepared by adding the component (A) while removing the solvent and water from a solution in which the silica-based condensation polymer (B) is dissolved in the solvent. Method of manufacturing a product.