JPWO2006004058A1 - Rubber-reinforced resin, method for producing the same, and rubber-reinforced resin composition - Google Patents

Abstract

The object of the present invention is to obtain a molded article having a high dimensional accuracy, high brightness, excellent colorability, slidability, impact resistance and weather resistance since the linear expansion coefficient is small and the molding shrinkage ratio is small. An object of the present invention is to provide a rubber-reinforced resin, a method for producing the same, and a rubber-reinforced resin composition. The rubber-reinforced resin of the present invention comprises 99 to 30% by mass of a vinyl monomer (m) containing an aromatic vinyl compound in the presence of 1 to 70% by mass of a polyorganosiloxane (p) [provided that the component (p) And the sum total of a component (m) is 100 mass%. ] Is a rubber-reinforced resin containing a grafted polyorganosiloxane obtained by polymerizing, and the grafted polyorganosiloxane has a number average particle diameter of 4 to 65 nm.

Description

  The present invention relates to a rubber-reinforced resin, a method for producing the same, and a rubber-reinforced resin composition. The present invention relates to a rubber reinforced resin capable of obtaining a molded article excellent in heat resistance, impact resistance and weather resistance, a method for producing the same, and a rubber reinforced resin composition.

ABS-based resins are frequently used as molding materials for components used in office automation equipment, home appliances, vehicles, etc., and exterior molded products. For these parts and exterior molded products, it is required to maintain and exhibit various performances at a high level. For example, the molded article is required to have high performance in terms of dimensional stability, slidability, impact resistance, weather resistance, and the like.
As molding materials having both slidability and weather resistance, Patent Document 1, Patent Document 2, and the like disclose rubber-reinforced resins (compositions) using polyorganosiloxane.

JP-A-60-252613 Japanese Patent Laid-Open No. 2-8209

However, the rubber-reinforced resin and the rubber-reinforced resin composition using a polyorganosiloxane having a large particle size may not have sufficient dimensional stability, colorability and impact resistance of the obtained molded product. In addition, when a metal layer is formed on the surface of the molded product, the luminance may be insufficient.
The present invention has been made against the background of the above problems, and since the linear expansion coefficient is small and the molding shrinkage ratio is small, the dimensional accuracy is high, the brightness is high, the colorability, the slidability, the impact resistance and the weather resistance. An object of the present invention is to provide a rubber-reinforced resin, a method for producing the same, and a rubber-reinforced resin composition capable of obtaining a molded article excellent in the above.

The present invention is as follows.
1. (A) 90 to 99.8% by weight of organosiloxane and (b) 10 to 0.2% by weight of graft crossing agent are obtained by cocondensation [provided that the sum of component (a) and component (b) is 100% by mass. In the presence of 1 to 70% by mass of polyorganosiloxane (p1) having a volume average particle diameter of 4 to 60 nm, 99 to 30% by mass of a vinyl monomer (m1) containing an aromatic vinyl compound [ However, the sum total of a component (p1) and a component (m1) is 100 mass%. ] A rubber-reinforced resin obtained by polymerizing
2. 2. The rubber-reinforced resin according to 1 above, wherein the graft crossing agent (b) is at least one selected from the following [i] to [iv].
[I] A compound having an unsaturated group represented by the following formula (1) and an alkoxysilyl group having 1 to 2 carbon atoms.
(In the formula, R ² is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)
[Ii] A compound containing a structural unit represented by the following formula (2).
(Wherein R ³ is a vinyl group or an allyl group, R ⁴ is a monovalent hydrocarbon group having 1 to 6 carbon atoms and having no aliphatic unsaturated group, and p is 1 And is an integer of 0 to 2. q is an integer of 0 to 2.)
[Iii] A compound containing a structural unit represented by the following formula (3).
(In the formula, R ⁵ has 1 to 18 carbon atoms and is a divalent or trivalent aliphatic saturated hydrocarbon group, and R ⁶ has 1 to 6 carbon atoms and has an aliphatic unsaturated group. Not a monovalent hydrocarbon group, and r is an integer of 0 to 2.)
[Iv] A compound containing a structural unit represented by the following formula (4).
(In the formula, R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, s is an integer of 1 to 6, and t is an integer of 0 to 2.)
3. In the presence of 1 to 70% by mass of polyorganosiloxane (p2), 99 to 30% by mass of a vinyl monomer (m2) containing an aromatic vinyl compound [however, the sum of component (p2) and component (m2) is 100% by mass. ] A rubber reinforced resin containing a grafted polyorganosiloxane obtained by polymerizing a polymer, wherein the grafted polyorganosiloxane has a number average particle diameter of 4 to 65 nm.
4). The polyorganosiloxane (p2) is obtained by co-condensing 90 to 99.8% by mass of an organosiloxane (a) and 10 to 0.2% by mass of a graft crossing agent (b) [provided that the component (a ) And component (b) is 100% by mass. And the volume average particle size is 4 to 60 nm,
4. The rubber reinforced resin according to 3 above, wherein the graft crossing agent (b) is at least one selected from the following [i] to [iv].
[I] A compound having an unsaturated group represented by the following formula (1) and an alkoxysilyl group having 1 to 2 carbon atoms.
(In the formula, R ² is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)
[Ii] A compound containing a structural unit represented by the following formula (2).
(Wherein R ³ is a vinyl group or an allyl group, R ⁴ is a monovalent hydrocarbon group having 1 to 6 carbon atoms and having no aliphatic unsaturated group, and p is 1 And is an integer of 0 to 2. q is an integer of 0 to 2.)
[Iii] A compound containing a structural unit represented by the following formula (3).
(In the formula, R ⁵ has 1 to 18 carbon atoms and is a divalent or trivalent aliphatic saturated hydrocarbon group, and R ⁶ has 1 to 6 carbon atoms and has an aliphatic unsaturated group. Not a monovalent hydrocarbon group, and r is an integer of 0 to 2.)
[Iv] A compound containing a structural unit represented by the following formula (4).
(In the formula, R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, s is an integer of 1 to 6, and t is an integer of 0 to 2.)
5. (A) 90 to 99.8% by weight of organosiloxane and (b) 10 to 0.2% by weight of graft crossing agent are obtained by cocondensation [provided that the sum of component (a) and component (b) is 100% by mass. In the presence of 1 to 70% by mass of polyorganosiloxane (p1) having a volume average particle diameter of 4 to 60 nm, 99 to 30% by mass of a vinyl monomer (m1) containing an aromatic vinyl compound [ However, the sum total of a component (p1) and a component (m1) is 100 mass%. ] To obtain a rubber-reinforced resin.
6). 6. The method for producing a rubber-reinforced resin according to 5 above, wherein the graft crossing agent (b) is at least one selected from the following [i] to [iv].
[I] A compound having an unsaturated group represented by the following formula (1) and an alkoxysilyl group having 1 to 2 carbon atoms.
(In the formula, R ² is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)
[Ii] A compound containing a structural unit represented by the following formula (2).
(Wherein R ³ is a vinyl group or an allyl group, R ⁴ is a monovalent hydrocarbon group having 1 to 6 carbon atoms and having no aliphatic unsaturated group, and p is 1 And is an integer of 0 to 2. q is an integer of 0 to 2.)
[Iii] A compound containing a structural unit represented by the following formula (3).
(In the formula, R ⁵ has 1 to 18 carbon atoms and is a divalent or trivalent aliphatic saturated hydrocarbon group, and R ⁶ has 1 to 6 carbon atoms and has an aliphatic unsaturated group. Not a monovalent hydrocarbon group, and r is an integer of 0 to 2.)
[Iv] A compound containing a structural unit represented by the following formula (4).
(In the formula, R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, s is an integer of 1 to 6, and t is an integer of 0 to 2.)
7). The rubber-reinforced resin according to the above 1 and another thermoplastic polymer are contained, and the content of the polyorganosiloxane (p1) used in the above 1 is 1 to 40% by mass with respect to the entire composition. A rubber-reinforced resin composition characterized by being.
8). 8. The rubber-reinforced resin composition according to 7 above, wherein the other thermoplastic polymer is a (co) polymer and / or polycarbonate of a vinyl monomer containing an aromatic vinyl compound.
9. The rubber-reinforced resin described in 3 above and another thermoplastic polymer are contained, and the content of the polyorganosiloxane (p2) used in 3 is 1 to 40% by mass with respect to the entire composition. A rubber-reinforced resin composition characterized by being.
10. 10. The rubber-reinforced resin composition according to 9 above, wherein the other thermoplastic polymer is a (co) polymer and / or polycarbonate of a vinyl monomer containing an aromatic vinyl compound.

The rubber-reinforced resin of the present invention is obtained by co-condensing (a) 90 to 99.8% by mass of an organosiloxane and (b) 10 to 0.2% by mass of a graft crossing agent [provided that the component (a) And the sum total of a component (b) is 100 mass%. In the presence of 1 to 70% by mass of polyorganosiloxane (p1) having a volume average particle diameter of 4 to 60 nm, 99 to 30% by mass of a vinyl monomer (m1) containing an aromatic vinyl compound [ However, the sum total of a component (p1) and a component (m1) is 100 mass%. ) Is obtained by polymerizing the rubber-reinforced resin, the linear expansion coefficient is small, the molding shrinkage is small, so the dimensional accuracy is high, the brightness is high, the colorability, the slidability, A molded article excellent in impact resistance and weather resistance can be easily obtained.
Another rubber-reinforced resin of the present invention is a vinyl monomer (m2) containing an aromatic vinyl compound in the presence of 1 to 70% by mass of polyorganosiloxane (p2) 99 to 30% by mass [however, The sum total of a component (p2) and a component (m2) is 100 mass%. ], A rubber-reinforced resin containing a grafted polyorganosiloxane obtained by polymerizing, and the number average particle size of the grafted polyorganosiloxane is 4 to 65 nm. Since the molding shrinkage ratio is small, the dimensional accuracy is high, the luminance is high, and the molded product having excellent colorability, slidability, impact resistance and weather resistance can be easily obtained.

  The rubber-reinforced resin composition of the present invention contains the above rubber-reinforced resin and another thermoplastic polymer, so that the linear expansion coefficient is small and the molding shrinkage rate is small, so the dimensional accuracy is high, the brightness is high, A molded product excellent in colorability, slidability, impact resistance and weather resistance can be easily obtained. When the other thermoplastic polymer is polycarbonate, a molded article having particularly excellent impact resistance can be obtained.

2 is an image representing a grafted polyorganosiloxane according to Example 1. 2 is an image showing a grafted polyorganosiloxane according to Comparative Example 1.

Hereinafter, the present invention will be described in more detail. In this specification, “(meth) acryl” means both “acryl” and “methacryl”. “(Co) polymerization” means homopolymerization and copolymerization.
1. Rubber Reinforced Resin and Method for Producing the Same The rubber reinforced resin of the present invention (hereinafter also referred to as “rubber reinforced resin [A1]”) comprises (a) 90 to 99.8% by mass of organosiloxane, and (b) a graft crossing agent. It is obtained by co-condensation with 10 to 0.2% by mass [provided that the total of component (a) and component (b) is 100% by mass. In the presence of 1 to 70% by mass of polyorganosiloxane (p1) having a volume average particle diameter of 4 to 60 nm, 99 to 30% by mass of a vinyl monomer (m1) containing an aromatic vinyl compound [ However, the sum total of a component (p1) and a component (m1) is 100 mass%. ] Is obtained by polymerization.
The rubber-reinforced resin production method of the present invention is obtained by co-condensing (a) 90 to 99.8% by mass of an organosiloxane and (b) 10 to 0.2% by mass of a graft crossing agent [provided that The sum of component (a) and component (b) is 100% by mass. In the presence of 1 to 70% by mass of polyorganosiloxane (p1) having a volume average particle diameter of 4 to 60 nm, 99 to 30% by mass of a vinyl monomer (m1) containing an aromatic vinyl compound [ However, the sum total of a component (p1) and a component (m1) is 100 mass%. ] To obtain a rubber reinforced resin.

Although it does not specifically limit as organosiloxane (a) used in order to obtain the said polyorganosiloxane (p1), For example, what contains the structural unit represented by following formula (5) etc. are mentioned.
R ¹ _n SiO _{(4-n) / 2} (5)
(Wherein, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 0 to 3.)

Examples of R ¹ include an aliphatic saturated hydrocarbon group such as a methyl group, an ethyl group, and a propyl group, an aliphatic unsaturated hydrocarbon group such as a vinyl group, an aromatic hydrocarbon group such as a phenyl group, and these groups. Examples thereof include a hydrocarbon group in which at least one of the hydrogen atoms contained is substituted with a halogen atom, a cyano group or the like.
The organosiloxane (a) may contain the structural unit represented by the formula (5) alone or in combination of two or more.

Further, the structure of the organosiloxane (a) is not particularly limited, and may be any of linear, branched and cyclic. In the present invention, an organosiloxane having a cyclic structure is preferred.
Examples of the cyclic structure organosiloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and trimethyltriphenylcyclotrisiloxane. Of these, hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane are preferred.

In addition, as said organosiloxane (a), the polyorganosiloxane condensed with the weight average molecular weight of the polystyrene conversion by gel permeation chromatography (GPC) (500-10,000) can also be used, for example. In this case, the molecular chain terminal may be blocked with a hydroxyl group, an alkoxyl group, a trimethylsilyl group, a dimethylvinylsilyl group, a methylphenylvinylsilyl group, a methyldiphenylsilyl group, or the like.
The organosiloxane (a) can be used alone or in combination of two or more.

On the other hand, the graft crossing agent (b) is a compound that acts as a graft active site when the vinyl (co) polymer formed from the vinyl monomer (m1) is chemically bonded to the polyorganosiloxane. Although not particularly limited, the following compounds [i] to [iv] and the like can be mentioned.
[I] A compound having an unsaturated group represented by the following formula (1) and an alkoxysilyl group having 1 to 2 carbon atoms.
(In the formula, R ² is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)

[Ii] A compound containing a structural unit represented by the following formula (2).
(Wherein R ³ is a vinyl group or an allyl group, R ⁴ is a monovalent hydrocarbon group having 1 to 6 carbon atoms and having no aliphatic unsaturated group, and p is 1 And is an integer of 0 to 2. q is an integer of 0 to 2.)

[Iii] A compound containing a structural unit represented by the following formula (3).
(In the formula, R ⁵ has 1 to 18 carbon atoms and is a divalent or trivalent aliphatic saturated hydrocarbon group, and R ⁶ has 1 to 6 carbon atoms and has an aliphatic unsaturated group. Not a monovalent hydrocarbon group, and r is an integer of 0 to 2.)

[Iv] A compound containing a structural unit represented by the following formula (4).
(In the formula, R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, s is an integer of 1 to 6, and t is an integer of 0 to 2.)

In the graft crossing agent of [i] above, the substituent R ² in the formula (1) is preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group.
Therefore, an example of the structural unit (5) having the unsaturated group represented by the above formula (1) and the alkoxysilyl group as the graft crossing agent of [i] is shown below.
(In the formula, R ⁸ has 0 to 6 carbon atoms and is a divalent or trivalent aliphatic saturated hydrocarbon group, R ⁹ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, u is an integer of 0-2.)

Examples of the graft crossing agent [i] include p-vinylphenylmethyldimethoxysilane, [1- (4-vinylphenyl) ethyl] methyldimethoxysilane, [2- (4-vinylphenyl) ethyl] methyldimethoxysilane, 1 -(M-vinylphenyl) methyldimethylisopropoxysilane, 3- (p-vinylphenoxy) propylmethyldiethoxysilane, 3- (p-vinylbenzoyloxy) propylmethyldimethoxysilane, 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-isopropenylbenzoy Amino) propyl] phenyl dipropoxy silane, and the like. These can be used alone or in combination of two or more.
Of these, p-vinylphenylmethyldimethoxysilane, [1- (4-vinylphenyl) ethyl] methyldimethoxysilane, [2- (4-vinylphenyl) ethyl] methyldimethoxysilane, 3- (p-vinyl) Benzyloxy) propylmethyldimethoxysilane is preferred, and p-vinylphenylmethyldimethoxysilane, [1- (4-vinylphenyl) ethyl] methyldimethoxysilane, [2- (4-vinylphenyl) ethyl] methyldimethoxy Silane is preferred.
The polyorganosiloxane using the graft crossing agent [i] above can be polymerized in the presence of a vinyl monomer to obtain a graft polymer having a high graft ratio.

Examples of the graft crossing agent [ii] include vinylmethyldimethoxysilane, tetravinyltetramethylcyclosiloxane, and allylmethyldimethoxysilane. These can be used alone or in combination of two or more.
Examples of the graft crossing agent [iii] include γ-mercaptopropylmethyldimethoxysilane. These can be used alone or in combination of two or more.
In the graft crossing agent [iv], R ⁷ in the formula (4) is preferably a methyl group, an ethyl group, a propyl group, or a phenyl group. Examples of the graft crossing agent [iv] include γ-methacryloxypropylmethyldimethoxysilane. These can be used alone or in combination of two or more.

  Of the graft crossing agents [i] to [iv], the graft crossing agent [i] is preferable. The graft crossing agents [i] to [iv] may be used in any combination.

  The organosiloxane (a) and the graft crossing agent (b) used for the cocondensation are cocondensed at the following ratio in order to obtain a polyorganosiloxane having a small particle size. That is, when the total of these is 100% by mass, it is 90 to 99.8% by mass / 10 to 0.2% by mass, preferably 95 to 99.5% by mass / 5 to 0.5% by mass. Preferably it is 97-98.5 mass% / 3-1.5 mass%. When the amount of the organosiloxane (a) used is less than 90% by mass (when the amount of the graft crossing agent (b) used exceeds 10% by mass), the rubber elasticity may be lost and the impact resistance may be lowered. Moreover, when the usage-amount of organosiloxane (a) exceeds 99.8 mass% (when the usage-amount of a graft crossing agent (b) is less than 0.2 mass%), the obtained graft polymer is sufficient. The graft ratio may not be obtained, and sufficient slidability and impact resistance may not be obtained.

  In the case of cocondensation of the organosiloxane (a) and the graft crossing agent (b), a crosslinking agent may be used in combination. Examples of the crosslinking agent include trifunctional crosslinking agents such as methyltrimethoxysilane, phenyltrimethoxysilane, and ethyltriethoxysilane; and tetrafunctional crosslinking agents such as tetraethoxysilane. The amount of the crosslinking agent used is usually 10% by mass or less, preferably 5% by mass or less, based on the total amount of the organosiloxane (a) and the graft crossing agent (b).

  The specific method of cocondensation of organosiloxane (a) and graft crossing agent (b) is not particularly limited, and organosiloxane (a) and graft crossing agent (b) are condensed at a predetermined temperature in the presence of an emulsifier. It can be set as the method of making it react. This emulsifier acts not only as an emulsifier for organosiloxane (a) but also as a condensation initiator.

As the emulsifier, an anionic surfactant or a cationic surfactant can be used.
As an anionic surfactant, an alkylbenzenesulfonic acid having 10 to 24 carbon atoms and a salt thereof (R—C ₆ H ₄ SO ₃ M, where M is Na, K, NH _4, etc.), and having 8 to 8 carbon atoms. 20 alkanesulfonic acids and salts thereof (R—SO ₃ M, where M is Na, K, NH _4, etc.), α-olefin sulfonic acids having an α-olefin having 15 to 18 carbon atoms and salts thereof (R _{-CH = CH-CH 2 SO 3} M, where, M is Na, K, NH ₄ and the like) and the like. Moreover, these can be used individually by 1 type or in combination of 2 or more types. Among the above, alkylbenzenesulfonic acid and its salt are preferable.

Examples of the aliphatic substituted benzenesulfonic acid include hexylbenzenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid and the like. Examples of these salts include sodium hexylbenzenesulfonate, sodium octylbenzenesulfonate, ammonium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, and the like.
Examples of the aliphatic sulfonic acid salt include sodium lauryl sulfonate and sodium cetyl sulfonate.

Examples of the cationic surfactant include quaternary ammonium salts. These can be used alone or in combination of two or more.
Examples of the quaternary ammonium salt include lauryl trimethyl ammonium hydroxide, stearyl trimethyl ammonium hydroxide, dioctyl dimethyl ammonium hydroxide, distearyl dimethyl ammonium hydroxide, lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, chloride Examples include dicocoyl dimethyl ammonium, distearyl dimethyl ammonium chloride, benzalkonium chloride, and stearyl dimethyl benzyl ammonium chloride.

  As a method for producing a polyorganosiloxane emulsion containing a polyorganosiloxane having a small particle size, in particular, an organosiloxane (a) and a graft crossing agent (b) are sheared together with an emulsifier (c1) and the like using a homomixer or the like. By mixing, a raw material mixture containing fine droplets is formed, and then this raw material mixture is subjected to a condensation reaction while continuously or intermittently added to an aqueous solution of the emulsifier (c2) (hereinafter also referred to as “emulsifier aqueous solution”). It is preferable. In addition, the same thing may be used for an emulsifier (c1) and an emulsifier (c2), and a different thing may be used.

The amount of the emulsifier (c1) used in the raw material mixture is preferably 0.01 to 1.45 parts by mass, more preferably 0.1 to 1.0 parts by mass with respect to 100 parts by mass of the organosiloxane (a). Parts, more preferably 0.2 to 0.8 parts by mass. In general, this raw material mixture is preferably a mixture in which organosiloxane (a), graft crossing agent (b) and emulsifier (c1) are dispersed (dissolved) in water. In this raw material mixture, the concentrations of organosiloxane (a), graft crossing agent (b) and emulsifier (c1) are not particularly limited.
The preparation method of this raw material mixture is not particularly limited, and the organosiloxane (a), the graft crossing agent (b), the emulsifier (c1) and water may be charged all at once into the container and mixed, or the emulsifier (c1) May be dissolved in water, and organosiloxane (a) and graft crossing agent (b) may be added all at once, continuously or intermittently, or either one may be added first and mixed. In addition, the mixing temperature of these components is 60-100 degreeC normally, Preferably it is 70-90 degreeC.

  Moreover, the amount of the emulsifier (c2) used in the emulsifier aqueous solution is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, and still more preferably 3 to 100 parts by mass of the organosiloxane (a). -15 parts by mass. The concentration of the emulsifier (c2) in the aqueous solution is not particularly limited, but is usually 0.5 to 20% by mass, preferably 0.7 to 15% by mass, and more preferably 1.0 to 15% by mass.

  A specific method for producing a polyorganosiloxane emulsion containing a polyorganosiloxane having a small particle size includes a method of adding an emulsion of an organosiloxane (a) to an aqueous emulsifier solution. For example, 100 parts by mass of organosiloxane (a), 0.2 to 11 parts by mass of graft crossing agent (b), 0.01 to 1.45 parts by mass of emulsifier (c1) and 200 to 500 parts by mass of water are shear mixed. And a method of continuously or intermittently adding it to 50 to 300 parts by mass of an aqueous emulsifier (c2) solution having a concentration of 0.5 to 20% by mass.

  The total amount of the emulsifier used when producing the polyorganosiloxane emulsion is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, and further preferably 3 to 15 parts per 100 parts by mass of the organosiloxane (a). Part by mass.

The reaction temperature for carrying out the condensation reaction of the organosiloxane (a) and the grafting agent (b) is usually 60 to 100 ° C, preferably 70 to 90 ° C. After the addition of the raw material mixture to the aqueous emulsifier solution, when the desired degree of polymerization is reached, the mixture is neutralized with an acidic or basic substance to stop the condensation polymerization, thereby reducing the polyorganosiloxane with a small particle size A polyorganosiloxane emulsion containing can be obtained.
Examples of the acidic substance include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, and the like. Examples of the basic substance include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, triethanolamine, triethylamine and the like. These can be used alone or in combination of two or more.

  The volume average particle diameter of the polyorganosiloxane is 4 to 60 nm, preferably 4 to 55 nm, more preferably 4 to 50 nm, and particularly preferably 4 to 48 nm. When the volume average particle diameter exceeds 60 nm, the total light reflectance and the diffuse reflectance are lowered, the colorability (blackness) is inferior, and the dynamic friction coefficient and the specific wear amount tend to increase. Therefore, by including such a small particle size polyorganosiloxane, this rubber-reinforced resin is used, and since the linear expansion coefficient is small and the molding shrinkage rate is small, the dimensional accuracy is high, the brightness is high, the coloration property, the sliding property is high. A molded article excellent in mobility, impact resistance and weather resistance can be easily obtained. The volume average particle diameter of the polyorganosiloxane is a volume average particle diameter measured by a dynamic light scattering method.

  The weight average molecular weight of the polyorganosiloxane is preferably 30,000 to 1,000,000, more preferably 50,000 to 500,000, when the organosiloxane (a) and the graft crossing agent (b) are used. . Moreover, when it consists of an organosiloxane (a), a graft crossing agent (b), and the said crosslinking agent, Preferably it is 30,000-1,000,000, More preferably, it is 50,000-500,000. is there. In addition, the said weight average molecular weight is a polystyrene conversion value by GPC.

  The rubber-reinforced resin [A1] of the present invention comprises 99 to 30% by mass of a vinyl monomer (m1) containing an aromatic vinyl compound in the presence of 1 to 70% by mass of the polyorganosiloxane (p1). The sum total of a component (p1) and a component (m1) is 100 mass%. ], The vinyl monomer (m1) may be any one containing an aromatic vinyl compound. That is, the vinyl monomer (m1) may be one or more aromatic vinyl compounds, or a combination of one or more aromatic vinyl compounds and one or more other vinyl compounds. It may be.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-hydroxystyrene, α-ethylstyrene, methyl-α-methylstyrene, dimethylstyrene, bromo. Examples thereof include styrene, dibromostyrene, tribromostyrene, sodium styrenesulfonate, and the like. These can be used alone or in combination of two or more. Of these, styrene, p-methylstyrene and α-methylstyrene are preferred.

  The usage-amount of the said aromatic vinyl compound is 5-100 mass% normally with respect to the said vinylic monomer (m1) whole quantity (100 mass%). In addition, this aromatic vinyl compound can be used in combination with other vinyl compounds depending on the purpose, application, etc., and the use ratio can be diversified. Therefore, the ratio of the aromatic vinyl compound used is preferably 50 to 95% by mass, more preferably 55 to 90% by mass. When other vinyl compounds are mainly used, the use ratio of the aromatic vinyl compound is preferably 5% by mass or more and less than 50% by mass, more preferably 10 to 45% by mass.

  Examples of other vinyl compounds include vinyl cyanide compounds, (meth) acrylic acid esters, maleimide compounds, and functional group-containing unsaturated compounds. Chemical resistance is imparted by using a vinyl cyanide compound. By using (meth) acrylic acid ester, transparency is imparted and colorability is improved. By using a maleimide compound, heat resistance is imparted. Moreover, compatibility can be improved when it mixes with other resin etc. by using a functional group containing unsaturated compound.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. These can be used alone or in combination of two or more. Of these, acrylonitrile is preferred.
The proportion of the vinyl cyanide compound used is preferably 1 to 60% by mass, more preferably 5 to 50% by mass, based on the total amount of the vinyl monomer (m1).

(Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Sec-butyl acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, (meth ) N-octyl acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate Etc. These can be used alone or in combination of two or more. Of these, methyl methacrylate and n-butyl acrylate are preferred.
The use ratio in the case of using the (meth) acrylic acid ester is preferably 1 to 90% by mass, more preferably 5 to 80% by mass, based on the total amount of the vinyl monomer (m1).

As maleimide compounds, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) ) Maleimide, N- (2,6-diethylphenyl) maleimide, N- (4-carboxyphenyl) maleimide, N- (4-hydroxyphenyl) maleimide and the like. These can be used alone or in combination of two or more. Of these, maleimide, N-phenylmaleimide and N-cyclohexylmaleimide are preferred. In order to introduce a maleimide unit, a method of (co) polymerizing maleic anhydride and then imidizing it may be used.
The use ratio in the case of using the maleimide compound is preferably 1 to 60% by mass, more preferably 5 to 50% by mass, based on the total amount of the vinyl monomer (m1).

Examples of the functional group-containing unsaturated compound include acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; (meth) acrylic acid esters having a functional group such as an epoxy group, a hydroxyl group and an amino group. . These can be used alone or in combination of two or more.
The use ratio in the case of using the functional group-containing unsaturated compound is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, based on the total amount of the vinyl monomer (m1). is there.

As the vinyl monomer (m1), preferred combinations when an aromatic vinyl compound and another vinyl compound are used in combination are shown below. In addition, these usage rates are not particularly limited.
(1) aromatic vinyl compound / vinyl cyanide compound (2) aromatic vinyl compound / (meth) acrylic acid ester (3) aromatic vinyl compound / vinyl cyanide compound / (meth) acrylic acid ester (4) aromatic Vinyl compounds / maleimide compounds (5) aromatic vinyl compounds / vinyl cyanide compounds / maleimide compounds (6) aromatic vinyl compounds / (meth) acrylic acid esters / maleimide compounds (7) aromatic vinyl compounds / cyanation Vinyl compounds / (meth) acrylic acid esters / maleimide compounds

  The use ratio of the polyorganosiloxane (p1) and the vinyl monomer (m1) polymerized in the presence thereof is 1 to 70% by mass / 99 to 30% by mass when the total of these is 100% by mass. %, Preferably 5-60 mass% / 95-40 mass%, more preferably 10-30 mass% / 90-70 mass%. When the amount of the polyorganosiloxane (p1) used is too large, the fluidity is not sufficient when the rubber-reinforced resin or rubber-reinforced resin composition obtained using the polyorganosiloxane (p1) is processed by injection molding or the like. The appearance of the resulting molded product may be poor. On the other hand, if the amount is too small, the impact resistance of the obtained molded product may be insufficient.

  The method for producing the rubber-reinforced resin [A1] of the present invention is not particularly limited, but a method by radical polymerization is preferred. Moreover, although emulsion polymerization, solution polymerization, etc. can be applied for the polymerization method, emulsion polymerization is preferable.

When the rubber-reinforced resin [A1] of the present invention is produced by emulsion polymerization, a polymerization initiator, an emulsifier, a chain transfer agent, water and the like are used.
The polymerization initiator includes an oxidizing agent composed of organic hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, a sugar-containing iron pyrophosphate formulation, a sulfoxylate formulation, and a sugar-containing pyrolin. Redox initiators in combination with reducing agents such as mixed prescriptions such as iron acid prescription / sulfoxylate prescription; persulfates such as potassium persulfate and ammonium persulfate; azobisisobutyronitrile, dimethyl-2,2 Examples include azo compounds such as' -azobisisobutyrate and 2-carbamoylazaisobutyronitrile; organic peroxides such as benzoyl peroxide and lauroyl peroxide. Of these, redox initiators are preferred.
The usage-amount of a polymerization initiator is 0.05-5 mass parts normally with respect to 100 mass parts of vinyl-type monomers (m1) used, Preferably it is 0.1-3 mass parts.

In the case of production by emulsion polymerization, when a polyorganosiloxane emulsion containing the polyorganosiloxane (p1) is used as it is, the polyorganosiloxane emulsion may be acidic. In such a case, since the polymerization initiator may hardly act, it is preferable to adjust the pH to 8 to 11 with a basic substance in advance.
Examples of the basic substance include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, triethanolamine, triethylamine and the like. These can be used alone or in combination of two or more.

Examples of the emulsifier include anionic emulsifiers such as potassium oleate and potassium rosinate; and nonionic emulsifiers such as polyoxyethylene alkyl ester and polyoxyethylene alkyl allyl ether. These can be used alone or in combination of two or more.
The usage-amount of an emulsifier is about 0.5-5 mass parts normally with respect to 100 mass parts of vinyl-type monomers (m1) used.

Examples of chain transfer agents include mercaptans such as t-dodecyl mercaptan, octyl mercaptan, n-tetradecyl mercaptan, n-hexyl mercaptan; halogen compounds such as carbon tetrachloride and ethylene bromide; terpinolene, α-methylstyrene Dimer etc. are mentioned. These can be used alone or in combination of two or more.
The usage-amount of a chain transfer agent is about 0.02-1 mass part normally with respect to 100 mass parts of vinyl-type monomers (m1) used.

In addition, when manufacturing by emulsion polymerization, you may use various electrolytes, a pH adjuster, etc. together as needed other than a polymerization initiator, an emulsifier, a chain transfer agent, etc.
Moreover, the usage-amount of water is 100-500 mass parts normally with respect to 100 mass parts of vinylic monomers (m1).
The polymerization temperature during the emulsion polymerization is usually 5 to 100 ° C, preferably 50 to 90 ° C. The polymerization time is usually 0.1 to 10 hours.

  A rubber containing a grafted polyorganosiloxane obtained by graft polymerization of a vinyl monomer (m1) to a polyorganosiloxane (p1) after emulsion polymerization, and a (co) polymer of the vinyl monomer (m1). An emulsion of reinforced resin is obtained. The rubber reinforced resin itself is obtained as a coagulated product by adding a coagulant to this emulsion. Thereafter, the solidified product is purified by washing with water and drying, and is usually obtained in a powder form. Examples of the coagulant include inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and lactic acid.

  The graft ratio (mass ratio of the monomer component grafted to the polyorganosiloxane (p1)) of the rubber-reinforced resin [A1] of the present invention is preferably 10% or more, more preferably 20% or more, and still more preferably 30 to 120%. When the graft ratio is less than 10%, molding shrinkage of a molded product obtained using the rubber-reinforced resin [A1] or a molded product obtained using a composition containing the rubber-reinforced resin [A1] may increase. In addition, appearance and impact resistance may deteriorate.

The method for measuring the graft ratio is as follows.
1 g of rubber reinforced resin is collected and weighed accurately, and this is put into 20 ml of acetone. After shaking for 10 hours, it is separated into a soluble part and an insoluble part using a centrifuge (rotation speed: 23,000 rpm). Thereafter, the insoluble matter is collected and dried by a vacuum dryer (the mass of the insoluble matter is X gram). On the other hand, the amount of rubber (R gram) in X grams of insoluble matter is calculated from the monomer component used for polymerization and the polymerization conversion rate, and the graft ratio is calculated from the following formula.
Graft rate (%) = [(X−R) / R] × 100

Further, the intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the acetone-soluble component of the rubber-reinforced resin [A1] of the present invention is preferably 0.2 to 0.8 dl / g, more preferably 0.8. It is 3-0.7 dl / g, Most preferably, it is 0.4-0.6 dl / g. If the intrinsic viscosity [η] is too large, the fluidity of the rubber-reinforced resin [A1] of the present invention or a composition containing the same may be reduced. On the other hand, if it is too small, the rubber-reinforced resin of the present invention [A1] In some cases, the impact strength of the molded product obtained using the above is not sufficient.
The graft ratio (%) and the intrinsic viscosity [η] are the type or amount of the graft crossing agent (b) used in the production of the polyorganosiloxane (p1), or the production of the rubber-reinforced resin [A1]. It can be easily controlled by appropriately selecting the amount of polyorganosiloxane (p1) used sometimes, polymerization initiator, chain transfer agent, emulsifier, type or amount of organic solvent, polymerization temperature, polymerization method, and the like.

  Another rubber-reinforced resin of the present invention (hereinafter also referred to as “rubber-reinforced resin [A2]”) is a vinyl-based monomer containing an aromatic vinyl compound in the presence of 1 to 70% by mass of polyorganosiloxane (p2). 99 to 30% by mass of the monomer (m2) [However, the total of the component (p2) and the component (m2) is 100% by mass. ] Is a rubber-reinforced resin containing a grafted polyorganosiloxane obtained by polymerizing the polymer, wherein the grafted polyorganosiloxane has a number average particle diameter of 4 to 65 nm.

The polyorganosiloxane (p2) is not particularly limited, and its configuration, molecular weight and the like are not particularly limited, but those having a volume average particle diameter of 4 to 60 nm are usually used. In the present invention, the polyorganosiloxane used in the rubber-reinforced resin [A1] of the present invention can be used as it is.
The vinyl monomer (m2) that is polymerized in the presence of the polyorganosiloxane (p2) may be any monomer that contains an aromatic vinyl compound, and is exemplified as the vinyl monomer (m1). Can be used in preferred amounts. Furthermore, the proportions of the polyorganosiloxane (p2) and the vinyl monomer (m2) used can be the same as in the rubber-reinforced resin [A1].

The production method of the rubber-reinforced resin [A2] of the present invention, the graft ratio of the grafted polyorganosiloxane, the intrinsic viscosity of the acetone-soluble component, and the like can be the same as those of the rubber-reinforced resin [A1].
The number average particle diameter of the grafted polyorganosiloxane contained in the rubber-reinforced resin [A2] of the present invention is 4 to 65 nm, preferably 9 to 60 nm, more preferably 15 to 55 nm, and particularly preferably 15 to 48 nm. . When the number average particle diameter exceeds 65 nm, when the rubber-reinforced resin [A2] of the present invention or a composition containing the same is used, dimensional accuracy, colorability, brightness, and the like may decrease. The number average particle size of the grafted polyorganosiloxane is a number average particle size measured with a transmission electron microscope.

  The rubber reinforced resin (rubber reinforced resins [A1] and [A2]) of the present invention can be used in combination with other components such as a polymer and various additives to form a thermoplastic resin composition.

2. Rubber Reinforced Resin Composition The rubber reinforced resin composition of the present invention comprises the above rubber reinforced resin [A1] or [A2] (hereinafter also referred to as rubber reinforced resin [A]) and another thermoplastic polymer (hereinafter referred to as “rubber reinforced resin”). Polyorganosiloxane (p1) used for forming rubber-reinforced resin [A1] or polyorganosiloxane used for forming rubber-reinforced resin [A2] Content of (p2) is 1-40 mass% with respect to the whole this composition, It is characterized by the above-mentioned.

  The thermoplastic polymer [B] may be a resin or rubber (elastomer). Specifically, styrene / acrylonitrile copolymer, styrene / (meth) acrylate ester copolymer, acrylonitrile / styrene / butyl acrylate copolymer, acrylonitrile / styrene / butadiene copolymer, methyl methacrylate / butadiene / Styrene copolymer, styrene (co) polymer such as polystyrene; polybutadiene, polyisoprene, styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, ethylene / propylene copolymer, ethylene / propylene / non-conjugated diene copolymer Polymer, ethylene / butene-1 copolymer, ethylene / butene-1 / non-conjugated diene copolymer, isobutylene / isoprene copolymer, styrene / butadiene / styrene block copolymer, styrene / butadiene / styrene radial teleblock In the presence of rubber polymers such as polymers, styrene / isoprene / styrene block copolymers, hydrogenated diene (block, random and homo) polymers such as SEBS, polyurethane rubber, acrylic rubber, silicone rubber, etc. Rubber-reinforced polymers such as ABS resins and AES resins obtained by polymerizing vinyl monomers such as aromatic vinyl compounds; polyethylene, polypropylene, ionomers, ethylene / vinyl acetate copolymers, ethylene / vinyl alcohol copolymers, Olefin polymers such as cyclic olefin copolymer and chlorinated polyethylene; Polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; Polycarbonate; Polyarylate; Polyacetal; Polyamide 6, Polyamide 6,6, Polyamide 6,1 Polyamides such as polytetrafluoroethylene and polyvinylidene fluoride; polyvinyl acetate; polyvinyl alcohol; polyvinyl ether; polyvinyl butyral; polyvinyl chloride, vinyl chloride such as ethylene / vinyl chloride polymer and polyvinylidene chloride Resin; Acrylic resin such as (co) polymer using one or more of (meth) acrylic acid ester such as polymethyl methacrylate (PMMA); polyphenylene ether; polyphenylene sulfide; liquid crystal polymer; polyether ketone, poly Examples thereof include ketone resins such as ether ether ketone; sulfone resins such as polysulfone and polyethersulfone; polyethylene oxide; phenoxy resin; biodegradable plastics and the like. These can be used alone or in combination of two or more. Of these, styrenic (co) polymers, rubber reinforced polymers and polycarbonates are preferred, styrenic (co) polymers and / or rubber reinforced polymers and polycarbonates in combination, and More preferably, the polycarbonate is used alone.

  As the styrene-based (co) polymer, a styrene / acrylonitrile copolymer is particularly preferable. The preferable composition ratio (mass%) of the styrene unit and the acrylonitrile unit in the styrene / acrylonitrile copolymer is 95 to 55 mass% and 5 to 45 mass%, more preferably 85 to 65 mass% and 15 to 35 mass%. %.

Examples of the rubber-reinforced polymer include polybutadiene, butadiene / styrene copolymer, ethylene / propylene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene / butene-1 / copolymer, ethylene / butene. -1. A rubber-reinforced polymer obtained by polymerizing a vinyl monomer such as an aromatic vinyl compound in the presence of a non-conjugated diene copolymer, an acrylic rubber, a hydrogenated diene rubber, or the like is particularly preferable.
As the vinyl monomer, the vinyl monomer (m1) used in the production of the rubber-reinforced resin [A1] can be applied. In addition to the aromatic vinyl compound, a vinyl cyanide compound, (meth) acrylic Acid esters, maleimide compounds, functional group-containing unsaturated compounds, and the like can be used. Preferred combinations are also the same as in the case of the vinyl monomer (m1).

The polycarbonate is not particularly limited as long as it has a carbonate bond in the main chain, and may be an aromatic polycarbonate or an aliphatic polycarbonate. These can be used individually by 1 type or in combination of 2 or more types. In the present invention, an aromatic polycarbonate containing an aromatic ring is preferable, and examples thereof include an aromatic polycarbonate and an aliphatic / aromatic copolymer polycarbonate.
As said aromatic polycarbonate, what is obtained by reaction of a dihydroxyaryl compound and phosgene (phosgene method), what is obtained by transesterification of a dihydroxyaryl compound and diphenyl carbonate (transesterification method), etc. can be used. .

  Here, as the dihydroxyaryl compound, bis (4-hydroxyphenyl) methane, 1,1′-bis (4-hydroxyphenyl) ethane, 2,2′-bis (4-hydroxyphenyl) propane, 2,2 ′ -Bis (4-hydroxyphenyl) butane, 2,2'-bis (4-hydroxyphenyl) octane, 2,2'-bis (4-hydroxyphenyl) phenylmethane, 2,2'-bis (4-hydroxy- 3-methylphenyl) propane, 2,2′-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2′-bis (4-hydroxy-3-bromophenyl) propane, 2,2′- Bis (4-hydroxy-3,5-dichlorophenyl) propane, 1,1′-bis (4-hydroxyphenyl) cyclopentane, 1,1′-bis (4 Hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 4,4′-dihydroxyphenyl sulfide, 4,4′-dihydroxyphenyl sulfide, 4,4 ′ -Dihydroxy-3,3'-dimethylphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxyphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4 ' -Dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone, hydroquinone, resorcin and the like. These can be used alone or in combination of two or more. Of these, 2,2'-bis (4-hydroxyphenyl) propane is preferred.

  The polycarbonate is a branched polycarbonate obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, a polyester carbonate obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, A copolymer polycarbonate copolymerized with a functional alcohol (including an alicyclic group), a polyester carbonate copolymerized with a bifunctional carboxylic acid and a bifunctional alcohol, and the like can be used.

The viscosity average molecular weight of the polycarbonate is preferably 13,000 to 32,000, more preferably 17,000 to 31,000, and particularly preferably 18,000 to 30,000. In the present invention, two or more kinds of polycarbonates having different viscosity average molecular weights can be used in combination within the above range.
If the viscosity average molecular weight of the polycarbonate is too large, the fluidity of the rubber-reinforced resin composition of the present invention may be reduced. On the other hand, if it is too small, the molded article obtained using the rubber-reinforced resin composition of the present invention. The impact resistance may be reduced.

In addition, the measuring method of a viscosity average molecular weight is as follows. That is, first, 0.7 g of polycarbonate is dissolved in 100 ml of methylene chloride, and the specific viscosity (η _SP ) at 20 ° C. is determined. Next, using this η _SP , [η] is calculated by the equation (6), and further, using this [η], the viscosity average molecular weight is calculated by the equation (7).
[Η] = [(η _SP × 1.12 + 1) ^1/2 −1] /0.56C (6)
(However, C is the concentration of methylene chloride (0.7 / 100).)
Viscosity average molecular weight = ([η] × 8,130) ^1.205 (7)

Although the content rate of the rubber reinforced resin [A] and the thermoplastic polymer [B] contained in the rubber reinforced resin composition of the present invention is not particularly limited, the content of the polyorganosiloxane (p1) or the polyorganosiloxane (p2) The amount is 1 to 40% by mass, preferably 3 to 30% by mass, and more preferably 5 to 20% by mass with respect to the entire composition.
A preferable content ratio of the rubber-reinforced resin [A] and the thermoplastic polymer [B] is 1 to 99% by mass and 99 to 1% by mass, more preferably 100% by mass. It is 5-85 mass% and 95-15 mass%, More preferably, it is 15-85 mass% and 85-15 mass%.

  The rubber reinforced resin [A] and the rubber reinforced resin composition of the present invention may contain an additive. These additives include compatibilizers, antioxidants, anti-aging agents, UV absorbers, heat stabilizers, plasticizers, lubricants, antibacterial agents, fillers, flame retardants, light proofing agents, and colorants (pigments and dyes). And silicone oil.

When the rubber-reinforced resin [A] and the thermoplastic polymer [B] are mixed, if the compatibility between the two is not sufficient, for example, a method of adding a compatibilizer, a specific rubber-reinforced resin [A] is used. It can be improved by a method or the like.
Examples of the compatibilizer include a functional group-containing copolymer that is a copolymer of the functional group-containing unsaturated compound and another monomer. As this functional group-containing copolymer, styrene / glycidyl methacrylate copolymer, styrene / maleic anhydride copolymer, styrene / methacrylic acid copolymer, styrene / acrylonitrile / methacrylic acid copolymer, and the like, Copolymers obtained by copolymerizing the above functional group-containing unsaturated compounds and, if necessary, other vinyl monomers copolymerizable therewith; ethylene / glycidyl methacrylate copolymers, ethylene / glycidyl Copolymers obtained by copolymerizing ethylene, the above functional group-containing unsaturated compounds, and other vinyl monomers that can be copolymerized with these, if necessary, such as methacrylate-vinyl acetate copolymers Examples include coalescence.
Further, in the presence of an ethylene copolymer, other polymers such as poly (meth) acrylic acid alkyl ester, polystyrene, styrene / acrylonitrile copolymer, styrene / (meth) acrylic acid alkyl ester copolymer, etc. A polymer obtained by grafting a polymer polymerized using a vinyl monomer capable of radical polymerization can also be used.
These can be used alone or in combination of two or more. In addition, since each said polymer is corresponded to the said thermoplastic polymer [B], the compounding quantity in the case of using as a compatibilizing agent is 100 mass in total of rubber-reinforced resin [A] and a thermoplastic polymer [B]. Among the parts, it is preferably 0.1 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass. If the content of the compatibilizer is too small, the compatibility improving effect may not be obtained. On the other hand, if the amount is too large, the molding processability and the heat deterioration resistance may decrease.
Moreover, as a method of using a specific rubber-reinforced resin [A], a rubber-reinforced resin [A] obtained by using a functional group-containing unsaturated compound in the vinyl monomer (m1) or (m2) is used. This method is used. The amount of the functional group-containing unsaturated compound used is the same as described above.

  Examples of the antioxidant include hindered amines, hydroquinones, hindered phenols, and sulfur-containing compounds. These can be used alone or in combination of two or more. The amount of the antioxidant used is preferably 0 with respect to 100 parts by mass of the rubber-reinforced resin [A] or 100 parts by mass of the rubber-reinforced resin [A] and the thermoplastic polymer [B]. .1 to 5 parts by mass, more preferably 0.5 to 2 parts by mass.

  Anti-aging agents include naphthylamine, diphenylamine, p-phenylenediamine, quinoline, hydroquinone derivatives, monophenol, bisphenol, trisphenol, polyphenol, thiobisphenol, hindered phenol, phosphorous acid Examples include ester compounds. These can be used alone or in combination of two or more. The blending amount in the case of using this antioxidant is preferably 0 with respect to 100 parts by mass of the rubber reinforced resin [A] or 100 parts by mass of the rubber reinforced resin [A] and the thermoplastic polymer [B]. .1 to 5 parts by mass, more preferably 0.5 to 2 parts by mass.

  Examples of the ultraviolet absorber include benzophenones, benzotriazoles, salicylic acid esters, metal complex salts and the like. These can be used alone or in combination of two or more. The blending amount when this ultraviolet absorber is used is preferably 0 with respect to 100 parts by mass of the rubber-reinforced resin [A] or 100 parts by mass of the rubber-reinforced resin [A] and the thermoplastic polymer [B]. .1 to 5 parts by mass, more preferably 0.5 to 2 parts by mass.

  Examples of the heat stabilizer include aliphatic carboxylates such as salts of sodium, calcium, aluminum, barium, magnesium, manganese, iron, zinc, lead, silver, copper and the like such as lactic acid and hydroxybutyric acid. These can be used alone or in combination of two or more. The blending amount in the case of using this heat stabilizer is preferably 0 with respect to 100 parts by mass of the rubber-reinforced resin [A] or 100 parts by mass of the rubber-reinforced resin [A] and the thermoplastic polymer [B]. .1 to 5 parts by mass, more preferably 0.5 to 2 parts by mass.

  Examples of the plasticizer include aliphatic dibasic acid esters, phthalic acid esters, hydroxy polyvalent carboxylic acid esters, polyester plasticizers, fatty acid esters, and epoxy plasticizers. These can be used alone or in combination of two or more. When this plasticizer is used, the blending amount is preferably 0.000 parts by weight relative to 100 parts by weight of the rubber-reinforced resin [A] or 100 parts by weight of the rubber-reinforced resin [A] and the thermoplastic polymer [B]. 1 to 5 parts by mass, more preferably 0.5 to 2 parts by mass.

  As the lubricant, fatty acid ester, hydrocarbon resin, paraffin, higher fatty acid, oxy fatty acid, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid polyglycol ester, aliphatic alcohol , Polyhydric alcohol, polyglycol, polyglycerol, metal soap, modified silicone and the like. These can be used alone or in combination of two or more. The blending amount when this lubricant is used is preferably 0.1 with respect to 100 parts by mass of the rubber reinforced resin [A] or 100 parts by mass of the rubber reinforced resin [A] and the thermoplastic polymer [B]. -10 parts by mass, more preferably 0.5-5 parts by mass.

  Antibacterial agents include zeolite antibacterial agents, silica gel antibacterial agents, glass antibacterial agents, calcium phosphate antibacterial agents, zirconium phosphate antibacterial agents, silicate antibacterial agents, titanium oxide antibacterial agents, ceramic antibacterial agents, Inorganic antibacterial agents such as whisker antibacterial agents; formaldehyde releasing agents, halogenated aromatic compounds, road propargyl derivatives, thiocyanate compounds, isothiazolinone derivatives, trihalomethylthio compounds, quaternary ammonium salts, biguanide compounds, aldehydes, phenols, Any of organic antibacterial agents such as benzimidazole derivatives, pyridine oxide, carbanilide, diphenyl ether, carboxylic acid, and organometallic compounds, and natural antibacterial agents can be used. The blending amount in the case of using this antibacterial agent is preferably 0.00 with respect to 100 parts by mass of the rubber reinforced resin [A] or the total of 100 parts by mass of the rubber reinforced resin [A] and the thermoplastic polymer [B]. 1 to 5 parts by mass, more preferably 0.5 to 2 parts by mass.

  As a filler, any of an organic filler, an inorganic filler, and an organic-inorganic composite filler may be used. Glass fiber, carbon fiber, glass bead, carbon black, rock filler, glass flake, milled fiber, magnesium oxide, calcium carbonate, Examples include barium sulfate, talc, wollastonite, mica, molybdenum disulfide, zinc oxide whisker, calcium titanate whisker, and wood flour. These can be used alone or in combination of two or more. In addition, the fiber diameter and fiber length in the case of using a fibrous filler are not specifically limited. When this filler is used, the blending amount is preferably 0.1 parts per 100 parts by mass of the rubber reinforced resin [A] or 100 parts by mass of the rubber reinforced resin [A] and the thermoplastic polymer [B]. 1-30 mass parts, More preferably, it is 1-20 mass parts.

Examples of the flame retardant include organic flame retardants, inorganic flame retardants, and reactive flame retardants.
Examples of the organic flame retardant include brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, brominated bisphenol polycarbonate, brominated polystyrene, brominated crosslinked polystyrene, brominated bisphenol cyanurate resin, brominated polyphenylene ether, deca Halogen flame retardants such as bromodiphenyl oxide, tetrabromobisphenol A and oligomers thereof, brominated alkyltriazine compounds; trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, toxyl phosphate, tricyclohexyl phosphate, tri Phenyl phosphate, tricresyl phosphate, trixylenyl phosphate, Phosphoric esters such as rudiphenyl phosphate, dicresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, compounds obtained by modifying these with various substituents, condensed phosphate compounds, Phosphorus flame retardants such as phosphazene derivatives containing phosphorus element and nitrogen element; polytetrafluoroethylene and the like. These can be used alone or in combination of two or more.

Examples of the inorganic flame retardant include aluminum hydroxide, magnesium hydroxide, borax, zirconium-based, molybdenum-based, zinc stannate, guanidine salt, silicone-based, and phosphazene-based compounds. These can be used alone or in combination of two or more.
Examples of the reactive flame retardant include tetrabromobisphenol A, dibromophenol glycidyl ether, brominated aromatic triazine, tribromophenol, tetrabromophthalate, tetrachlorophthalic anhydride, dibromoneopentyl glycol, poly (pentabromobenzyl polyacrylate) ), Chlorendic acid (hett acid), chlorendic anhydride (hett acid anhydride), brominated phenol glycidyl ether, dibromocresyl glycidyl ether, and the like. These can be used alone or in combination of two or more.
The blending amount in the case of using this flame retardant is preferably 2 to 100 parts by mass of the rubber reinforced resin [A] or 100 parts by mass of the rubber reinforced resin [A] and the thermoplastic polymer [B] in total. 30 parts by mass, more preferably 5 to 25 parts by mass.

  In addition, when mix | blending a flame retardant, you may use a flame retardant adjuvant together. As this flame retardant auxiliary, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, antimony tartrate, antimony compounds, zinc borate, barium metaborate, hydrated alumina, zirconium oxide, Examples thereof include ammonium polyphosphate, tin oxide, and iron oxide. These can be used alone or in combination of two or more.

  The rubber-reinforced resin composition of the present invention can be obtained by putting each raw material component into various extruders, Banbury mixers, kneaders, rolls and the like and kneading them. A preferred kneading method is a method using a twin screw extruder. Further, when kneading the raw material components, the raw material components may be kneaded in a lump or may be kneaded by a multistage addition method.

  When both the rubber-reinforced resin [A] and the thermoplastic polymer [B] are produced by emulsion polymerization, the emulsions are mixed so that the content of the polyorganosiloxane becomes a predetermined ratio, The combined components can be co-coagulated to form a composite. Since this composite is a mixture of the rubber-reinforced resin [A] and the thermoplastic polymer [B] more uniformly, kneading for making the rubber-reinforced resin composition of the present invention more smoothly is performed. Can do.

  The rubber-reinforced resin or rubber-reinforced resin composition of the present invention is a molded product having a predetermined shape, and excellent colorability by a known method such as injection molding, sheet extrusion, film extrusion, vacuum molding, deformed shape, and foam molding. It can be set as the molded article which has. Various molded products may be film-like, sheet-like, linear, lump-like, etc., utilizing their excellent dimensional stability, slidability, impact resistance, weather resistance, etc., copying machines, facsimiles, computers OA equipment such as printers and remote controllers, vacuum cleaners, refrigerators, air conditioners, microwave ovens, audio appliances and other parts (tray, buttons, switches, display frames, etc.), exterior materials (housing, covers, etc.) Or it is suitable as containers, housings, cases, covers, etc. for cosmetics, daily necessities, foods, medical products, various nursing care products and the like.

  When a lamp housing used in a vehicle or the like is formed, a reflection layer that reflects the lamp light is usually provided in order to further increase the luminance of the lamp. As a method for forming the reflective layer, there are a method of forming a metal, an alloy or the like by vapor deposition or sputtering, a method of applying a reflective paint, or the like. However, undercoatless metalizing that can reduce VOC is becoming mainstream due to recent environmental problems. Even when the rubber-reinforced resin or rubber-reinforced resin composition of the present invention is formed into a molded product, it is difficult for fine irregularities to exist on the surface. High luminance light can be obtained by a lamp body formed by vapor deposition, sputtering or the like.

  Hereinafter, the present invention will be described more specifically with reference to examples. In the following description, parts and% are based on mass unless otherwise specified.

1. Production of polyorganosiloxane emulsion Production Example 1
First, 98 parts of octamethylcyclotetrasiloxane as an organosiloxane, 2 parts of γ-methacryloyloxypropyldimethoxysilane as a grafting agent, 0.67 parts of sodium dodecylbenzenesulfonate as an emulsifier, and 300 parts of ion-exchanged water Were stirred for 15 minutes using a homomixer (rotation speed: 10,000 rpm) to prepare a raw material mixture.
On the other hand, 10 parts of dodecylbenzenesulfonic acid as an emulsifier was dissolved in 90 parts of ion-exchanged water to obtain an emulsified solution.
Thereafter, the emulsified solution was brought to 85 ° C., and the raw material mixture was added dropwise over 4 hours while stirring. After the total amount was dropped, the mixture was further stirred for 1 hour, cooled to 5 ° C., and maintained for 24 hours to complete the condensation reaction. The polymerization conversion rate was 98%. Subsequently, it neutralized using sodium carbonate aqueous solution, it was set to pH 7, and the polyorganosiloxane emulsion containing a polyorganosiloxane (p-1) particle | grain was obtained. The volume average particle diameter of the polyorganosiloxane (p-1) particles was measured by a light scattering method using a “laser particle size analyzer UPA-150 type” manufactured by Nikkiso Co., Ltd. and found to be 40 nm.

Production Example 2
A polyorganosiloxane emulsion containing polyorganosiloxane (p-2) particles was obtained by performing a condensation reaction in the same manner as in Production Example 1, except that the amount of sodium dodecylbenzenesulfonate was 0.64 part. The volume average particle diameter of the polyorganosiloxane (p-2) particles was 55 nm.

Production Example 3
A mixture of 98.5 parts of octamethylcyclotetrasiloxane and 1.5 parts of p-vinylphenylmethyldimethoxysilane is placed in 300 parts of an emulsified solution obtained by dissolving 2.0 parts of dodecylbenzenesulfonic acid in distilled water. The mixture was stirred for 3 minutes using a mixer (rotation speed: 10,000 rpm) to obtain an emulsified dispersion. This emulsified dispersion was transferred to a separable flask equipped with a condenser, a nitrogen gas inlet and a stirrer, and heated at 90 ° C. for 6 hours with stirring. Thereafter, the condensation reaction was completed by cooling to 5 ° C. and holding for 24 hours. The polymerization conversion rate was 98.0%. Subsequently, it neutralized using sodium carbonate aqueous solution, it was set to pH 7, and the polyorganosiloxane emulsion containing a polyorganosiloxane (p-3) particle | grain was obtained. The volume average particle diameter of the polyorganosiloxane (p-3) particles was 280 nm.

2. Production and Evaluation of Rubber Reinforced Resin [A] Example 1
A stirrer and a nitrogen atmosphere flask were charged with 40 parts of polyorganosiloxane (p-1) contained in the polyorganosiloxane emulsion obtained in Production Example 1, 15 parts of styrene, 5 parts of acrylonitrile, 0.542 potassium laurate. And 172 parts of ion exchange water were added and heated with stirring. When the temperature in the flask reached 55 ° C, 0.24 parts of ion-exchanged water, 0.2 parts of tetrasodium pyrophosphate, 0.25 parts of anhydrous crystalline glucose and 0.004 parts of ferrous sulfate heptahydrate And a solution of 0.54 parts of diisopropylbenzene peroxide were added to initiate polymerization (batch polymerization).
After the reaction for 1 hour, the temperature in the flask was set to 70 ° C., 30 parts of styrene, 10 parts of acrylonitrile, 0.064 parts of diisopropylbenzene hydroperoxide, 1.084 parts of potassium laurate, and 42 parts of ion-exchanged water. The mixture was added dropwise continuously over 4 hours and the reaction continued (increment polymerization). After the total amount was added, a solution in which 0.067 parts of tetrasodium pyrophosphate, 0.0833 parts of anhydrous crystalline glucose and 0.0013 parts of ferrous sulfate heptahydrate were dissolved in 2.74 parts of ion-exchanged water, and diisopropylbenzene The graft polymerization was completed by adding 0.064 part of hydroperoxide and further stirring for 1 hour. The polymerization conversion rate at this time was 98.0%.
Next, 1 part of a reaction product of p-cresol, dicyclopentadiene and isobutylene was added to the obtained emulsion as an anti-aging agent, and the temperature was raised to 100 ° C. while stirring. Then, it solidified using the magnesium sulfate aqueous solution with a density | concentration of 0.49%, and the powdery rubber reinforced resin [A-1] was obtained by isolate | separating, dehydrating, wash | cleaning (washing with water), and drying. This rubber-reinforced resin [A-1] had a graft ratio of 81.5% and an intrinsic viscosity [η] of 0.50 dl / g.
Furthermore, the number average particle diameter of the grafted polyorganosiloxane constituting the rubber-reinforced resin [A-1] was measured using a “transmission electron microscope H-7500 type” manufactured by Hitachi, Ltd. and found to be 45 nm. (See FIG. 1).

The graft ratio and intrinsic viscosity [η] were measured by the following methods.
(1) Graft rate 1 g of rubber-reinforced resin was sampled and weighed precisely, and this was put into 20 ml of acetone. After shaking for 10 hours, it was separated into soluble and insoluble using a centrifuge (rotation speed: 23,000 rpm). Thereafter, the insoluble matter was recovered and dried with a vacuum dryer (the mass of the insoluble matter was X gram). On the other hand, the rubber amount (R gram) in the insoluble matter X gram was calculated from the monomer component used for the polymerization and the polymerization conversion rate. The graft ratio was determined from the following formula.
Graft rate (%) = [(X−R) / R] × 100

(2) Intrinsic viscosity [η]
The acetone-soluble matter obtained during the measurement of the graft ratio was dried by a vacuum dryer and solidified. The obtained solid content was dissolved in methyl ethyl ketone, and the intrinsic viscosity [η] at a temperature of 30 ° C. was measured with an Ubbelohde viscometer.

Examples 2 and 3
According to the formulation shown in Table 1, rubber reinforced resins [A-2] and [A-3] were obtained in the same manner as in Example 1. The polymerization conversion ratio, graft ratio, intrinsic viscosity, and number average particle diameter of the grafted polyorganosiloxane are also shown in Table 1.

Comparative Example 1
A stirrer and a nitrogen atmosphere flask, 40 parts of polyorganosiloxane (p-3) contained in the polyorganosiloxane emulsion obtained in Production Example 3 above, 15 parts of styrene, 5 parts of acrylonitrile, 100 parts of ion-exchanged water, 1.5 parts of potassium oleate, 0.01 part of potassium hydroxide and 0.1 part of t-dodecyl mercaptan were added and heated in a nitrogen atmosphere with stirring. When the temperature in the flask reached 45 ° C., 0.1 part of sodium ethylenediaminetetraacetate, 0.003 part of ferrous sulfate, 0.2 part of sodium formaldehyde sulfoxylate dihydrate and 15 parts of ion-exchanged water An aqueous solution of an activator comprising 0.1 part of diisopropylbenzene hydroperoxide was added to initiate polymerization (batch polymerization).
After reacting for 1 hour, 30 parts of styrene, 10 parts of acrylonitrile, 50 parts of ion-exchanged water, 1 part of potassium oleate, 0.02 part of potassium hydroxide, 0.1 part of t-dodecyl mercaptan and diisopropylbenzene hydroperoxide 0.2 part of the mixture was added continuously over 3 hours and the reaction continued (incremental polymerization). After addition of the entire amount, the reaction was continued while stirring for another hour, and 0.2 part of 2,2-methylenebis (4-ethylene-6-t-butylphenol) was added to complete the graft polymerization. The polymerization conversion rate at this time was 98.7%.
Then, 1.5 parts of sulfuric acid was coagulated, and the solidified product was separated, dehydrated, washed (washed with water), and dried to obtain a powdery rubber-reinforced resin [A-4]. The graft ratio and intrinsic viscosity [η] of this rubber-reinforced resin [A-4] were measured in the same manner as in Example 1 and are shown in Table 1. Further, the number average particle diameter of the grafted polyorganosiloxane constituting the rubber-reinforced resin [A-4] was measured in the same manner as in Example 1 and found to be 290 nm (see FIG. 2).

3. Evaluation of Physical Properties of Rubber Reinforced Resin and Rubber Reinforced Resin Composition A rubber reinforced resin composition was produced using the rubber reinforced resin [A] obtained above and the following thermoplastic polymer [B].
(1) Thermoplastic polymer [B-1]
75 parts of styrene, 25 parts of acrylonitrile, 1.5 parts of potassium oleate, 1 part of potassium persulfate and 100 parts of ion-exchanged water are put into a reaction vessel, emulsion polymerized at 70 ° C., and then solidified using 2 parts of sulfuric acid. The solidified product was dehydrated, washed with water, and dried to obtain a powdery acrylonitrile / styrene copolymer (thermoplastic polymer [B-1]) (see Table 2).

(2) Thermoplastic polymer [B-2]
In a 7-liter glass flask equipped with a stirrer, a polybutadiene rubber latex having a volume average particle size of 290 nm and a gel content of 85% (in terms of solid content), 43.8 parts of styrene, 16.2 parts of acrylonitrile, ion exchange 250 parts of water, 0.3 part of dodecyl mercaptan and 2 parts of potassium oleate were added and heated in a nitrogen atmosphere with stirring. While controlling the jacket at 70 ° C., when the temperature in the flask reached 50 ° C., 0.3 part of potassium persulfate dissolved in 4 parts of ion-exchanged water and 0% sodium sulfite dissolved in 1 part of ion-exchanged water .1 part was added and graft polymerization was carried out for 3 hours. Thereafter, sulfuric acid or calcium chloride (a ratio of 2 parts with respect to 100 parts of the polymer) was added to the obtained styrenic polymer emulsion and coagulated at 90 ° C. Next, the solidified product was separated, washed with water, dehydrated, and dried to obtain a rubber-reinforced styrene-based resin (thermoplastic polymer [B-2]) containing grafted polybutadiene (see Table 2).

(3) Thermoplastic polymer [B-3]
Polycarbonate (trade name “Iupilon S-3000”, manufactured by Mitsubishi Gas Chemical Company) was used.

Example 4
The rubber-reinforced resin [A-1] obtained in Example 1 and the thermoplastic polymer [B-1] were mixed in a Henschel mixer at the ratio shown in Table 3, and this mixture was mixed with an inner diameter of 50 mm. Using an extruder, the mixture was melt-kneaded at a temperature of 200 to 230 ° C. to produce pellets. After drying the obtained pellets at 80 ° C., using Toshiba Machine's “Injection Molding Machine IS-80A Model”, molding was performed at a temperature of 220 ° C. to produce test pieces for evaluation, linear expansion coefficient, molding The shrinkage rate, the dynamic friction coefficient, the specific wear amount, the Izod impact strength, the weather resistance, the luminance (total light reflectance and diffuse reflectance), and the colorability (blackness) were evaluated. The results are shown in Table 3.

In addition, the evaluation method in each said item is as follows.
(1) Linear expansion coefficient Izod impact strength test specimen (length 63.5 mm, width 12.7 mm, thickness 6.35 mm) according to ASTM-D256, the elongation when the temperature was raised from 23 ° C to 60 ° C, The measurement was performed using “Laser Scan Micrometer Model 1000” manufactured by Mitoyo Seisakusho, and the linear expansion coefficient was obtained from the elongation.
(2) Mold Shrinkage Rate ASTM No. 1 dumbbell test pieces were produced by injection molding, and the mold shrinkage rate was calculated based on the ratio to the mold dimensions.
(3) Slidability The slidability was evaluated based on the dynamic friction coefficient and the specific wear amount.
The coefficient of dynamic friction μ between a hollow cylindrical specimen having an outer diameter of 25.6 mm, an inner diameter of 20.0 mm and a height of 15.0 mm and a counterpart material made of steel of the same shape and size (S45C) Using a sliding tester, the following measurement conditions and calculation formula were used.
<Measurement conditions>
Load: 5kg
Traveling speed: 3.75 cm / sec Temperature: 23 ° C
Humidity; 50%
<Calculation formula>
μ = [3 × F × R × (r ₂ ² −r ₁ ² )] / [P × (r ₂ ³ −r ₁ ³ )]
(In the formula, F is the force applied to the load cell, R is the arm length to the load cell, P is the pressurizing load, r ₁ is half the inner diameter, and r ₂ is half the outer diameter.)

Moreover, the specific wear amount A was calculated | required by the following measurement conditions and calculation formula using the said testing machine. The unit is mm ² / N · km.
<Measurement conditions>
Load: 10kg
Traveling speed: 15 cm / sec.
Temperature: 23 ° C
Humidity; 50%
<Calculation formula>
A = (ΔW) / (P × L × α)
(In the formula, A represents a specific wear amount, ΔW represents a change in mass of the test material, P represents a pressurizing load, L represents a travel distance, and α represents a density of the test piece.)

(4) Izod impact strength Measured at 23 ° C. according to ASTM-D256. The unit is kgf · cm / cm.
(5) Weather resistance Using a “Sunshine weatherometer” manufactured by Suga Test Instruments Co., Ltd., exposure was performed for 1000 hours at a rain cycle of 18 minutes / 120 minutes and a black panel temperature of 63 ° C., and a color change value ΔE before and after exposure was calculated.
ΔE was calculated by the following equation by measuring the degree of discoloration Lab (L: brightness, a: redness, b: yellowness) using a “multi-light source spectrometer” manufactured by Suga Test Instruments Co., Ltd.
ΔE = √ [(L ₁ −L ₂ ) ² + (a ₁ −a ₂ ) ² + (b ₁ −b ₂ ) ² ]
(In the formula, L ₁ , a ₁ , and b ₁ represent values before exposure, and L ₂ , a ₂ , and b ₂ represent values after exposure.)
The smaller the value of ΔE, the smaller the color change and the better the color tone.
(6) Luminance (total light reflectance and diffuse reflectance)
Sputtering is performed on the surface of the test piece (length 80 mm, width 55 mm, thickness 2.5 mm) under the following conditions by using a “vacuum film forming apparatus VRSP350MD type” manufactured by Shin-Maywa Kogyo Co., Ltd., to form an aluminum deposited film I let you. The total light reflectance and diffuse reflectance of the deposited film surface were measured using “Digital Reflectometer TR-1100AD type” manufactured by Tokyo Denshoku Co., Ltd., and the luminance was evaluated. The unit is%.
<Sputtering conditions>
Pressure after completion of roughing; 5.0 Pa
Pressure after completion of main pulling; 5.0 × 10 ⁻³ Pa
Introducing gas: 100 SCCM of argon
Degree of vacuum during film formation: 0.7 Pa
Aluminum film thickness: 120 nm
(7) Colorability (blackness)
Manufactured by blending 0.5 parts of carbon black (trade name “Mitsubishi Carbon Black # 45B”, manufactured by Mitsubishi Chemical Corporation) with 100 parts of the total polymer components contained in the polymer composition. did. A test piece made of this composition was prepared by injection molding, and the black sharpness was visually determined to evaluate the colorability. “◯” indicates that jetness is sufficient and excellent in colorability, and “x” indicates that jetness is not sufficient and the colorability is inferior.

Example 5
A rubber-reinforced resin composition was produced and evaluated in the same manner as in Example 4 except that a predetermined amount of the blending components shown in Table 3 was used. The results are shown in Table 3.

Example 6
A test piece consisting only of the rubber-reinforced resin [A-2] was prepared and evaluated in the same manner as in Example 4 above. The results are shown in Table 3.

Example 7
A rubber-reinforced resin composition was produced and evaluated in the same manner as in Example 4 except that a predetermined amount of the blending components shown in Table 3 was used. The results are shown in Table 3.

Comparative Example 2
A rubber-reinforced resin composition was produced and evaluated in the same manner as in Example 4 except that a predetermined amount of the blending components shown in Table 3 was used. The results are shown in Table 3.

Comparative Example 3
A rubber-reinforced resin composition was produced and evaluated in the same manner as in Example 4 except that a predetermined amount of the blending components shown in Table 3 was used. The results are shown in Table 3.

Comparative Example 4
A rubber-reinforced resin composition was produced and evaluated in the same manner as in Example 4 except that a predetermined amount of the blending components shown in Table 3 was used. The results are shown in Table 3.

From Table 3, since Comparative Examples 3 and 4 do not use the rubber-reinforced resin of the present invention, the impact resistance is sufficient, but the linear expansion coefficient and molding shrinkage ratio are high, the dynamic friction coefficient and the specific wear amount are high, It was inferior in brightness. Moreover, the weather resistance was also poor.
In Comparative Example 2, since the volume average particle diameter of the polyorganosiloxane used for making the rubber reinforced resin was as large as 290 nm, the linear expansion coefficient and the molding shrinkage ratio were high, the luminance was inferior, and the colorability was also inferior. It was.
On the other hand, it can be seen that Examples 4 and 6 in which the volume average particle diameter of the polyorganosiloxane was as small as 40 nm are balanced in physical properties in terms of dynamic friction coefficient, specific wear amount, Izod impact strength, luminance and colorability. Further, Example 5 using polycarbonate as the thermoplastic polymer showed a sufficient balance of physical properties even when the content was as high as 80 parts.

Claims (10)

  (A) 90 to 99.8% by weight of organosiloxane and (b) 10 to 0.2% by weight of graft crossing agent are obtained by cocondensation [provided that the sum of component (a) and component (b) is 100% by mass. In the presence of 1 to 70% by mass of polyorganosiloxane (p1) having a volume average particle diameter of 4 to 60 nm, 99 to 30% by mass of a vinyl monomer (m1) containing an aromatic vinyl compound [ However, the sum total of a component (p1) and a component (m1) is 100 mass%. ] A rubber-reinforced resin obtained by polymerizing The rubber-reinforced resin according to claim 1, wherein the graft crossing agent (b) is at least one selected from the following [i] to [iv].
[I] A compound having an unsaturated group represented by the following formula (1) and an alkoxysilyl group having 1 to 2 carbon atoms.
(In the formula, R ² is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)
[Ii] A compound containing a structural unit represented by the following formula (2).
(Wherein R ³ is a vinyl group or an allyl group, R ⁴ is a monovalent hydrocarbon group having 1 to 6 carbon atoms and having no aliphatic unsaturated group, and p is 1 And is an integer of 0 to 2. q is an integer of 0 to 2.)
[Iii] A compound containing a structural unit represented by the following formula (3).
(In the formula, R ⁵ has 1 to 18 carbon atoms and is a divalent or trivalent aliphatic saturated hydrocarbon group, and R ⁶ has 1 to 6 carbon atoms and has an aliphatic unsaturated group. Not a monovalent hydrocarbon group, and r is an integer of 0 to 2.)
[Iv] A compound containing a structural unit represented by the following formula (4).
(In the formula, R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, s is an integer of 1 to 6, and t is an integer of 0 to 2.)   In the presence of 1 to 70% by mass of polyorganosiloxane (p2), 99 to 30% by mass of a vinyl monomer (m2) containing an aromatic vinyl compound [however, the sum of component (p2) and component (m2) is 100% by mass. ] A rubber reinforced resin containing a grafted polyorganosiloxane obtained by polymerizing a polymer, wherein the grafted polyorganosiloxane has a number average particle diameter of 4 to 65 nm. The polyorganosiloxane (p2) is obtained by co-condensing 90 to 99.8% by mass of an organosiloxane (a) and 10 to 0.2% by mass of a graft crossing agent (b) [provided that the component (a ) And component (b) is 100% by mass. And the volume average particle size is 4 to 60 nm,
The rubber-reinforced resin according to claim 3, wherein the graft crossing agent (b) is at least one selected from the following [i] to [iv].
[I] A compound having an unsaturated group represented by the following formula (1) and an alkoxysilyl group having 1 to 2 carbon atoms.
(In the formula, R ² is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)
[Ii] A compound containing a structural unit represented by the following formula (2).
(Wherein R ³ is a vinyl group or an allyl group, R ⁴ is a monovalent hydrocarbon group having 1 to 6 carbon atoms and having no aliphatic unsaturated group, and p is 1 And is an integer of 0 to 2. q is an integer of 0 to 2.)
[Iii] A compound containing a structural unit represented by the following formula (3).
(In the formula, R ⁵ has 1 to 18 carbon atoms and is a divalent or trivalent aliphatic saturated hydrocarbon group, and R ⁶ has 1 to 6 carbon atoms and has an aliphatic unsaturated group. Not a monovalent hydrocarbon group, and r is an integer of 0 to 2.)
[Iv] A compound containing a structural unit represented by the following formula (4).
(In the formula, R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, s is an integer of 1 to 6, and t is an integer of 0 to 2.)   (A) 90 to 99.8% by weight of organosiloxane and (b) 10 to 0.2% by weight of graft crossing agent are obtained by cocondensation [provided that the sum of component (a) and component (b) is 100% by mass. In the presence of 1 to 70% by mass of polyorganosiloxane (p1) having a volume average particle diameter of 4 to 60 nm, 99 to 30% by mass of a vinyl monomer (m1) containing an aromatic vinyl compound [ However, the sum total of a component (p1) and a component (m1) is 100 mass%. ] To obtain a rubber-reinforced resin. The method for producing a rubber-reinforced resin according to claim 5, wherein the graft crossing agent (b) is at least one selected from the following [i] to [iv].
[I] A compound having an unsaturated group represented by the following formula (1) and an alkoxysilyl group having 1 to 2 carbon atoms.
(In the formula, R ² is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)
[Ii] A compound containing a structural unit represented by the following formula (2).
(Wherein R ³ is a vinyl group or an allyl group, R ⁴ is a monovalent hydrocarbon group having 1 to 6 carbon atoms and having no aliphatic unsaturated group, and p is 1 And is an integer of 0 to 2. q is an integer of 0 to 2.)
[Iii] A compound containing a structural unit represented by the following formula (3).
(In the formula, R ⁵ has 1 to 18 carbon atoms and is a divalent or trivalent aliphatic saturated hydrocarbon group, and R ⁶ has 1 to 6 carbon atoms and has an aliphatic unsaturated group. Not a monovalent hydrocarbon group, and r is an integer of 0 to 2.)
[Iv] A compound containing a structural unit represented by the following formula (4).
(In the formula, R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, s is an integer of 1 to 6, and t is an integer of 0 to 2.)   The rubber-reinforced resin according to claim 1 and another thermoplastic polymer are contained, and the content of the polyorganosiloxane (p1) used in claim 1 is 1 to 40 mass based on the entire composition. % Rubber reinforced resin composition characterized by the above-mentioned.   The rubber-reinforced resin composition according to claim 7, wherein the other thermoplastic polymer is a (co) polymer and / or polycarbonate of a vinyl monomer containing an aromatic vinyl compound.   The rubber-reinforced resin according to claim 3 and another thermoplastic polymer are contained, and the content of the polyorganosiloxane (p2) used in claim 3 is 1 to 40 mass based on the entire composition. % Rubber reinforced resin composition characterized by the above-mentioned.   The rubber-reinforced resin composition according to claim 9, wherein the other thermoplastic polymer is a (co) polymer of a vinyl monomer containing an aromatic vinyl compound and / or a polycarbonate.