KR100991025B1 - Silica-containing silicone resin composition and its molded product - Google Patents

Abstract

The present invention relates to a silica-containing silicone resin composition for imparting high heat resistance, high transparency, and high dimensional stability suitable for optical applications such as lenses, optical disks, optical fibers, flat panel display substrates, and window materials for automobiles. This silica-containing silicone resin composition is represented by [RSi0 _3/2 ] _n ( _where R is an organic functional group having a (meth) acryloyl group and n is 8, 10 or 12), and is a cage-like structure in the structural unit. Silicone resin containing polyorganosilsesquioxane having a main component and -R ³ -CR ⁴ = CH ₂ or -CR ⁴ = CH _{2 in the} molecule, wherein R ³ is an alkylene group, an alkylidene group, or -OCO -At least two unsaturated groups represented by-and R ⁴ represents hydrogen or an alkyl group. It is obtained by mix | blending a silica fine particle in 5 to 70weight% of a range with a silicone resin composition.

Silica-containing silicones, resin compositions, shaped bodies, lenses, optical discs

Description

Silica-containing silicone resin composition and molded article thereof {SILICA-CONTAINING SILICONE RESIN COMPOSITION AND ITS MOLDED PRODUCT}

The present invention relates to a silica-containing silicone resin composition and a resin molded article that is a three-dimensional crosslinked product thereof.

Since inorganic glass has high transparency, heat resistance, and dimensional stability, it has been used in a wide range of industries since it is a structure that separates the space and transmits visible light and does not interfere with visibility. Inorganic glass with such outstanding characteristics, but the two major drawbacks are the heavy weight of more than 2.5, and the fragile fragile. In particular, in recent years, as a result of downsizing such as light weight and thinning in all industrial fields, voices that demand improvement of the above-mentioned shortcomings from users are becoming stronger.

As a material that meets the demands from such industries, expectations are concentrated on transparent thermoplastics and thermosetting plastics. Examples of the transparent thermoplastic plastics include PMMA (polymethyl methacrylate), PC (polycarbonate), and the like. Among them, PMMA is also called organic glass, attracting attention as a material that is excellent in transparency and overcomes two major drawbacks of glass. However, these transparent plastics have a problem in that their heat resistance and coefficient of thermal expansion are significantly lower than those of inorganic glass, and their use is limited.

On the other hand, as a transparent thermosetting plastic, an epoxy resin, a curable (meth) acrylate resin, a silicone resin, etc. can be illustrated, and these generally have higher heat resistance than said thermoplastics. Among these, epoxy resins have excellent curing properties due to their low curing shrinkage, but have the disadvantage of being low in impact resistance and soft. In addition, the curable (meth) acrylate resin has excellent balance between heat resistance, moldability, and physical properties of the molded product, but has a drawback in that the rate of dimensional change due to water absorption and the coefficient of linear expansion due to heat are large.

Among the thermosetting plastics, silicone resins are excellent in heat resistance, weather resistance, and water resistance, and thus solve the problems of the above plastics and are the materials most likely to replace inorganic glass. In particular, it is known that the polyorgano silsesquioxane of a ladder structure shows heat resistance which is inferior to a polyimide.

The following documents are related to the present invention.

Patent Document 1: Japanese Patent Application Publication No. 40-15989

Patent Document 2: Japanese Patent Application Laid-open No. 50-139900

Patent Document 3: Japanese Unexamined Patent Publication No. 2003-137944

Patent Document 4: Japanese Unexamined Patent Publication No. 2004-12396

Patent Document 5: Japanese Unexamined Patent Publication No. 2004-143449

[Non-Patent Document 1] J. Polymer Sci. Part C, No. 1, PP. 83-97 (1963)

Non-Patent Document 2: Japanese Chemical Society, 571-580 (1998)

As an example of such polyorganosilsesquioxane, phenyltrichlorosilane is hydrolyzed in an organic solvent to form phenyltrihydroxysilane, and the hydrolysis product is used in an alkali free solvent using an alkaline potential and a condensation catalyst. Cage-type octaphenylsilsesquioxane obtained by heating and dehydrating-condensation polymerization, and said cage-type octaphenylsilsesquioxane separated, and the phenylsiloxane prepolymer with low intrinsic viscosity which was heat-polymerized again using alkaline potential and a condensation catalyst, Alternatively, Patent Literatures 1 and 2 and Non-Patent Literature 1 disclose methods for producing a high intrinsic viscosity phenylsilsesquioxane polymer obtained by heating and polymerizing them using an alkaline potential and a condensation catalyst.

However, the silicone resin containing such polyorganosilsesquioxane also has a high flexibility in siloxane bonds, so that the crosslinking density must be increased in order to express the elastic modulus required for the structure. However, when the crosslinking density is increased, the curing shrinkage is remarkably increased, and the molded article becomes brittle, which is not preferable. In addition, since the residual stress due to curing shrinkage increases, it is extremely difficult to obtain a thick molded article. For this reason, silicone resins having a high crosslinking density are limited to coating applications, and those used for molding applications are limited to silicone rubbers having a low crosslinking density. A method of copolymerizing with an acrylic resin having excellent molding processability, for example, as a non-ladder type silicone resin, is copolymerized with an alkoxysilane using an acrylic polymer having an alkoxysilyl group in a side chain, and the acrylic polymer is converted into an organic component. Non-Patent Document 2 discloses a technique for forming a hybrid body having a polysiloxane as an inorganic component. However, since silicone resins are not sufficiently compatible with original acrylate resins, optical properties such as light transmittance are often impaired even when there is no problem in mechanical strength or the like.

Moreover, the silicone resin composition and silicone resin molded object which used the silicone resin which does not contain the silanol group disclosed by patent document 3, 4 showed the outstanding heat resistance, optical characteristic, and absorption characteristic. However, silicone resins prepared by equilibrating a cage-type polyorganosilsesquioxane with a disiloxane compound having a reactive functional group in the presence of an alkaline potential and a condensation catalyst have a small number of reactive functional groups per molecule on an average of 1.1, and a three-dimensional crosslinked structure in the molded body. It is assumed that there is little involvement in. In other words, increasing the proportion of the silicone resin contributing to the properties of heat resistance, weather resistance, and water resistance decreases the absolute number of reactive functional groups in the molded body, decreases the crosslinking density, and fails to construct a sufficient three-dimensional crosslinked structure, and consequently, heat resistance. This results in a molded article having reduced mechanical characteristics.

On the other hand, as a method of reducing the coefficient of linear expansion, there is generally a method of adding an inorganic filler in the resin and increasing the proportion of the inorganic component in the resin. There was a problem that the resin became uneven. JP5-209027A, JP10-231339A, and JP10-298252A disclose a cured composition having excellent transparency and rigidity by uniformly dispersing colloidal silica in a radically polymerizable vinyl compound such as methyl methacrylate using a silane compound. However, these were mainly designed for hard coats and were not applicable as glass substitutes. Moreover, the composite hardened | cured material which consists of alicyclic (meth) acrylate, a silica fine particle, a silane compound, and a tertiary amine compound disclosed by JP2003-213067A has transparency, and it is excellent in low linear expansion property. However, in order to reduce the linear expansion coefficient to less than 40 ppm / K, it is necessary to add more than 70% by weight of silica fine particles to the alicyclic acrylate, and to disperse uniformly using a large amount of silica fine particles, In order to use it, the viscosity of a composition increased and manufacture of the molded object was difficult.

By the way, cage type polyorgano silsesquioxane represented by (RSiO _3/2 ) _n is known from the said patent document 5, and it has also described that this can be mixed and used with another resin. R is an organic functional group containing acryloyl group etc., and n is 8, 10, 12, or 14.

Accordingly, an object of the present invention is to provide a silica-containing silicone resin molded article having excellent dimensional stability (low linear expansion) property only by blending a small amount of silica fine particles while maintaining the properties possessed by the silicone resin such as optical properties such as transparency, heat resistance and weather resistance. It is providing the silica containing silicone resin composition which can be provided.

MEANS TO SOLVE THE PROBLEM As a result of repeating | researching in order to achieve the said subject, the present inventors mix | blended silica microparticles | fine-particles with the unsaturated compound which can be radically copolymerized, and cage type silicone resin in specific ratio, and it is suitable for the alternative use of inorganic glass excellent in low thermal expansion and transparency. It was found that it is possible to give a transparent silica-containing silicone resin molded article to be used, and completed the present invention.

The present invention is general formula (1),

(Wherein R is an organic functional group having a (meth) acryloyl group, n is 8, 10 or 12), and a silicone resin containing polyorganosilsesquioxane having a cage-like structure as its main component And represented by -R ³ -CR ⁴ = CH ₂ or -CR ⁴ = CH _{2 in the} molecule, provided that R ³ represents an alkylene group, an alkylidene group or an -OCO- group, and R ⁴ represents hydrogen or an alkyl group. 5 to 70 weights of silica fine particles treated with a silane compound in a silicone resin composition comprising at least two unsaturated groups, wherein the unsaturated resin capable of radical copolymerization with the silicone resin is contained at a weight ratio of 10:90 to 80:20. It is a silica containing silicone resin composition characterized by the above-mentioned.

Silicone resin used here is general formula (3),

The hydrolysis product obtained by subjecting the silicon compound represented by (R is an organic functional group having a (meth) acryloyl group and X represents a hydrolyzable group) to undergo hydrolysis reaction in the presence of a polar solvent and a basic catalyst and partially condensed. Furthermore, it is preferable that it is prepared by recondensation in the presence of a nonpolar solvent and a basic catalyst, and it is preferable that it is a silicone resin which has the same number of silicon atoms and the number of (meth) acryl groups, and has a cage structure in the molecule | numerator.

The unsaturated compound capable of radical copolymerization to be mixed in the silicone resin composition is represented by the following general formula (4)

(Wherein R is an organic functional group having a (meth) acryloyl group, X is an organic functional group having hydrogen or a (meth) acryloyl group, n is an unsaturated compound having a hydroxyl group represented by 0 or 1 It is preferable to include.

In addition, the silica fine particles added to the silicone resin composition have an average particle diameter of 1 to 100 nm of silica fine particles, and 0.1 to 80% by weight of the general formula (5) based on the silica fine particles.

(Wherein R is an organic functional group having a (meth) acryloyl group, A is an alkyl group, X is an alkoxyl group or a halogen atom, m and n satisfy that m + n is an integer of 1 to 3, and m is 0 or It is preferable that 1 and n are processed with the silane compound represented by the integer of 0-3, and the compounding quantity of a silica microparticle is 1-70 weight% with respect to a silicone resin composition.

Moreover, this invention is a silica containing silicone resin molded object obtained by carrying out radical copolymerization of the silica containing silicone resin composition mentioned above. Furthermore, the present invention is a silica-containing silicone resin molded product having a total light transmittance of 85% or more and a glass transition temperature of 300 ° C or more while being 40 ppm / K or less.

The silica-containing silicone resin composition of the present invention contains a silicone resin, an unsaturated compound copolymerizable therewith, and silica fine particles as main components. The silica containing silicone resin copolymer of this invention is obtained by radically copolymerizing this silica containing silicone resin composition. The molded article of the present invention is obtained by molding the silica-containing silicone resin composition and molding the silica-containing silicone resin copolymer. The silica-containing silicone resin copolymer of the present invention is a crosslinked polymer, and in this case, a molding hardening method such as a thermosetting resin can be employed.

The silicone resin used for this invention is represented by the said General formula (1), and has a polyorgano silsesquioxane (also called cage polyorgano silsesquioxane) which has a cage-like structure in a structural unit as a main component.

In General Formula (1), R is an organic functional group having a (meth) acryloyl group, and n is 8, 10 or 12, but R is preferably an organic functional group represented by the following General Formula (9). In general formula (9), m is an integer of 1-3, R <_1> is a hydrogen atom or a methyl group.

Conventional silicone resins, regardless of ladder type or non-ladder type, have low compatibility with organic compounds having functional groups such as acrylic resins, and transparent moldings could not be obtained from these compositions. However, in the silicone resin, a reactive functional group having high compatibility with organic compounds sticks out of the cage, and a siloxane skeleton portion having low compatibility with organic compounds is blown into the cage to form a similar micelle structure. Therefore, it can mix with unsaturated compounds, such as an acryl monomer and an oligomer, in arbitrary ratios.

Cage-type polyorganosilsesquioxane represented by the said General formula (1) has a reactive functional group on the silicon atom in a molecule | numerator. As a specific structure of cage-type polyorgano silsesquioxane whose n in General formula (1) is 8, 10, and 12, cage-type structures as shown to following structural formula (6), (7), and (8) are mentioned. . In addition, R in following formula represents the same thing as R in General formula (1).

Cage-type polyorgano silsesquioxane represented by General formula (1) can be manufactured by the method of patent document 5 etc. For example, the silicon compound represented by the general formula (3) is partially condensed at the same time as the hydrolysis reaction in the presence of a polar solvent and a basic catalyst, and the obtained hydrolysis product is also obtained by recondensation in the presence of a nonpolar solvent and a basic catalyst. Can be. In General formula (3), R is an organic functional group which has a (meth) acryloyl group, X represents a hydrolysable group, Preferably R is group represented by the said General formula (9). When the specific example of preferable R is shown, 3-methacryloxypropyl group, methacryloxymethyl group, and 3-acryloxypropyl group are illustrated.

In general formula (3), if hydrolyzable group X is group which has hydrolyzability, it will not specifically limit, Although an alkoxy group, an acetoxy group, etc. are mentioned, It is preferable that it is an alkoxyl group. Examples of the alkoxyl group include a methoxy group, an ethoxy group, n- and i-propoxy groups, n-, i- and t-butoxy groups, and the like. It is preferable that it is a methoxy group with high reactivity among these.

If a preferable compound is shown among the silicon compounds represented by General formula (3), methacryloxymethyl triethoxysilane, methacryloxymethyl trimethoxysilane, 3-methacryloxypropyl trichlorosilane, 3-methacryloxypropyl Trimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, and 3-acryloxypropyl trichlorosilane are mentioned. Especially, it is preferable to use 3-methacryloxypropyl trimethoxysilane which is easy to acquire a raw material.

As a basic catalyst used for a hydrolysis reaction, alkali metal hydroxides, such as potassium hydroxide, sodium hydroxide, and cesium hydroxide, or tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyl trimethylammonium hydroxide Ammonium hydroxide salts, such as a seed and benzyl triethylammonium hydroxide, are illustrated. Among them, tetramethylammonium hydroxide is preferably used in view of high catalytic activity. Basic catalysts are usually used as aqueous solutions.

About hydrolysis reaction conditions, 0-60 degreeC is preferable and 20-40 degreeC of reaction temperature is more preferable. If the reaction temperature is lower than 0 ° C., the reaction rate is slowed, and the hydrolyzable groups remain in the unreacted state, resulting in a large amount of reaction time. On the other hand, if it is higher than 60 DEG C, the reaction rate is too fast, so that a complicated condensation reaction proceeds, resulting in high molecular weight of the hydrolysis product. Moreover, 2 hours or more of reaction time is preferable. If the reaction time is less than 2 hours, the hydrolysis reaction does not proceed sufficiently and the hydrolyzable group remains in an unreacted state.

The presence of water is essential for the hydrolysis reaction, which may be supplied from an aqueous solution of a basic catalyst or may be added separately as water. The amount of water is at least an amount sufficient to hydrolyze the hydrolyzable group, preferably 1.0 to 1.5 times the theoretical amount. In addition, it is necessary to use an organic polar solvent at the time of hydrolysis, and alcohols, such as methanol, ethanol, 2-propanol, or another organic polar solvent can be used as an organic polar solvent. Preferably they are C1-C6 lower alcohols which are soluble in water, and it is more preferable to use 2-propanol. Using a nonpolar solvent is not preferable because the reaction system is not uniform and the hydrolysis reaction does not proceed sufficiently and unreacted alkoxyl groups remain.

After completion of the hydrolysis reaction, water or a water-containing reaction solvent are separated. Separation of water or a reaction solvent containing water may employ means such as reduced pressure evaporation. In order to sufficiently remove water and other impurities, a means such as adding a nonpolar solvent to dissolve the hydrolysis reaction product, washing the solution with saline solution, and then drying with a drying agent such as anhydrous magnesium sulfate may be employed. Can be. If the nonpolar solvent is separated by a means such as evaporation, the hydrolysis reaction product can be recovered. If the nonpolar solvent can be used as the nonpolar solvent used in the following reaction, it is not necessary to separate it.

In the hydrolysis reaction of the present invention, condensation reaction of the hydrolyzate occurs with hydrolysis. The hydrolysis product accompanying the condensation reaction of the hydrolyzate is usually a colorless viscous liquid having a number average molecular weight of 1400 to 5000. The hydrolysis products are different depending on the reaction conditions, but the oligomers having a number average molecular weight of 1400 to 3000 are substituted, and most, preferably almost all, of the hydrolyzable groups X represented by the general formula (3) are substituted with OH groups, and further, the OH Most of the groups are preferably condensed at least 95%. The structure of the hydrolysis product is plural kinds of cage type, ladder type and random type silsesquioxane, and in the case of a compound having a cage type structure, the ratio of the complete cage structure is small and the incomplete cage in which part of the cage is opened. The structure of the terrain is becoming the main one. Therefore, the silsesquioxanes having a cage-like structure are selectively prepared by condensing (recondensing) the siloxane bonds by heating the hydrolysis product obtained by this hydrolysis in the presence of a basic catalyst and in an organic solvent.

After separating water or a water-containing reaction solvent, a recondensation reaction is carried out in the presence of a nonpolar solvent and a basic catalyst. About the reaction conditions of a recondensation reaction, the reaction temperature is preferable in the range of 100-200 degreeC, Furthermore, 110-140 degreeC is more preferable. In addition, when the reaction temperature is too low, sufficient driving force cannot be obtained to cause the recondensation reaction, and the reaction does not proceed. If the reaction temperature is too high, the (meth) acryloyl group may cause self-polymerization reaction. Therefore, it is necessary to suppress the reaction temperature or add a polymerization inhibitor or the like. The reaction time is preferably 2 to 12 hours. The amount of the nonpolar solvent is preferably sufficient to dissolve the hydrolysis reaction product, and the amount of the basic catalyst is in the range of 0.1 to 10% by weight based on the hydrolysis reaction product.

As a nonpolar solvent, what is necessary is just to have little or no solubility with water, but a hydrocarbon solvent is preferable. As such a hydrocarbon solvent, there is a nonpolar solvent having a low boiling point such as toluene, benzene or xylene. Especially, it is preferable to use toluene. As a basic catalyst, the basic catalyst used for a hydrolysis reaction can be used, Alkali metal hydroxides, such as potassium hydroxide, sodium hydroxide, cesium hydroxide, or tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide Although ammonium hydroxide salts, such as a seed, benzyl trimethylammonium hydroxide, and benzyl triethylammonium hydroxide, are mentioned, A catalyst soluble in nonpolar solvents, such as tetraalkylammonium, is preferable.

In addition, the hydrolyzate used for recondensation is preferably washed with water, dehydrated and concentrated, but can be used without washing with water or dehydrating. In this reaction, although water may be present, it is not necessary to actively add it, and it is preferable to stop at about the amount of water introduced from the basic catalyst solution. If the hydrolysis product is not sufficiently hydrolyzed, water of more than the theoretical amount required to hydrolyze the remaining hydrolyzable group is required, but usually the hydrolysis reaction is sufficiently performed. After the recondensation reaction, the catalyst is washed with water, removed and concentrated to give a silsesquioxane mixture.

The silsesquioxanes thus obtained vary depending on the reaction conditions and the state of the hydrolysis product, but the constituents are 70% or more of the total cage-type silsesquioxanes, and The constituents are 20 to 40% of T8 represented by the general formula (6), 40 to 50% of T10 represented by the general formula (7), and the other components are T12 represented by the general formula (8). T8 can be separated by precipitated as needle-shaped crystals by leaving the siloxane mixture at 20 ° C or lower. The silicone resin used in the present invention may be a mixture of T8 to T12, or may be one obtained by separating or concentrating one or two such as T8 from this. In addition, the silicone resin used by this invention is not limited to the silicone resin obtained by the said manufacturing method.

In the silica-containing silicone resin composition of the present invention, the unsaturated compound used with the silicone resin contains at least two unsaturated groups represented by -R ³ -CR ⁴ = CH ₂ or -CR ⁴ = CH ₂ in the molecule, and the silicone It is an unsaturated compound capable of radical copolymerization with a resin. Here, R <^3> represents an alkylene group, an alkylidene group, or -OCO- group, As a alkylene group and an alkylidene group, a C1-C6 lower alkylene group and an alkylidene group are preferable. R ⁴ represents hydrogen or an alkyl group, but is preferably hydrogen or a methyl group. As a preferable unsaturated group, at least 1 sort (s) chosen from the group which consists of acryloyl group, methacryloyl group, allyl group, and a vinyl group is mentioned. Examples of preferred unsaturated compounds in addition to the unsaturated compound having a hydroxyl group represented by the formula ^{(4), A 1 - (} R 3 -CR 4 = CH 2) n or ^{A 2 - (CR 4 = CH} 2) unsaturated compounds expressed by the _n There is this. Here, it is preferable that A <^1> and A <^2> are C1-C20, n-valent aliphatic hydrocarbon group or aromatic hydrocarbon group, and an aliphatic hydrocarbon group may be a cyclic aliphatic hydrocarbon group, but it is preferable that it does not have an olefinic double bond. It is preferable that n is an integer of 1-8. Moreover, it is preferable that this unsaturated compound does not have Si in a molecule | numerator.

The silica-containing silicone resin composition of the present invention contains A) a silicone resin and B) an unsaturated compound having an unsaturated group and copolymerizable with a silicone resin as a main component. The mixing ratio is in the range of 1:99 to 99: 1, but when the silicone resin content is A and the unsaturated compound content is B, preferably 10/90 ≦ A / B ≦ 80/20, more preferably 20 / 80≤A / B≤60 / 40. If the silicone resin ratio is less than 10%, physical properties such as heat resistance, transparency, and water absorption of the molded body after curing decrease, which is not preferable. Moreover, since the viscosity of a composition increases when silicone resin ratio exceeds 80%, manufacture of a molded object becomes difficult, too, which is also unpreferable.

This unsaturated compound is classified into the unsaturated compound which has a hydroxyl group as represented by the said General formula (4), and the unsaturated compound which does not have a hydroxyl group. In general formula (4), R is an organic functional group which has a (meth) acryloyl group, X is an organic functional group which has hydrogen or a (meth) acryloyl group. n is an integer of 0 or 1. In order to obtain a molded article having good transparency, an unsaturated compound containing a hydroxyl group is preferable. It is considered that this is because the hydroxyl group acts on the silanol group present on the surface of the silica fine particles to suppress the aggregation of the silica fine particles and improve the dispersibility of the silica fine particles in the resin. On the other hand, in the unsaturated compound which does not have a hydroxyl group, when silica fine particle is mix | blended in large quantity, it may not disperse | distribute uniformly in resin by aggregation, and transparency may deteriorate. Moreover, from another viewpoint, an unsaturated compound is divided roughly into the reactive oligomer which is a polymer of the repeating number of 2-20 of a structural unit, and the reactive monomer of low molecular weight and a low viscosity. Moreover, it is largely divided into the monofunctional unsaturated compound which has one unsaturated group, and the polyfunctional unsaturated compound which has two or more unsaturated groups. In addition, polyfunctional unsaturated compounds are classified into non-alicyclic unsaturated compounds having no alicyclic structure in their molecular structure and alicyclic unsaturated compounds having alicyclic structure. In order to obtain a good three-dimensional crosslinked product, it is preferable to include a very small amount (about 1% or less) of a polyfunctional unsaturated compound.However, in view of heat resistance, strength, etc. of the copolymer, an average of 1.1 or more per molecule, preferably 1.5 or more More preferably, it is 1.6-5. For this purpose, it is good to mix and use a monofunctional unsaturated compound and the polyfunctional unsaturated compound which has 2-5 unsaturated groups, and to adjust the average number of functional groups.

Examples of the reactive oligomer include epoxy acrylate, epoxidized oil acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinyl acrylate, polyene / thiol, silicone acrylate, polybutadiene, and polystyrylethylmetha. Crylate etc. can be illustrated. These include monofunctional unsaturated compounds and polyfunctional unsaturated compounds.

Reactive monofunctional monomers include styrene, vinyl acetate, N-vinylpyrrolidone, butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylate , Dicyclopentenyloxyethyl acrylate, phenoxyethyl acrylate, trifluoroethyl methacrylate, etc. can be illustrated.

Reactive non-cyclic polyfunctional monomers include tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, bisphenol A diglycidyl ether diacrylate, tetraethylene glycol diacrylate, and hydroxypivalate neopentyl Glycol diacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like. Among the reactive acyclic polyfunctional monomers, pentaerythritol triacrylate, glycerin dimethacrylate, glycerol acrylate methacrylate and the like can be given as a monomer having a hydroxyl group represented by the general formula (4). Since they have a hydroxyl group in the molecule, it is possible to interact with the hydroxyl groups present on the surface of the silica fine particles, and controlling the silica fine particles in the resin composition enables a uniform amount of compounding into the resin.

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As a reactive alicyclic polyfunctional monomer, General formula (2)

(Wherein Z represents any one group represented by (2a) or (2b), and R represents hydrogen or a methyl group), and as a specific compound in the case where Z is a group represented by formula (2a) As a specific compound in the case of pentacyclo [6.5.1.1 ^{3,6 2,7 9,13} ] pentadecane dimethylol diacrylate and Z is a group represented by Formula (2b), this hydrogen is a dish where R is hydrogen. Copenpentanyldimethylol diacrylate (or tricyclo [5.2.1.0 ^2,6 ] decanedimethylol diacrylate) can be exemplified.

As the unsaturated compound used in the present invention, various reactive oligomers and monomers can be used in addition to those exemplified above. In addition, these reactive oligomers and monomers may be used independently, respectively, or may mix and use two or more types. However, when using A) silicone resin, B) unsaturated compounds, and C) unsaturated compounds, monomers or oligomers other than these, the weight% calculated by C / (B + C) is 50% by weight or less, preferably 20% by weight. It is better to stop below%.

The silica fine particles of the silica-containing silicone resin composition of the present invention are not particularly limited as long as they are silicon oxide and have an average particle diameter in the range of 1 to 100 nm. The silica fine particles may be dried silica fine particles or colloidal silica dispersed in an organic solvent. In order to disperse | distribute to a silicone resin composition and to process a silica fine particle with a silane compound, it is preferable to use the colloidal silica disperse | distributed to the organic solvent. In the case of using colloidal silica dispersed in an organic solvent, it is preferable to dissolve the silicone resin composition, and alcohols, ketones, esters and glycol ethers are used. Among them, treatment with silane compounds and silicone It is preferable to use alcohols, such as methanol, ethanol, propyl alcohol, isopropyl alcohol, and butyl alcohol, as an organic solvent from the ease of the desolvent after dispersing in resin.

As for the average particle diameter of a silica microparticle, 1-100 nm is preferable, More preferably, a 5-50 nm thing can be used from the balance of transparency and a viscosity of a silica containing silicone resin composition, and the compounding quantity and dispersibility of a silica fine particle. Moreover, plural kinds of silica fine particles having different average particle diameters can be used as long as the average particle diameter is in the range of 1 to 100 nm. When the average particle diameter of the silica fine particles is less than 1 nm, the viscosity of the silica-containing resin composition increases due to the silica fine particle blending, which makes it difficult to uniformly disperse and manufacture the molded body, so that the amount of the silica fine particles is limited. In addition, when the average particle diameter is 100 nm or more, the transparency of the molded body is significantly deteriorated.

It is preferable that the silica fine particle compounding quantity of the silica containing silicone resin composition of this invention is added to the silicone resin composition in the range of 1-70 weight%, and it is the point of balance of the viscosity of a silica containing silicone resin composition, and a thermal expansion coefficient. More preferably, it is 5 to 70 weight%, More preferably, it is 10 to 50 weight%. If it is this range, the molded object which is easy to manufacture excellent in low thermal expansion and transparency can be obtained. If the compounding quantity of silica microparticles is less than 1 weight%, low thermal expansion property cannot be expressed, and when it is a compounding quantity of 70 weight% or more, the viscosity of a silica containing resin composition will increase and molding will become difficult.

Although the viscosity of the silica containing silicone resin composition of this invention is 100-120000 mPa * s normally from a viewpoint of moldability, Preferably it is 500-90000 mPa * s, More preferably, it is 1000-50000 mPa * s. If it is this range, the molded object of predetermined thickness can be produced efficiently. Since the viscosity is too low below 100 mPa · s, a molded article having a predetermined thickness cannot be produced, and above 120000 mPa · s, the productivity significantly decreases due to the high viscosity.

The silane compound is used to treat the surface of the silica fine particles, and is effective because it suppresses the aggregation of the silica fine particles, improves the dispersion stability of the silica fine particles, and reduces the viscosity of the silica-containing silicone resin composition. The amount of the silane compound is in the range of 0.1 to 80% by weight relative to the silica fine particles, but is preferably treated in the range of 0.5 to 50% by weight, more preferably 0.5 to 30% by weight. If the amount of the silane compound is less than 0.5% by weight, the effect of suppressing the aggregation of the silica fine particles is lost, and since the viscosity of the silica-containing silicone resin composition increases, it becomes difficult to manufacture a molded article. If the amount of the silane compound is 50% by weight or more, the effect of low thermal expansion of the silica fine particle blend is reduced, which is not preferable. As a method of treating silica fine particles with a silane compound, a silane compound is blended with colloidal silica dispersed in an organic solvent, and optionally, a small amount of water is added, and the method is heated so as not to reduce the organic solvent by heating. There is this.

As a silane compound, the compound represented by the said General formula (5) is used preferably.

Specifically, 3-acryloxypropyldimethylmethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyldiethylmethoxysilane, 3-acryloxypropylethyldimethoxysilane, 3-acryloxypropyltri Methoxysilane, 3-acryloxypropyldimethylethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropyldiethylethoxysilane, 3-acryloxypropylethyldiethoxysilane, 3-acryloxypropyl Triethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyldiethylmethoxysilane, 3-methacryloxypropylethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyldiethylethoxysilane, 3-methacryloxy profile Butyl diethoxysilane, 3-methacryloxypropyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane, triethylmethoxysilane, Propyltrimethoxysilane, Dipropyltrimethoxysilane, Tripropylmethoxysilane, Isopropyltrimethoxysilane, Diisopropyldimethoxysilane, Triisopropylmethoxysilane, Methyltriethoxysilane, Dimethyldiethoxysilane , Triethoxysilane, ethyltriethoxysilane, diethyldiethoxysilane, triethylethoxysilane, propyltriethoxysilane, dipropyltriethoxysilane, tripropylethoxysilane, isopropyltriethoxysilane, Diisopropyl diethoxysilane, triisopropyl ethoxysilane, etc. can be illustrated. In addition, these may be used independently and may be used in combination of 2 or more types.

The silica-containing silicone resin copolymer of the present invention can obtain a silica-containing silicone resin copolymer by radical copolymerization thereof. Various additives can be mix | blended with the silica containing silicone resin composition of this invention in order to improve the physical property of a silica containing silicone resin copolymer, or for the purpose of promoting radical copolymerization. Examples of the additive that promotes the reaction include a thermal initiator, a thermal polymerization accelerator, a photopolymerization initiator, a photoinitiator, a preliminary agent and the like. When mix | blending a photoinitiator or a thermoinitiator, the addition amount should be 0.1-5 weight part with respect to a total of 100 weight part of a silicone resin, an unsaturated compound, and a silica fine particle, and should be 0.1-3 weight part. More preferred. If this addition amount is less than 0.1 part by weight, curing will be insufficient, and the strength and rigidity of the resulting molded article will be lowered. On the other hand, if it exceeds 5 parts by weight, problems such as coloring of the molded article may occur.

As a photoinitiator used when making a silica containing silicone resin composition into a photocurable composition, compounds, such as an acetphenone type, a benzoin type, a benzophenone type, a thioxanthone type, an acylphosphine oxide type, can be used preferably. Specifically, trichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methyl Thiophenyl) -2-morpholinopropane-1-one, benzoin methyl ether, benzyl dimethyl ketal, benzophenone, thioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, Camphorquinone, benzyl, anthraquinone, Michler's ketone and the like can be exemplified. Moreover, the photoinitiator and the presensitizer which show an effect in combination with a photoinitiator can also be used together.

Examples of thermal polymerization initiators used for this purpose include various organic peroxides such as ketone peroxides, peroxy ketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters. It can be used preferably. Specifically, cyclohexanone peroxide, 1, 1-bis (t-hexaperoxy) cyclohexanone, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, diisopropyl peroxide, t-butyl peroxy-2 Although ethyl hexanoate etc. can be illustrated, it is not limited to this at all. In addition, these thermal polymerization initiators may be used independently, or may mix and use two or more types.

Various additives can be added to the silica containing silicone resin composition of this invention in the range which does not deviate from the objective of this invention. Examples of the various additives include organic / inorganic fillers, plasticizers, flame retardants, heat stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents, mold release agents, foaming agents, nucleating agents, colorants, crosslinking agents, dispersion aids, resin components, and the like. .

Although a silicone resin copolymer can be obtained by radically copolymerizing the silica containing silicone resin composition of this invention, the molded object of a silica containing silicone resin copolymer can also be obtained by radical copolymerizing a silica containing silicone resin composition as a predetermined shape. When the silica-containing silicone resin copolymer obtained is thermoplastic, various formation methods can be adopted. When the number of reactive substituents or unsaturated groups per molecule exceeds 1.0, the copolymer has a three-dimensional crosslinked structure. Is employed. So radical copolymerization is also called curing. Heating or irradiation of energy rays, such as an electron beam and an ultraviolet-ray, is suitable for radical copolymerization.

The silica containing silicone resin copolymer of this invention can be manufactured by hardening the silica containing silicone resin composition containing a radical polymerization initiator by heating or light irradiation. When producing a copolymer (molded product) by heating, the molding temperature can be selected in a wide range from room temperature to around 200 ° C by selection of a thermal polymerization initiator and an accelerator. In this case, a silica-containing silicone resin molded article having a desired shape can be obtained by polymerizing and curing the mold inside or on a steel belt.

Moreover, when manufacturing a copolymer (molded object) by light irradiation, a molded object can be obtained by irradiating an ultraviolet-ray with a wavelength of 10-400 nm and visible light with a wavelength of 400-700 nm. The wavelength of the light to be used is not particularly limited, but particularly near ultraviolet rays having a wavelength of 200 to 400 nm are preferably used. As a lamp used as an ultraviolet light source, a low pressure mercury lamp (output: 0.4 to 4 W / cm), a high pressure mercury lamp (40 to 160 W / cm), an ultra high pressure mercury lamp (173 to 435 W / cm), and a metal halide lamp (80 to 160 W /) cm), pulse xenon lamps (80 to 120 W / cm), electrodeless discharge lamps (80 to 120 W / cm), and the like. Since these ultraviolet lamps are characterized by their spectral distribution, they are selected according to the type of photoinitiator to be used.

As a method of obtaining a silica containing silicone resin copolymer (molded body) by light irradiation, it has an arbitrary cavity shape, for example, it injects into the metal mold | die comprised of transparent materials, such as quartz glass, and irradiates an ultraviolet-ray with the said ultraviolet lamp and superposes | polymerizes it. By hardening and demolding in a mold, a method of manufacturing a molded article of a desired shape, or in the case of not using a mold, for example, using a doctor blade or a roll coater on a moving steel belt The method of manufacturing a sheet-like molded object etc. can be illustrated by apply | coating the silica containing silicone resin composition of this invention, and polymerizing and hardening with said ultraviolet lamp.

The silica-containing silicone resin copolymer (molded product) of the present invention thus obtained does not exhibit a glass transition temperature of 300 ° C. or lower, measured by a dynamic thermomechanical analyzer (DMA), and has a total light transmittance of 85% or more and a linear expansion coefficient of 40 ppm /. K or less, and therefore, it can be said to have high heat resistance, high transparency, and high dimensional stability.

Hereinafter, the Example of this invention is shown. In addition, the silicone resin used for the following example is obtained by the method shown to the following synthesis example 1.

Synthesis Example 1

To a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 40 ml of 2-propanol (IPA) as a solvent and 5% aqueous tetramethylammonium hydroxide solution (TMAH aqueous solution) as a basic catalyst were added. Into the dropping funnel, add 15 ml of IPA and 12.69 g of 3-methacryloxypropyltrimethoxysilane (SZ-6030, manufactured by Torre Dow Corning Silicone), and 3-methacryloxypropyl at room temperature while stirring the reaction vessel. The IPA solution of trimethoxysilane was dripped over 30 minutes. After completion | finish of dripping of 3-methacryloxypropyl trimethoxysilane, it stirred for 2 hours, without heating. After stirring for 2 hours, the solvent was removed under reduced pressure and dissolved in 50 ml of toluene. The reaction solution was washed with saturated brine until neutral and dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to give 8.6 g of a hydrolysis product (silsesquioxane). This silsesquioxane was a colorless viscous liquid soluble in various organic solvents.

Next, 20.65 g of silsesquioxane, 82 ml of toluene and 3.0 g of 10% TMAH aqueous solution were added to a reaction vessel equipped with a stirrer, Dean-Stark, and a cooling tube, and the mixture was slowly heated to distill water off. . Furthermore, it heated to 130 degreeC and carried out the recondensation reaction of toluene at reflux temperature. The temperature of the reaction solution at this time was 108 ° C. After stirring for 2 hours after toluene reflux, the reaction was terminated. The reaction solution was washed with saturated brine until neutral and dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 18.77 g of a cage-type silsesquioxane (mixture) as a target product. The cage-type silsesquioxane obtained was a colorless viscous liquid soluble in various organic solvents.

Mass spectrometry after liquid chromatography separation of the reactants after the recondensation reaction confirmed the molecular ions with ammonium ions in the molecular structures of the structural formulas (6), (7) and (8), and the constituent ratio was T8: TlO: T12 and others are about 2: 4: 1: 3, and it can be confirmed that the silicone resin has a cage-like structure as a main component. In addition, T8, T10, and T12 respond | correspond in order of Formula (6), (7), and (8).

Example 1

Isopropanol-dispersed colloidal silica sol (particle diameter 10-20 nm, solid content 30 weight%, moisture 0.5 weight%, Nissan Kagaku Kyo KK) manufactured by IPA- as a silica fine particle in the reaction container provided with a stirrer, a thermometer, and a cooling tube. 150 parts by weight of ST) (30 parts by weight of silica solid content) and 7.2 parts by weight of 3-methacryloxypropyltrimethoxysilane (SZ-6030, manufactured by Torre, Dow Corning, and Silicon Co., Ltd.) as a silane compound were added and stirred. After heating gradually, the temperature of the reaction solution reached 68 ° C, heating was further performed for 5 hours, and silica fine particles were treated. 55 weight part of silicone resin compositions (25 weight part of cage-type silicone resins which have the methacryloyl group obtained by the synthesis example 1 on all the silicon atoms, and dipentaerythritol hexaacrylate: 75 weight part) are mixed, and it is made under reduced pressure. The volatile solvent fraction was removed while heating slowly, and the final temperature was 80 ° C. 1-hydroxycyclohexylphenyl ketone: 2.5 weight part was mixed as a photoinitiator, and the transparent silica containing silicone resin composition was obtained.

Next, using a roll coater to cast a thickness of 0.4 mm, using a high pressure mercury lamp of 30 W / cm, cured to an integrated exposure dose of 8000 mJ / cm ² , and sheet-shaped silicon having a predetermined thickness. The resin molding was obtained.

Examples 2-6

Except having made the compounding composition into the ratio shown in Table 1, it carried out similarly to Example 1, and obtained the resin molded object. The physical property values of the obtained molded object are summarized and shown in Table 2.

Comparative Example 1

Cage-type silicone resin which has the methacryloyl group obtained by the synthesis example 1 on all the silicon atoms: 25 weight part, dipentaerythritol hexaacrylate: 75 weight part, 1-hydroxycyclohexyl phenyl ketone as a photoinitiator: 2.5 weight part The part was mixed and the transparent silicone resin composition was obtained.

Next, using a roll coater, the sheet was cast to a thickness of 0.4 mm, and then cured to a cumulative exposure amount of 8000 mJ / cm ² using a high pressure mercury lamp of 30 W / cm, and the sheet shape was formed into a predetermined thickness. The silicone resin molded body of was obtained.

Comparative Example 2

A resin molded article was obtained in the same manner as in Comparative Example 1 except that the blending composition was used as the weight ratio shown in Table 1. The physical property values of the obtained molded object are summarized and shown in Table 2.

The abbreviations in the table are as follows.

A: Silica Solids

B: 3-methacryloxypropyl trimethoxysilane (SZ-6030 made by Torre Dow Corning Silicone)

C: silicone resin composition 1 (compound obtained by the synthesis example 1: 25 weight part, dipentaerythritol hexaacrylate: 75 weight part)

D: silicone resin composition 2 (compound obtained in Synthesis Example 1: 25 parts by weight, pentaerythritol triacrylate: 75 parts by weight)

E: Silicone resin composition 3 (compound obtained in Synthesis Example 1: 25 parts by weight, glycerin dimethacrylate: 75 parts by weight)

F: Silicone resin composition 4 (compound obtained by the synthesis example 1: 25 weight part, pentaerythritol triacrylate: 55 weight part, glycerin dimethacrylate: 20 weight part)

G: 1-hydroxycyclohexylphenyl ketone (polymerization initiator)

1) Glass transition temperature: Dynamic thermal field analysis, temperature rise rate 5 ℃ / min, chuck distance 10mm

2) Total light transmittance (reference standard JIS K 7361-1): sample thickness 0.4mm)

3) Coefficient of linear expansion: Thermomechanical analysis, temperature increase rate 5 ℃ / min, compressive load 0.1N

4) Viscosity: E type viscometer (23 degrees Celsius)

5) Molding: 30 g of the resin was cast and cured after 40 minutes under a load of 40 kg. The molded article obtained was less than ± 5% of the predetermined thickness, and less than ± 10%, and less than ± 10%.

According to the present invention, a molded article having high heat resistance, high transparency and high dimensional stability can be obtained. For example, optical materials such as lenses, optical disks, optical fibers, and flat panel display substrates, and window materials for various transportation machines and houses ( I) It can be used for various uses. The molded article is a lightweight, high impact, transparent member, and its use range is wide as a glass substitute material, and its industrial use value is also high.

Claims (9)

General formula (1)

(Wherein R is an organic functional group having a (meth) acryloyl group and n is 8, 10 or 12), and K is a polyorganosilsesquioxane having a cage-like structure as a main component -R ³ -CR ⁴ = CH ₂ or -CR ⁴ = CH ₂ (wherein R ³ represents an alkylene group, an alkylidene group or an -OCO- group, and R ⁴ represents hydrogen or an alkyl group in the molecule) Particulate silica having an average particle diameter of 1 to 100 nm in a silicone resin composition comprising at least two unsaturated groups represented by the formula (I)) and blending an unsaturated compound capable of radical copolymerization with the silicone resin at a weight ratio of 10:90 to 80:20. Silica-containing silicone resin composition characterized in that it contains in the range of 5 to 70% by weight. The silicone resin according to claim 1, wherein the silicone resin is represented by General Formula (3),

Wherein the silicon compound represented by R is an organic functional group having a (meth) acryloyl group, and X represents a hydrolyzable group, and is partially condensed at the same time as the hydrolysis reaction in the presence of a polar solvent and a basic catalyst. The product is also obtained by recondensation in the presence of a nonpolar solvent and a basic catalyst, the silica-containing silicone resin composition characterized in that the number of silicon atoms in the molecule and the number of (meth) acryloyl groups are the same, and at the same time have a cage structure. The unsaturated compound of claim 1, wherein the unsaturated compound capable of radical copolymerization is represented by the following general formula (4).

Wherein R is an organic functional group having a (meth) acryloyl group, X is an organic functional group having hydrogen or a (meth) acryloyl group, n is an integer compound having a hydroxyl group represented by 0 or 1 Silica containing silicone resin composition characterized by the above-mentioned. The silica-containing silicone resin composition according to claim 1, wherein the particulate silica is treated with 0.1 to 80% by weight of a silane compound. The method of claim 4, wherein the silane compound is represented by the general formula (5)

(Wherein R is an organic functional group having a (meth) acryloyl group, A is an alkyl group, X is an alkoxyl group or a halogen atom, m and n satisfy that m + n is an integer of 1 to 3, and m is 0 or 1, n is an integer of 0-3), the silica containing silicone resin composition characterized by the above-mentioned. The silica containing silicone resin copolymer obtained by carrying out radical copolymerization of the silica containing silicone resin composition in any one of Claims 1-5. It is obtained by carrying out radical copolymerization of the silica containing silicone resin composition of any one of Claims 1-5, The resin molded object characterized by the above-mentioned. The resin molded product according to claim 7, wherein the resin molded article has a linear expansion coefficient of 40 ppm / K or less, a total light transmittance of 85% or more, and a glass transition temperature of 300 ° C or more. The silica-containing silicone resin composition according to any one of claims 1 to 5 is subjected to radical copolymerization by heating or irradiating an energy ray.