JP3274147B2 - Thermoplastic resin and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[Object of the invention]

[0002]

The present invention relates to a colloidal silica obtained by graft polymerization of a vinyl monomer onto a colloidal silica-silicone core-shell body obtained by bonding a reactive unsaturated group-containing polyorganosiloxane to a colloidal silica via a siloxane bond. The present invention relates to a thermoplastic resin containing a copolymer which has remarkably excellent impact resistance, abrasion resistance, weather resistance and the like, and a method for producing the same.

[0003]

2. Description of the Related Art It is known that colloidal silica is added to a water-based resin coating for the purpose of improving and improving the performance of a coating film formed from a water-based resin coating which has attracted attention from the viewpoint of environmental protection and safety and health. . However, the added colloidal silica has a drawback that the bonding with the organic polymer emulsion is weak, resulting in deterioration in durability. Attempts to improve the interfacial adhesion by grafting an organic polymer to colloidal silica as a remedy have been widely studied in the field of coating agents.

For example, Japanese Patent Publication No. Sho 62-58630 discloses that colloidal silica and a chromium compound are added to an acrylic resin obtained by multistage emulsion polymerization of an organosilicon compound having both a reactive unsaturated group and an alkoxy group and an acrylic monomer. When blended, it imparts high corrosion resistance and paint base to the metal surface,
It describes that a metal surface treating agent excellent in adhesion, deep drawing workability and blocking resistance can be obtained. However, in the production of the acrylic resin, the alkoxysilyl group is hydrolyzed into a silanol group at the time of its production, and in some cases, a siloxane (-SiOSi-) bond is formed by a subsequent condensation reaction. That is, the formed acrylic resin has a form in which siloxane bonds are unevenly distributed in the molecule. However, in improving and improving the above-mentioned properties, it is desired that the site capable of interacting with the colloidal silica to be added and mixed is uniformly dispersed in the acrylic resin, whereas the siloxane bond is Since it is unevenly distributed in the molecule and does not entirely exist at the interface with the added colloidal silica, sufficient interfacial adhesion cannot be obtained.

JP-A-59-71316 discloses an emulsion copolymerization of an acrylic monomer, a styrene monomer and an organosilicon compound having both a reactive unsaturated group and an alkoxy group in an aqueous medium in the presence of colloidal silica. It is disclosed that by doing so, an aqueous resin dispersion capable of forming a coating film having excellent durability and stain resistance can be obtained. Further, JP-A-61-155474 discloses an aqueous resin dispersion obtained by emulsion polymerization of an acrylic monomer and an organosilicon compound having both a reactive unsaturated group and an alkoxy group in the presence of colloidal silica, and an alkoxysilyl compound. An aqueous coating composition having durability, heat resistance, stain resistance, anti-condensation and the like, using a water-soluble or water-dispersible acrylic copolymer having a group as a binder component is disclosed.

However, in each of the above two examples, the emulsion copolymerization of an organosilicon compound and an organic monomer is carried out in the presence of colloidal silica. And the condensation reaction between alkoxysilyl groups proceed simultaneously. Therefore, not only is the condensation reaction of the desired alkoxysilyl group with Si-OH on the silica surface difficult to complete, but also colloidal silica that does not participate in the condensation reaction coexists, resulting in sufficient interfacial adhesion between the organic polymer and the colloidal silica. It does not lead to imparting properties. Therefore, in order to carry out these means more effectively, a siloxy group containing a reactive unsaturated group having high radical copolymerizability is introduced in advance on the surface of colloidal silica, and then an organic monomer is copolymerized. It is considered that emulsion polymerization may be performed in two stages, but no studies have been made so far.

Recently, as one direction of the development of high-performance polymer materials, an organic polymer is modified with silicone to impart excellent properties such as heat resistance, cold resistance, weather resistance, and flame retardancy of silicone. Attempts have been made. However, silicone is a specific polymer having a siloxane skeleton and is incompatible with other general polymers having a carbon skeleton. Therefore, with a simple blend, the effect of imparting the properties of silicone to the obtained composition is not so significant. Therefore, it is necessary to chemically bond the siloxane skeleton to the carbon skeleton by grafting or the like.

As such a method, for example, Japanese Patent Application Laid-Open
Japanese Patent Application No. 50-1092828 describes that a graft copolymer is formed by polymerizing a vinyl monomer in the presence of a polyorganosiloxane containing a vinyl group or an allyl group to improve impact strength. In addition,
JP-A-60-252613, JP-A-61-106614 and JP-A-61-136510 disclose that a vinyl monomer is polymerized in an emulsion of a polyorganosiloxane containing an acryl group or a methacryl group. It is disclosed that a graft copolymer having graft efficiency and excellent impact strength is obtained. However, since the obtained graft copolymer uses only a polyorganosiloxane having insufficient strength as a rubber component, the mechanical properties such as impact resistance have not been sufficiently improved. Also,
As a measure for improving the mechanical properties, attempts have been made to improve the strength of the polyorganosiloxane by using a tri- or tetra-functional crosslinking agent such as an alkyl trialkoxysilane or a tetraalkoxysilane in combination, but there is a limit. No satisfactory has been obtained.

[0009]

To solve the above-mentioned problems in the above-mentioned measures for modifying and improving characteristics of general organic resins by adding a reinforcing agent such as silicone modified or colloidal silica, the following means can be considered. . That is, if a reinforcing material such as silica is introduced into the domain of the polyorganosiloxane, it is expected that the mechanical properties of the graft copolymer will be improved and that new properties will be imparted. However, for this purpose, a silicone emulsion containing a polyorganosiloxane and silica in the same micelle, preferably a silica core-silicone shell having a core of colloidal silica coated with a polyorganosiloxane shell via siloxane bonds. Emulsions are desired.

[0010] Although there is no document clearly indicating a method for producing such a core-shell body so far,
There is a patent publication in which a core-shell body may be formed. For example, JP-A-61-16929, JP-A-61-2
JP-A-71352 and JP-A-61-272264 disclose a silicone reinforced with colloidal silica by condensing a polyorganosiloxane having a hydroxyl group at a molecular end with a sulfonic acid emulsifier in the presence of acidic colloidal silica. It is disclosed that an aqueous emulsion is obtained. However, since polysiloxane having a relatively high degree of polymerization is used as a raw material, it is very difficult to include the polysiloxane and colloidal silica in the same micelle in the initial homogenization. In addition to the core-shell body, an emulsion in which colloidal silica not involved in polycondensation and polyorganosiloxane coexist is obtained. Therefore, even if this technique is applied to the production of the above graft copolymer, the effect of introducing colloidal silica hardly appears. Also, JP-A-1-234468 discloses that
An organic silane compound having a polymerizable unsaturated double bond and an alkoxy group, optionally mixed with other alkoxysilane and silica sol, and cured by radiation or heat resulting from hydrolysis to provide excellent coating film properties. A reactive microgel composition that provides a coating is disclosed. However, this does not give the organic polymer the properties of silicone resin such as heat resistance, cold resistance, weather resistance, etc., and does not aim or suggest such use.

The inventors of the present invention have conducted intensive studies on such problems, and as a result, formed a core-shell body of colloidal silica and silicone, and graft-polymerized a vinyl monomer onto the core-shell body to obtain impact resistance and abrasion resistance. It has been found that a thermoplastic resin having remarkably excellent weather resistance and the like can be obtained.

[0012]

Configuration of the Invention

[0013]

The thermoplastic resin of the present invention In order to achieve the above object, according, (A) a core from 99.9 to 5% by weight of colloidal silica, (B) the average compositional formula _{^{R 2a SiO (4-a)}} / 2 ... ( II) (wherein, R ² may be the same or different and may have 1 to 8 carbon atoms)
A substituted or unsubstituted monovalent hydrocarbon group, a is 0.8 to 3.
0 polyorganosiloxane shells represented by a is) the number of (here among R ^2, .02 to 100 mol% is a group containing a reactive unsaturated group) 0.1 to 95% by weight and consisting of silica core - It is characterized in that the silicone shell (i) contains a graft copolymer (iii) obtained by graft-polymerizing at least one vinyl monomer (ii). Also,
The method of manufacturing the thermoplastic resin of the present invention, (A) a core from 99.9 to 5% by weight of colloidal silica, (B) the average compositional formula _{^{R 2a SiO (4-a)}} / 2 ... (II) ( wherein, R ² and a are as defined above. polyorganosiloxane represented by) a shell (where the sale of R ² <br/> Chi, from 0.02 to 100 mol% is a group containing a reactive unsaturated group A) a step of graft-polymerizing at least one vinyl monomer (ii) to the core-shell body in an emulsion containing 0.1 to 95% by weight of a silica core-silicone shell body (i).

The colloidal silica of the component (A) used in the present invention refers to a dispersion in water containing SiO ₂ as a basic unit.
m, particularly preferably those having an average particle diameter of 30 to 150 nm. The colloidal silica has both an acidic side and an alkaline side, and these can be appropriately selected depending on conditions at the time of emulsion polymerization.

[0015] silica core according to the present invention - one component constituting the silicone shells body (i), i.e., component (B)
Po polyorganosiloxane shell, a group containing a reactive unsaturated group with respect to the total amount of organic groups bonded to the silicon atom,
It has both in the range of 0.02 to 100%.

The reactive unsaturated group is represented by the following general formula: CH ₂ CHCH—O— (CH ₂ ) _n − (V)

[0017]

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General formula:

[0019]

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The following is an example. Others
Examples of the group containing an ethylenically unsaturated group include a general formula: CH ₂ CH— (CH ₂ ) _n −... (VIII) (where n represents an integer of 0 to 10).

Examples of the group containing ethylenic unsaturation represented by the above formula (V) include a vinyloxypropyl group, a vinyloxyethoxypropyl group, a vinyloxyethyl group, a vinyloxyethoxyethyl group and the like, and preferably a vinyloxypropyl group. A vinyloxyethoxypropyl group.

When the ethylenically unsaturated group is represented by the formula (VI), R ⁶ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, Preferably it is a hydrogen atom or a methyl group. Examples of the group represented by the formula (VI) include a vinylphenyl group and an isopropenylphenyl group, and are preferably a vinylphenyl group. Examples of the group containing an ethylenically unsaturated group represented by the formula (VI) include a vinylphenyl group, a 1- (vinylphenyl) ethyl group, a 2- (vinylphenyl) ethyl group, a (vinylphenyl) methyl group,
Isopropenylphenyl, 2- (vinylphenoxy) ethyl, 3- (vinylbenzoyloxy) propyl, 3-
Examples thereof include an (isopropenylbenzoylamino) propyl group, and preferred are a vinylphenyl group, a 2- (vinylphenyl) ethyl group, and a 1- (vinylphenyl) ethyl group.

When the ethylenically unsaturated group is represented by the above formula (VII), R ⁷ is a hydrogen atom or a methyl group. R ⁸ is an alkylene group having 1 to 6 carbon atoms, -O-, -S-
Or -N (R ⁹⁾ R ¹⁰ - a group represented by wherein R ⁹ is a monovalent hydrocarbon group or (meth) acryloyl group to six carbon number of 1, R ¹⁰ is C 1 -C 6 Alkylene groups. Examples of the group containing an ethylenically unsaturated group represented by the formula (VII) include γ-acryloxypropyl, γ-methacryloxypropyl, N-methacryloyl-N-methyl
-γ-aminopropyl group, N-methacryloyl-N-methyl
-γ-aminopropyl group, N-acryloyl-N-methyl-
γ-aminopropyl group, N, N-bis (methacryloyl)-
γ-aminopropyl group, and examples thereof, preferably N-
Methacryloyl-N-methyl-γ-aminopropyl group, N-
Acryloyl-N-methyl-γ-aminopropyl group.

The group containing an ethylenically unsaturated group is
In the case of the formula (VIII), n is an integer of 0 to 10. Examples of the group containing an ethylenically unsaturated group represented by the formula (VIII) include a vinyl group, an allyl group, a homoallyl group, a 5-hexenyl group, and a 7-octenyl group. is there.

When the content of the group containing a reactive unsaturated group is less than 0.02% with respect to the total amount of organic groups bonded to silicon atoms, a high graft ratio can be obtained in graft polymerization with other organic monomers. Absent.

The silica core-silicone shell according to the present invention comprises: the above-mentioned colloidal silica of the component (A);
It is obtained by polycondensing the organosilicon compound (a) alone or the polyorganosiloxane (b) as the component (B) in an aqueous medium in the presence of an effective amount of an emulsifier or an emulsifier mixture.

The organosilicon compound of the component (B) (a) used in the present invention has a structure represented by the above formula (III).
Examples of such organosilicon compounds which have a constitutional unit include (vinyloxypropyl) methyldimethoxysilane, (vinyloxyethoxypropyl) methyldimethoxysilane, and p-vinylphenylmethyldimethoxysilane. , 1- (m-vinylphenyl) methyldimethylisopropoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, 3- (p-vinylphenoxy) propyltriethoxysilane, 3- (p-vinylbenzoyloxy ) Propylmethyldimethoxysilane, 1- (p-vinylphenyl) ethylmethyldimethoxysilane, 1- (o-vinylphenyl) -1,1,2-trimethyl-2,2-dimethoxydisilane,
1- (p-vinylphenyl) -1,1-diphenyl-3-ethyl-
3,3-diethoxydisiloxane, m-vinylphenyl [3-
Triethoxysilyl) propyl] diphenylsilane,
[3- (p-isopropenylbenzoylamino) propyl]
Phenyldipropoxysilane, γ-acryloxypropylmethyldiethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-methacryloyl-N-methyl-
γ-aminopropylmethyldimethoxysilane, N-acryloyl-N-methyl-γ-aminopropylmethyldimethoxysilane, N, N-bis (methacryloyl) -γ-aminopropylmethyldimethoxysilane, N, N-bis (acryloyl)- γ-aminopropylmethyldimethoxysilane, N-
Methacryloyl-N-methyl-γ-aminopropylphenyldiethoxysilane, 1-methacryloxypropyl-1,1,3
-Trimethyl-3,3-dimethoxydisiloxane, vinylmethyldimethoxysilane, vinylethyldiisopropoxysilane, vinyldimethylethoxysilane, allylmethyldimethoxysilane, 5-hexenylmethyldiethoxysilane, γ-octenylethyldiethoxysilane, etc. And these may be used alone or as a mixture of two or more.

The above-mentioned organosilicon compounds are preferably (vinyloxypropyl) methyldimethoxysilane, (vinyloxyethoxypropyl) methyldimethoxysilane, p-vinylphenylmethyldimethoxysilane, 2- (p-vinylphenyl) Ethylmethyldimethoxysilane, 3- (p-vinylbenzoyloxy) propylmethyldimethoxysilane, 1- (p-vinylphenyl) ethylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, N-methacryloyl-N-methyl- γ-
Aminopropylmethyldimethoxysilane, N-acryloyl-N-methyl-γ-aminopropylmethyldimethoxysilane, vinylmethyldimethoxysilane, allylmethyldimethoxysilane, more preferably p-vinylphenylmethyldimethoxysilane, γ-methacryloxypropyl Silane compounds such as methyldimethoxysilane, N-methacryloyl-N-methyl-γ-aminopropylmethyldimethoxysilane, and vinylmethyldimethoxysilane.

The polyorganosiloxane (B) or (b) used in the present invention has a structural unit represented by the above formula (IV) and a silicon number not containing a hydroxyl group.
The structure is not particularly limited, such as linear, branched or cyclic, but a polyorganosiloxane having a cyclic structure is preferred. In other words, the number of silicon atoms is 10
In the above, when emulsion polymerization is carried out, colloidal silica particles are hardly taken into the polyorganosiloxane micelles, so that those which cannot participate in the formation of the core-shell body occur.As a result, in addition to the target core-shell body, colloidal silica in a free state and An emulsion in which polyorganosiloxane micelles coexist is obtained. In addition, in the case of hydroxyl group-containing silicone, a polycondensation reaction occurs at the time of initial emulsification, resulting in an organosiloxane having 10 or more silicon atoms.

Examples of the substituted or unsubstituted monovalent hydrocarbon group of the polyorganosiloxane (B) or (b) include methyl, ethyl, propyl, vinyl, phenyl, and halogen. Examples thereof include a substituted hydrocarbon group substituted with an atom or a cyano group. Further, examples of the reactive unsaturated group include those described above. Examples of the polyorganosiloxane of the components (B) and (b) include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and 1,3,5-trimethyl-1. 1,3,5-triphenylcyclotrisiloxane, tris (3,3,3-trifluoropropyl) trimethylcyclotrisiloxane, 1,3,5,7-tetra
(Vinyloxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (vinyloxyethoxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (p-vinylphenyl) tetramethylcyclo Tetrasiloxane, 1,3,5,7-tetra [1- (m-vinylphenyl) methyl] tetramethylcyclotetrasiloxane, 1,3,5,7-
Tetra [2- (P-vinylphenyl) ethyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra [3- (P-vinylphenoxy) propyl] tetramethylcyclotetrasiloxane, 1,3,5, 7-tetra [3- (P-vinylbenzoyloxy) propyl] tetramethylcyclotetrasiloxane,
1,3,5,7-tetra [3- (P-isopropenylbenzoylamino) propyl] tetramethylcyclotetrasiloxane,
1,3,5,7-tetra (γ-acrylosipropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (γ-methacrylosipropyl) tetramethylcyclotetrasiloxane, 1,3,5, 7-tetra (N -methacryloyl-N-methyl-
γ-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (N-acryloyl-N-methyl-
γ-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra [N, N- (methacryloyl) γ-aminopropyl] tetramethylcyclotetrasiloxane,
1,3,5,7-tetra [N, N-bis (acryloyl) γ-aminopropyl] tetramethylcyclotetrasiloxane, 1,3,
5,7-tetravinyltetramethylcyclotetrasiloxane, octavinylcyclotetrasiloxane, 1,3,5-trivinyltrimethylcyclotrisiloxane, 1,3,5,7-tetraallyltetramethylcyclotetrasiloxane, 1,3 ,Five,
Examples include compounds such as 7-tetra (5-hexenyl) tetramethylcyclotetrasiloxane and 1,3,5,7-tetra (7-octenyl) tetramethylcyclotetrasiloxane, which may be used alone or as a mixture of two or more. Can be used. Further, another linear or branched organosiloxane may be used. However, in the case of a linear or branched organosiloxane, the molecular chain terminal is an organic group other than a hydroxyl group, for example, an alkoxy group, a trimethylsilyl group, a dimethylvinylsilyl group, a methylphenylvinylsilyl group,
Those blocked with a methyldiphenylsilyl group, 3,3,3-trifluoropropyldimethylsilyl group or the like are preferable. The organosilicon compound of component (B) (a), or the organosilicon compound of component (B) (a) and the polyorganosiloxane of component (B) (b) are as described above. The silicone shell portion in the silicone shell body is 0.1 to 95% by weight, and the group containing a reactive unsaturated group is 0.02 to 100% based on the total amount of organic groups bonded to silicon atoms in the silicone shell portion.
It is selected or blended so that This selection or blending is carried out, for example, by adding the colloidal silica of the component (A) to 99.9 to
5% by weight, (B) 0.1 to 95% by weight of the organosilicon compound (a) alone or the organosiloxane as the component (b) [(A) + (B) (a) + (B) (b) =
100% by weight. ].

The silica core-silicone shell according to the present invention comprises the above-mentioned colloidal silica (A) and the organosilicon compound (a) alone (B) or the organosilicon compound (b) and an organosiloxane (b) in an aqueous medium. It can be produced by shearing and condensing with a homogenizer or the like in the presence of an emulsifier. This emulsifier is used in the presence of (a) in the presence of an appropriate amount of water and the component (A).
While acting as a surfactant for emulsifying the component alone or the component (a) and the component (b), the alkoxy group of the component (a) is hydrolyzed and further polycondensed,
Alternatively, it functions as a catalyst for the hydrolyzate of the component (a) or the polycondensation reaction of the component (b), and includes an anionic emulsifier and a cationic emulsifier. Examples of the anionic emulsifier include an aliphatic substituted benzenesulfonic acid, an aliphatic substituted naphthalenesulfonic acid, an aliphatic sulfonic acid, a silylalkylsulfonic acid, and an aliphatic substituted benzenesulfonic acid having a carbon chain having a carbon atom length of 6 to 18. Substituted diphenyl ether sulfonic acid and the like can be mentioned, and aliphatic substituted benzene sulfonic acid is more preferable. As the cationic emulsifier, an alkyltrimethylammonium salt (for example,
Octadecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride) type, dialkyldimethylammonium salt (eg, dioctadecyldimethylammonium chloride, dihexadecyldimethylammonium chloride, didodecyldimethylammonium chloride) type, benzalkonium chloride (for example, octadecyl) Dimethylbenzylammonium chloride, hexadigisyldimethylbenzylammonium chloride)
And a quaternary ammonium salt type surfactant such as a type. However, since these quaternary ammonium salt type surfactants have low catalytic action depending on the kind, it is necessary to add an alkali catalyst such as sodium hydroxide or potassium hydroxide.

In the above, the amount of the emulsifier used is usually 0.1 part by weight based on 100 parts by weight of the total amount of the components (A) and (B).
To 5 parts by weight, preferably about 0.3 to 3 parts by weight. If necessary, a nonionic emulsifier may be used in combination.

In the production of the silica core-silicone shell according to the present invention, in order to keep the colloidal silica in a stable state, when an anionic emulsifier is used, acidic colloidal silica is used and a cationic emulsifier is used. In this case, it is necessary to use alkaline colloidal silica. The amount of water used for producing the silica core-silicone shell is usually 100 to 500 parts by weight, preferably 200 to 400 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). Parts by weight, and the condensation temperature is usually 5-100 ° C. In the production of the silica core-silicone shell, a crosslinking agent may be added as a fourth component in order to improve the strength of the silicone shell. Examples of the crosslinking agent include trifunctional crosslinking agents such as methyltrimethoxysilane, phenyltrimethoxysilane, ethyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, and 4-functional crosslinking agents such as tetraethoxysilane. Functional crosslinking agents may be mentioned. The amount of the crosslinking agent to be added is generally about 10% by weight or less, preferably about 5% by weight or less, based on the total amount of the component (B).

The silica core-silicone shell emulsion thus obtained is acidic or alkaline depending on the emulsion polymerization conditions. Therefore, it is necessary to neutralize the emulsion with an alkali or an acid as necessary. Examples of the alkaline substance include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate,
Triethanolamine, triethylamine and the like are used, and as the acidic substance, hydrochloric acid, sulfuric acid, nitric acid, acetic acid,
Oxalic acid or the like is used. The silica core-silicone shell thus obtained has an average particle size of 4 to 400.
The silica core-silicone shell having such an average particle diameter in nm can easily participate in the graft polymerization and contribute to the synthesis of a reinforced polymer when interposed in an organic polymer polymerization reaction system described below as an emulsion type. I do.

That is, in the silica core-silicone shell emulsion obtained as described above, a vinyl monomer is graft-polymerized to the core-shell body, whereby a desired thermoplastic resin comprising the graft copolymer of the present invention is obtained. can get.

The vinyl monomers used in the present invention include, for example, aromatic alkenyl compounds such as styrene, α-methylstyrene, dichlorostyrene, dibromostyrene and sodium styrenesulfonate; methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, Methacrylates such as butyl methacrylate and allyl methacrylate; acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl methacrylate, and dimethylaminoethyl methacrylate; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; ethylene and propylene Olefins; conjugated diolefins such as butadiene, isoprene and chloroprene; and vinyl acetate Vinyl chloride, vinylidene chloride,
Vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, triallyl isocyanurate, acrylic acid, methacrylic acid, N-phenylmaleimide, N-cyclohexylmaleimide, maleic anhydride, etc., and these may be used alone or in combination. Is done. Among these vinyl monomers, the purpose of further improving the impact resistance of the thermoplastic resin according to the present invention is 65 to 75% by weight.
Of styrene and 35 to 25% by weight of acrylonitrile are preferred.

The charge composition for graft polymerization of the vinyl monomer onto the silica core / silicone shell was 1 to 90% by weight of component (i) of the silica core / silicone shell.
Preferably from 5 to 80% by weight of the vinyl monomer (ii) component 99
-10% by weight, preferably 95-20% by weight, provided that (i) +
(ii) = 100% by weight], and if the component (i) is less than 1% by weight, the effect of modifying the impact strength and abrasion resistance cannot be obtained,
On the other hand, if it exceeds 90% by weight, the proportion of the vinyl polymer to be grafted decreases, and as a result, sufficient interfacial adhesion between the silica core-silicone shell body and the vinyl polymer cannot be obtained, and the strength of the obtained thermoplastic resin is reduced. descend. The graft ratio of the thus obtained graft copolymer is usually about 5% by weight or more, preferably about 10% by weight or more, and more preferably about 20% by weight or more. When the graft ratio of the graft copolymer is high as described above, the interfacial adhesion between the graft copolymer and the vinyl polymer that has not been directly grafted increases, so that the silica core-silicone shell body is uniformly formed in the vinyl polymer. Disperses and provides excellent strength, weather resistance, appearance, etc. Further, the thermoplastic resin of the present invention contains, in addition to the thus obtained graft copolymer, a vinyl polymer which is a polymer of a non-grafted vinyl monomer. % By weight, preferably 10% by weight or more.

In producing the thermoplastic resin of the present invention, a vinyl monomer is graft-polymerized on a silica core-silicone shell by ordinary radical polymerization to obtain a composition containing a graft copolymer. Examples of the radical polymerization initiator include an oxidizing agent composed of an organic hydroperoxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, and paramenthane hydroperoxide, a sugar-containing iron pyrophosphate formulation, a sulfoxylate formulation, Redox initiators in combination with reducing agents such as a mixture of iron sugar pyrophosphate formulation / sulfoxylate formulation; persulfates such as potassium persulfate and ammonium persulfate; azobisisobutyronitrile, dimethyl-2, Azo compounds such as 2'-azobisisobutyrate and 2-carbamoylazaisobutyronitrile; organic peroxides such as benzoyl peroxide and lauroyl peroxide; and the like. Preferred are redox initiators. is there. The amount of these radical polymerization initiators used is usually 0.05 to 5 parts by weight, preferably about 0.1 to 3 parts by weight, based on 100 parts by weight of the vinyl monomer used. It is preferably carried out by emulsion polymerization. In the emulsion polymerization, a known emulsifier, the above-mentioned radical initiator, a chain transfer agent and the like are used. Here, examples of the emulsifier include anionic emulsifiers such as sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium diphenylether disulfonate, and sodium alkali succinate sulfonate; and polyoxyethylene alkyl esters and polyoxyethylene alkyl allyl ethers. One or more nonionic emulsifiers can be used. The amount of the emulsifier used here is usually about 0.5 to 5% by weight based on the vinyl monomer. As the chain transfer agent, mercaptans such as t-dodecyl mercaptan, octyl mercaptan, n-tetradecyl mercaptan, n-hexyl mercaptan; halogen compounds such as carbon tetrachloride and ethylene bromide are usually used for vinyl monomers. 0.02-1% by weight is used. At the time of emulsion polymerization, in addition to a radical polymerization initiator, an emulsifier, a chain transfer agent, and the like, various electrolytes, a pH adjuster, and the like are used as needed, and the radical polymerization initiator is used for 100 parts by weight of the vinyl monomer. , An emulsifier, a chain transfer agent, etc. in an amount within the above range, and a polymerization temperature of 5 to 100.
The emulsion polymerization is carried out at a temperature of 50 DEG to 90 DEG C. and a polymerization time of 0.1 to 10 hours. Thus, the emulsion polymerization proceeds by adding a vinyl monomer and a radical initiator to an emulsion containing a colloidal silica-silicone core-shell body. The method of adding the vinyl monomer to the reactor in the polymerization step may be batch, divided, continuous addition, or a combination thereof. Further, the thermoplastic resin of the present invention is purified by coagulation by a usual salt coagulation method, washing the obtained powder with water, and then drying.

The thermoplastic resin of the present invention containing the above graft copolymer obtained by these methods can be pelletized by a kneading machine such as an extruder. On this occasion,
Other known polymers, usually 99, depending on the performance required
It may be used as a thermoplastic resin composition (hereinafter simply referred to as “thermoplastic resin composition”) by appropriately blending it in an amount of up to about 90% by weight, preferably up to about 90% by weight. Such polymers include, for example, diene rubbers such as polybutadiene, butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, polyisoprene, and natural rubber; acrylic rubber, ethylene-propylene copolymer, ethylene-propylene- Olefinic rubbers such as diene copolymers, chlorinated butyl rubber, and chlorinated polyethylene; styrene
Butadiene block copolymer, styrene-butadiene-
Aromatic vinyl-conjugated diene-based block copolymers such as styrene block copolymers and styrene-butadiene-styrene radial tereblock copolymers; hydrides of the block copolymers; polypropylene, polyethylene, polystyrene, styrene-acrylonitrile copolymers Polymer, rubber reinforced polystyrene (HIPS), acrylonitrile-butadiene-styrene resin (ABS resin), acrylonitrile-ethylenepropylene-styrene resin (AES resin), methyl methacrylate-butadiene-styrene resin (MBS resin), acrylonitrile-butadiene- Methyl methacrylate-styrene resin, acrylonitrile-n-butyl acrylate-styrene resin (AAS resin), polyvinyl chloride, polycarbonate, polyethylene terephthalate,
Pobutylene terephthalate, polyacetal, polyamide, epoxy resin, polyvinylidene fluoride, polysulfone, ethylene-vinyl acetate copolymer, PPS resin, polyetheretherketone, PPO resin, styrene-methyl methacrylate copolymer, styrene Examples include a maleic anhydride copolymer, a rubber-modified PPO resin, a styrene-maleimide copolymer, a rubber-modified styrene-maleimide copolymer, a polyamide elastomer, and a polyester elastomer. The pelletized thermoplastic resin (composition) is appropriately subjected to processing and molding by ordinary means such as compression molding and injection molding.

(Operation) In the thermoplastic resin according to the present invention, the core of colloidal silica is coated with an organosiloxy group containing a reactive unsaturated group and / or a shell of polyorganosiloxane through a siloxane bond, Further, the vinyl monomer is graft-polymerized. In other words, the silicone shell having a reactive unsaturated group is easily graft-polymerized with a vinyl monomer to exhibit a graft copolymer having a high graft ratio, and the reinforcing properties of the colloidal silica are effectively exhibited. . That is, the graft copolymer, when blended with itself or other thermoplastics, has excellent impact strength,
It exhibits sliding characteristics, weather resistance, etc., and can be used for various molded products, exterior parts in automobiles, electric / electronic parts, building materials, and also paints. Then, the vinyl monomer is easily graft-polymerized to the core-shell body in an emulsion containing a core-shell body composed of a core of colloidal silica and an organosiloxy group containing a reactive unsaturated group and / or a shell of polyorganosiloxane. Obtainable.

(Examples) Hereinafter, examples of the present invention will be described. Parts and% in the examples are parts by weight and% by weight unless otherwise specified.

In the examples, measurements in various tests were performed in accordance with the following.

First, the graft ratio and the graft efficiency are as follows:
It was determined by the following method. That is, a constant weight (x) of the graft polymerization product is put into acetone, shaken with a shaker for 2 hours to dissolve the free copolymer, and then centrifuged at 23,000 rpm using a centrifuge at 23,000 rpm. Centrifuge for 2 minutes to obtain insoluble matter. Next, it is dried at 120 ° C. for 1 hour using a vacuum dryer,
The weight (y) of the insoluble matter was obtained, and the graft ratio and the graft efficiency were calculated by the following equations. Next, physical properties were evaluated according to the following evaluation methods. * Izod impact strength ASTM-D256, 1/4 ", Notched at 23 ° C Unit: kgf · cm / cm * Gloss ASTM-D523, 45 ° Unit:% * Sliding characteristics The same material or steel (S45C) was used as the mating material, and the test piece used was a hollow cylinder with an outer diameter of 25.6 mm and an inner diameter of 20.0 mm. The dynamic friction coefficient was measured in a 23 ° C. room temperature, 50% humidity atmosphere at a load of 5 kg and a running speed of 3.75 cm / sec.

The dynamic friction coefficient was calculated by the following equation.

[0045]

(Equation 1)

(Where, μ is the coefficient of dynamic friction, F is the force applied to the load cell, P is the load, R is the arm length to the load cell, r ₁ is the inside diameter, and r ₂ is the outside diameter.) Measurement of the specific wear amount The conditions are as follows: In the atmosphere of room temperature 23 ° C and humidity 50%, the same material is measured at a load of 5 kg, running speed of 3.75 cm / sec, 12,600 revolutions (running speed of 0.24 km), and for steel (S45C) , Load 10kg, running speed 15cm / sec, 80,000 revolutions (running speed 6km)
Was measured. The specific wear amount is calculated by the following equation. (Where A is the specific wear amount, ΔW is the weight change of the sample, P
Is the load, l is the mileage, and α is the density of the sample. )
* Weather resistance test method Izod impact strength and gloss were measured after exposure for 200 hours (63 ° C, with rain) using a sunshine weather meter (WE-USN-HC type, manufactured by Toyo Rika Co., Ltd.). The average particle size of the colloidal silica and silica core-silicone shell used as the raw material was measured using a laser particle size analysis system LPA-3000S / 3100 manufactured by Otsuka Electronics Co., Ltd., which employed a dynamic light scattering method.

Example 1 Acidic colloidal silica (Snowtex OZL manufactured by Nissan Chemical Industries, Ltd., average particle size 122 nm, SiO ₂ 21.14%, Na
₂ O 0.101%, PH2.02) (Abbreviated as A-1 in the table below)
100 parts, distilled water 47 parts, dodecylbenzenesulfonic acid 0.84
A mixture of 0.32 parts of P-vinylphenylmethyldimethoxysilane (abbreviated as b-1 in the following table) and 21 parts of octamethylcyclotetrasiloxane (abbreviated as a-1 in the following table) and the mixture was preliminarily stirred by a homomixer, a homogenizer at a pressure of 300 kgf / cm ² 2
It was emulsified and dispersed by passing through.

The emulsified and dispersed liquid mixture was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer, heated at 85 ° C. for 5 hours while stirring and mixing, and cooled at 5 ° C. for 48 hours to conduct condensation. Completed. Next, this polyorganosiloxane emulsion was neutralized to pH 7 with an aqueous solution of sodium carbonate to terminate the condensation. The condensation rate of octamethylcyclotetrasiloxane in the obtained polyorganosiloxane (abbreviated as condensation rate of a-1 in the following table) was 99.6%. The particle size analysis based on the dynamic light scattering method and observation with an electron microscope confirmed that the polyorganosiloxane was a silica core / silicone shell (abbreviated as shell in the following table).
That is, a laser particle size analysis system (Otsuka Electronics Co., Ltd.)
When the particle size was analyzed using LPA-3000S / 3100), the monodisperse particle size distribution having a peak near 122 nm of the raw colloidal silica completely disappeared, and the monodisperse particle having a peak near 175 nm was completely eliminated. A new particle size distribution has emerged. Further, when observed with an electron microscope, only the silicone particle image was confirmed, and no raw material silica particle image was observed at all. Next, the core-shell emulsion was poured into a large amount of acetone, and the core-shell body was bent out.
It was dried at 50 ° C. for 12 hours with a vacuum dryer to obtain a core-shell aggregate. And elemental analysis of this core-shell aggregate,
As a result of IR and ¹ H, ¹³ C, ²⁹ Si-NMR analysis, the ratio of the silicone shell portion was 49.2%, and the ratio of the p-vinylphenyl group in the organic group of the silicone shell portion was 0.1%.
27%. Next, a graft copolymer with a vinyl monomer was synthesized using the silica core-silicone shell obtained above. That is, the core-shell emulsion was mixed with 35 parts in terms of solid content, 0.5 part of sodium dodecylbenzenesulfonate and 140 parts of distilled water, and transferred to a separable flask equipped with a dropping funnel, a condenser, a nitrogen inlet, and a stirrer. 15.81 parts of styrene corresponding to 34% of the total amount of styrene (abbreviated as ST in the following table), 6.29 parts of acrylonitrile corresponding to 34% of the total amount of acrylonitrile (abbreviated to AN in the following table), and ethylenediamine 0.2 parts of sodium acetate, 0.25 parts of sodium formaldehyde sulfoxylate, ferrous sulfate 0.00
4 parts and 0.074 parts of cumene hydroperoxide were added, and the temperature was raised to 70 ° C. while flowing nitrogen. After polymerization for 1 hour, the remaining 30.69 parts of styrene and the remaining 1 part of acrylonitrile
2.21 parts, sodium dodecylbenzenesulfonate 1.084
, 42 parts of distilled water, 0.12 parts of cumene hydroperoxide and 0.06 parts of t-dodecyl mercaptan were added using a dropping funnel over 3 hours. After the completion of the dropping, a polymerization reaction was performed for 1 hour, and then the reaction system was cooled. The graft copolymer latex obtained by the above reaction was poured into warm water in which 2 parts of calcium chloride dihydrate had been dissolved, and subjected to salting out and coagulation to separate a thermoplastic resin containing the graft copolymer. Thereafter, the thermoplastic resin was thoroughly washed with water, dried at 80 ° C. for 16 hours, purified, and measured for the graft ratio and graft efficiency. Table 1 shows the results. Then
Using the thermoplastic resin obtained in Example 1 in this manner,
A composition was prepared as Example 1 and obtained from the composition.
Various physical properties of the molded article were measured. That is, 57% of this thermoplastic resin powder was mixed with 43% of a copolymer (abbreviated as AS resin in the following table) obtained by emulsion polymerization of styrene and acrylonitrile at a charged monomer weight ratio of 75:25. Then, a thermoplastic resin composition was prepared. This thermoplastic resin composition is heated at a cylinder temperature using a twin-screw extruder.
Extruded at 230 ° C to obtain pellets. As shown in Table 1, the molded article obtained by molding using the pelletized thermoplastic resin composition obtained above had excellent weather resistance, slidability, impact resistance, and appearance.

Examples 2 and 3 The acidic colloidal silica, distilled water, dodecylbenzenesulfonic acid, p-vinylphenylmethyldimethoxysilane and octamethylcyclotetrasiloxane used in Example 1 were used in the proportions shown in Table 1. Except for changing, polyorganosiloxane emulsions were obtained under the same conditions as in Example 1. Each of the polyorganosiloxane emulsions obtained above was confirmed to be a silica core-silicone shell having a monodispersed particle size distribution by particle size analysis based on dynamic light scattering and observation with an electron microscope.
Table 1 shows the evaluation results of these core-shell bodies in the same manner as in Example 1. Further, using these core-shell bodies, a graft copolymer with a vinyl monomer was obtained under the same conditions as in Example 1 . Then, a reference example
Graphs obtained in Examples 2 and 3 as 2, 3 respectively
The copolymer was mixed with the AS resin to obtain pellets of the thermoplastic resin composition. Table 1 shows the results of the graft ratio, graft efficiency and physical properties of the thermoplastic resin composition in these examples.
Shown in

Examples 4 to 6 As organosilicon compounds, γ-methacryloxypropylmethyldimethoxysilane (abbreviated as b-2 in the following table), N-methacryloyl-N-methyl-γ-aminopropylmethyldimethoxysilane ( In the following table, abbreviated as b-3), vinylmethyldimethoxysilane (b-4 in the following table)
Polyorganosiloxane emulsions were obtained under the same conditions as in Example 1 except that each of these was used in the proportions shown in Table 1.

These polyorganosiloxanes obtained above were confirmed to be a silica core-silicone shell having a monodispersed particle size distribution by particle size analysis based on dynamic light scattering and observation with an electron microscope.

Table 1 shows the results of evaluating each of these core-shell bodies in the same manner as in Example 1. Further, using these core-shell bodies, a graft copolymer with a vinyl monomer was formed under the same conditions as in Example 1.
Was. Then, as Reference Examples 4 to 6,
Each of the obtained graft copolymers was mixed with an AS resin to obtain pellets of a thermoplastic resin composition. Table 1 shows the results of the graft ratio, graft efficiency and physical properties of the thermoplastic resin composition in these examples.

Example 7 As an acidic colloidal silica, Snowtex OL (manufactured by Nissan Chemical Industries, Ltd .; average particle diameter 84 nm, SiO ₂ 20.66)
_{%, Na 2 O0.019%, PH2.78} ) ( below abbreviated as A-2 in the table) were obtained using a polyorganosiloxane emulsion if the same conditions of Example 1. The polyorganosiloxane obtained as described above was confirmed to be a silica core-silicone shell having a monodispersed particle size distribution by particle size analysis based on dynamic light scattering and observation with an electron microscope.
Table 1 shows the results of evaluation of the core-shell body in the same manner as in Example 1. Further, using this core-shell body, a graft copolymer with a vinyl monomer was obtained under the same conditions as in Example 1 . Then, Reference Example 7
As a result, the graft copolymer obtained in Example 7 was mixed with an AS resin to obtain pellets of a thermoplastic resin composition. Table 1 shows the results of the graft ratio, graft efficiency and physical properties of the thermoplastic resin composition in this example.

Example 8 Alkaline colloidal silica (Snowtex ZL, Nissan Chemical Industries, Ltd., average particle diameter 110 nm, SiO ₂ 40.23%, N
a ₂ O0.036%, (abbreviated in the Table A-3 below) PH9.72 10
0 parts, 194 parts of distilled water, 6.5 parts of dioctadecyldimethylammonium chloride, and 1.5 parts of potassium hydroxide in a mixed solution of p-
A mixture of 0.64 parts of vinylphenylmethyldimethoxysilane and 42 parts of octamethylcyclotetrasiloxane was added, and the mixture was preliminarily stirred with a homomixer, and then passed twice with a homogenizer at a pressure of 300 kgf / cm ² to emulsify.
Dispersed. The emulsified and dispersed mixture was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer, heated at 85 ° C. for 5 hours while stirring and mixing, and cooled at 5 ° C. for 48 hours to complete the condensation. Next, the polyorganosiloxane emulsion was neutralized to pH 7 with hydrochloric acid to terminate the condensation. The condensation rate of octamethylcyclotetrasiloxane in the obtained polyorganosiloxane was 97.9%. The obtained polyorganosiloxane was confirmed to be a colloidal silica-silicone core-shell body having a monodispersed particle size distribution by particle size analysis based on dynamic light scattering and observation with an electron microscope. Table 1 shows the results of evaluation of this core-shell body in the same manner as in Example 1. Further, using these core-shell bodies, a graft copolymer with a vinyl monomer was obtained under the same conditions as in Example 1 . Then, as Reference Example 8,
The graft copolymer obtained in Example 8 was mixed with an AS resin to obtain a pellet of a thermoplastic resin composition. Table 1 shows the results of the graft ratio, graft efficiency and physical properties of the thermoplastic resin composition in these examples.

Example 9 Acidic colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex O average particle diameter 31 nm, SiO ₂ 20.53%, Na ₂ O)
0.034%, PH2.58) (abbreviated as A-4 in the table below) 100
Part, 0.43 part of dodecylbenzenesulfonic acid in a mixture of
After adding 0.32 parts of p-vinylphenylmethyldimethoxysilane and preliminarily stirring with a homomixer, the mixture was passed twice with a homogenizer at a pressure of 300 kgf / cm ² to obtain
Emulsified and dispersed. The emulsified and dispersed mixture was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer, and heated at 85 ° C for 5 hours while stirring and mixing.
The condensation was completed by cooling for 24 hours. Next, the emulsion was neutralized to pH 7 with an aqueous sodium carbonate solution to terminate the condensation. The solid content in the obtained emulsion was 21.6%. The obtained polyorganosiloxane was confirmed to be a silica core-silicone shell having a monodispersed particle size distribution by particle size analysis based on dynamic light scattering and observation with an electron microscope. Table 1 shows the results of evaluation of this core-shell body in the same manner as in Example 1. Next, using this core-shell body mainly composed of colloidal silica, copolymerization with a vinyl monomer was carried out under the same conditions as in Example 1. The conversion of the vinyl monomer was considered. The recovery rate after salting out coagulation / drying purification was 98.2%, and it was confirmed that the core-shell body was almost completely incorporated into the obtained copolymer. Furthermore, Reference Example 9 and
Then, this graft copolymer was mixed with an AS resin under the same conditions as in Example 1 to obtain a pellet of a thermoplastic composition. Table 1 shows the results of the graft ratio, graft efficiency, and physical properties of the thermoplastic resin composition of the above graft copolymer. In addition, the obtained resin was a transparent resin because the particle diameter of the core-shell body was extremely small.

Examples 10 to 25 As vinyl monomers for graft polymerization, methyl methacrylate (abbreviated as MM in the following table), N-phenylmaleimide (abbreviated as PMI in the following table), and glycidyl methacrylate (as shown in the following table) GM), methacrylic acid (abbreviated as MA in the table below), and 2-hydroxyethyl methacrylate (abbreviated as HEMA in the table below), respectively.
Example 1 except that the composition ratios shown in Tables 2 and 3 were selected.
A thermoplastic resin was obtained in the same manner as in the above case. Next, a reference example
Nylon-6, a polybutylene terephthalate resin (abbreviated as PBT in the table below) as a thermoplastic resin blended with the thermoplastic resin obtained in the examples in the above manner ,
Polycarbonate resin (abbreviated as PC in the table below), polystyrene resin (abbreviated as PS in the table below), polyvinyl chloride resin (abbreviated as PVC in the table below), polypropylene resin (PP as Abbreviated), polyethylene resin (abbreviated as PE in the table below), polyacetal resin (abbreviated as POM in the table below), polyvinylidene fluoride resin (abbreviated as PVDF in the table below), polyphenylene sulfide resin (hereinafter abbreviated as PVDF) In Tables 2 and 3, a polyphenylene oxide resin (abbreviated as PPO in the following table), and a polyester ether amide block copolymer (abbreviated as PEA in the following table) have the compositions shown in Tables 2 and 3, respectively. A thermoplastic resin composition was obtained in the same manner as in Example 1 except that the ratio was selected . Heat obtained in the examples
Tables 2 and 3 show the results of the evaluation of the characteristics of the thermoplastic resin and the thermoplastic resin composition obtained in Reference Examples .

Comparative Example 1 A polyorganosiloxane emulsion was obtained under the same conditions as in Example 1 except that P-vinylphenylmethyldimethoxysilane was not used. The polyorganosiloxane obtained above was confirmed to be a silica core-silicone shell having a monodispersed particle size distribution by particle size analysis based on dynamic light scattering and observation with an electron microscope. Table 3 shows the results of evaluation of this core-shell body in the same manner as in Example 1. Further, using this core-shell body, a graft copolymer with a vinyl monomer was formed under the same conditions as in Example 1 and then mixed with an AS resin to obtain a pellet of a thermoplastic resin composition. Table 3 shows the results of the graft ratio, graft efficiency and physical properties of the thermoplastic resin composition in this example.

Comparative Example 2 Example 9 was repeated under the same conditions as in Example 9 except that P-vinylphenylmethyldimethoxysilane was not used.
The colloidal silica was heated and cooled. Next, using this colloidal silica, a vinyl monomer was copolymerized under the same conditions as in Example 1. The recovery rate after salting-out coagulation and drying and purification in consideration of the conversion rate of the vinyl monomer was 48.6%, and it was confirmed that colloidal silica was hardly incorporated into the obtained resin.

Comparative Example 3 A thermoplastic resin composition was obtained in the same manner as in Example 4 except that the component (A) in the core-shell emulsion composition was not used. Table 3 shows the results of the evaluation of the thermoplastic resin composition prepared above. It is recognized that the Izod impact strength was inferior to that of Example 4. (Below)

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3]

[0063]

As can be seen from the above description, the thermoplastic resin of the present invention is obtained by graft polymerizing a vinyl monomer onto a colloidal silica core covered by a polyorganosiloxane shell via a siloxane bond. Yes, it is possible to sufficiently bring out the reinforcing properties of colloidal silica. In addition, since a reactive unsaturated group is bonded to the siloxane side chain in the silicone shell, a graft copolymer having a higher graft ratio is formed by graft polymerization of this core-shell body with another organic monomer. I have. Further, in the present invention, a colloidal silica and / or polyorganosiloxane is conventionally used by using a polymer monomer which is compatible with the polymer to be blended as a monomer to be graft-polymerized to the silica core-silicone shell. Since it can be compatible with other incompatible polymers, it is possible to obtain a thermoplastic resin composition that focuses on new characteristics. This also implies that colloidal silica and / or
Alternatively, it means that the properties of polyorganosiloxane can be imparted, and a polymer having improved impact strength, sliding properties, weather resistance, and the like can be obtained. Thus, the present invention contributes greatly to the so-called polymer alloying technology, in parallel with the fact that the required monomers can be easily and efficiently graft-copolymerized onto the silica core-silicone shell.
The industrial significance is extremely large.

Continued on the front page (72) Inventor Takashi Kurata 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Inventor Ijuin Noriaki 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Inventor Tateki Furuyama 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.Examiner Yasue Uchida (58) Field surveyed (Int.Cl. ⁷ , DB name) C08F 283 / 12

Claims (4)

(57) [Claims] (A) Colloidal silica core
99.9 to 5% by weight and (B) the average composition formula ^{_{R 2 a SiO (4-a}} ) / 2 ... (II) ( wherein, R ² is 1-8 may carbon atoms or mutually different in the same
A substituted or unsubstituted monovalent hydrocarbon group, a is 0.8 to 3.
0) (wherein 0.02 to 100 mol% of R ² is a group containing a reactive unsaturated group)
A silica core-silicone shell (i) comprising 0.1 to 95% by weight of a graft copolymer (iii) obtained by graft-polymerizing at least one vinyl monomer (ii). Thermoplastic resin. 2. The thermoplastic resin according to claim 1, wherein the core of the core-shell body is derived from water-dispersible colloidal silica. 3. The shell of the core-shell body has an average composition formula of R ³ _b Si (OR ⁴ ) _4-b (III) (wherein R ³ may be the same or different, and may have 1 to 8 carbon atoms).
R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group
An alkyl group of 1 to 6, b is an integer of 1 to 3; The organic silicon compound represented by) (a) alone or the organic silicon compound (a) and the average composition formula ^{_{R 5 c SiO (4-c}} ) / 2 ... (IV) ( wherein, R ⁵ is a phase in the same May be different 1-8 carbon atoms
A substituted or unsubstituted monovalent hydrocarbon group, c is 0.8 to 3.
Indicates the number of zeros. A condensate with a polyorganosiloxane (b) having 2 to 10 silicon atoms and having no hydroxyl group and having a structural unit represented by the following formula (here, 0.02 to 100 mol of the total of R ³ and R ⁵ ) % Is a group containing a reactive unsaturated group). 4. A core of colloidal silica
99.9 to 5% by weight and (B) the average composition formula ^{_{R 2 a SiO (4-a}} ) / 2 ... (II) ( wherein, R ² and a are as defined above.) Polyorganosiloxane represented by (Here, 0.02 to 100 mol% of R ^{2 is} a group containing a reactive unsaturated group) in an emulsion containing 0.1 to 95% by weight of a silica core-silicone shell (i). At least one
A method for producing a thermoplastic resin, comprising a step of graft-polymerizing a kind of vinyl monomer (ii) to the core-shell body.