JP2002020443A - Graft copolymer, thermoplastic resin composition containing the same, and molded item thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition which is excellent in resistances to impact and weathering not only at normal temperature but also at low temperatures and has high clarity. SOLUTION: A graft copolymer (E) is used which is prepared by grafting monomer units (D') onto a composite rubbery polymer (C) prepared by compositing a polyorganosiloxane (A) having aryl groups with a polymer (B) composed of at least one kind of monomer units selected from among vinyl cyanide monomer units, aromatic alkenyl units, and alkyl (meth)acrylate units. A thermoplastic resin composition containing the graft copolymer (E) is excellent in resistances to impact and weathering not only at normal temperature but also at low temperatures and has a high clarity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition which is excellent in impact resistance and weather resistance in a normal temperature and low temperature environment and is excellent in transparency.

[0002]

2. Description of the Related Art Acrylic resin is a molding material which is excellent in transparency and weather resistance and has a beautiful appearance, but has the disadvantage of low impact resistance. 2. Description of the Related Art It has been generally practiced to provide a shock resistance by reinforcing a hard resin such as an acrylic resin with an elastic body. As the elastic body, an ABS resin is typical. However, since the ABS resin contains a diene rubber as an elastic component, the weather resistance is poor,
Outdoor use of resin reinforced with ABS resin is often restricted. For this reason, various proposals have been made to produce an impact-resistant resin having weather resistance using an elastic body having an elastic body component other than a diene-based material. For example, an alkyl (meth) acrylate rubber or polydimethyl Elastic components represented by siloxane are exemplified.

[0003] However, the impact resistance when a graft copolymer containing a polyalkyl (meth) acrylate rubber as a rubber substrate is blended with a resin is satisfactory at ordinary temperature conditions, but the impact resistance at low temperatures such as below freezing points is low. Under such conditions, there is a marked decrease, and for example, there is a limit to the use in applications that require strength in a cold atmosphere, such as automotive exterior parts and electrical equipment parts. On the other hand, when a copolymer containing polydimethylsiloxane as a rubber substrate is blended with the resin, the impact resistance in a low-temperature environment is improved. However, the acrylic resin composition obtained by blending this copolymer with an acrylic resin has a very low transparency because of a large difference in the refractive index between the copolymer and the acrylic resin. It is shown in US Pat. No. 3,898,300 that it is difficult to use as a substrate. Therefore, a method of improving impact resistance and transparency by compounding a composite of a polyalkyl (meth) acrylate rubber and a polyorganosiloxane in an acrylic resin is disclosed in Japanese Patent Application Laid-Open No. Hei 8-2.
No. 83359 has been proposed.

[0004]

However, in an acrylic resin composition obtained by blending such a polyalkyl (meth) acrylate / polyorganosiloxane composite rubber with an acrylic resin, the transparency of the resin composition is reduced. In order to ensure the properties, it was necessary to limit the amount of the polyorganosiloxane used in the composite rubber. On the other hand, in order to improve the impact resistance of the resin composition under a low temperature environment,
It was necessary to increase the amount of polyorganosiloxane. As described above, when the conventional polydimethylsiloxane or polyalkyl (meth) acrylate / polyorganosiloxane-based composite rubber is used, it is difficult to achieve both transparency and impact resistance in a low-temperature environment.

The present invention has been made in view of the above circumstances, and provides a thermoplastic resin composition having excellent impact resistance and weather resistance and excellent transparency not only at room temperature but also in a low temperature environment. That is the task.

[0006]

Means for Solving the Problems As a result of diligent studies in view of the present situation, the present inventors have found that by blending a graft copolymer containing an aryl group-containing polyorganosiloxane with a resin, the excellent resin composition can be obtained. A method for improving impact resistance in a low-temperature environment while maintaining transparency and weather resistance has been found. The graft copolymer (E) of the present invention comprises a polyorganosiloxane (A) containing an aryl group and at least one selected from a vinyl cyanide monomer unit, an aromatic alkenyl unit and an alkyl (meth) acrylate unit. With respect to the composite rubber-like polymer (C) in which the polymer (B) having one kind of monomer unit as a component is complexed, a vinyl cyanide-based monomer unit, an aromatic alkenyl unit, an alkyl (meth) ) At least one monomer unit (D ') selected from acrylate units is graft-polymerized. The thermoplastic resin composition of the present invention comprises the above graft copolymer (E) and at least one monomer selected from a vinyl cyanide monomer unit, an aromatic alkenyl unit and an alkyl (meth) acrylate unit. And a (co) polymer (F) having a monomer unit as a constituent component.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polyorganosiloxane containing an aryl group (A) used in the present invention contains siloxane units having at least one aryl group on a silicon atom. Examples of the aryl group include a phenyl group, a naphthyl group, an alkyl nucleus-substituted phenyl group, an alkyl nucleus-substituted naphthyl group, a halogen nucleus-substituted phenyl group, and a halogen nucleus-substituted naphthyl group, preferably a phenyl group or a nucleus-substituted phenyl group It is.

[0008] Such an aryl group-containing polyorganosiloxane (A) can be produced, for example, by polymerizing a monomer mixture containing an aryl group-containing linear organosiloxane in the presence of an acid catalyst. Examples of the aryl group-containing linear organosiloxane to be used include, for example, an organo having an aryl group on at least one of silicon atoms forming a siloxane bond and having a hydroxyl group or an alkoxy group as a substituent at both ends. Siloxane.
Specific examples of such an aryl group-containing linear organosiloxane include those having a structure represented by the following chemical formula (I) or (II).

Embedded image (In the chemical formula (I), R ¹ , R ² , R ⁵ and R ⁶ are hydrogen or an alkyl group, and are the same or different substituents. R ³ and R ⁴ are an aryl group, and are the same or different substituents. X is a hydroxyl group or an alkoxy group, m is an integer of 1 or more, and n is an integer.)

Embedded image (In the chemical formula (II), R ¹ , R ² , R ³ , R ⁵ and R
⁶ is a hydrogen or an alkyl group, which is the same or different substituent. R ⁴ is an aryl group, X is a hydroxyl group or an alkoxy group, m is an integer of 1 or more, and n is an integer. )

Specific examples of the alkoxy group in the aryl group-containing linear organosiloxane include a methoxy group, an ethoxy group and a normal propoxy group, and a methoxy group is preferable. Specific examples of the aryl group in the aryl group-containing linear organosiloxane include a phenyl group, a naphthyl group, an alkyl nucleus-substituted phenyl group, an alkyl nucleus-substituted naphthyl group, a halogen nucleus-substituted phenyl group, and a halogen nucleus-substituted naphthyl group. Is mentioned. Specific examples of the alkyl group optionally contained in the aryl group-containing linear organosiloxane include a methyl group, an ethyl group, a normal butyl group, an isobutyl group, a normal propyl group, and an isopropyl group. A more specific example of such an aryl group-containing linear organosiloxane is an organosiloxane having a structure represented by the following chemical formula (III) or (IV).

Embedded image (In the chemical formula (III), X is a hydroxyl group or a methoxy group,
m is an integer of 1 or more, and n is an integer. )

Embedded image (In the chemical formula (IV), X is a hydroxyl group or a methoxy group, m
Is an integer of 1 or more, and n is an integer. )

As the aryl group-containing linear organosiloxane, when the content of the aryl group in the aryl group-containing linear organosiloxane is 100 when the number of bonding groups other than the siloxane bond bonded to all silicon atoms is 100 The number of aryl groups is preferably 5 to 95, more preferably 5 to 50, and even more preferably 10 to 40. When such an aryl group-containing linear organosiloxane is used, the transparency of the finally obtained thermoplastic resin composition is more excellent and preferable. If the number of aryl groups is less than 5 or more than 95, the transparency and impact resistance of the finally obtained thermoplastic resin composition may be insufficient. Further, the aryl group-containing linear organosiloxane has a viscosity of 0.01 to 10 Pa measured at 25 ° C.
S, more preferably 0.01
１1 Pa · s, more preferably 0.01 to 0.2 Pa
-It is s. When the aryl group-containing linear organosiloxane having such a viscosity is used, the transparency and impact resistance of the finally obtained thermoplastic resin composition are more excellent and are preferable. If the viscosity is less than 0.01, the resin composition containing these may volatilize when extruded or molded, and may have a viscosity of 10P.
When the value exceeds a · s, poor dispersion may occur during production of the polyorganosiloxane latex, and the stability of the latex may decrease. Such an aryl group-containing linear organosiloxane is, for example, polymethylphenylmethoxysiloxane (“XF40” manufactured by Toshiba Silicone Co., Ltd.).
-B6197 "), polymethylphenylsiloxane (" YF3804 ") and polymethylphenylmethoxysiloxane (" XF40-B6626 ").

The monomer mixture constituting the aryl group-containing polyorganosiloxane (A) may optionally contain a siloxane component other than the above-mentioned aryl group-containing linear organosiloxane. Examples of the siloxane component include linear diorganosiloxanes and cyclic diorganosiloxanes that do not contain an aryl group such as dimethylsiloxane. When such a siloxane component is used, 1 to 80% by mass of the aryl group-containing linear diorganosiloxane is used.
It is preferably used in the range of mass%. As the cyclic diorganosiloxane, a cyclic dialkylsiloxane having a three-membered ring or more is preferable because the productivity at the time of producing the polyorganosiloxane (A) containing an aryl group is excellent. Specific examples thereof include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like. These can be used alone or in combination of two or more.

The polyorganosiloxane (A) containing an aryl group can be produced by emulsion polymerization of the above monomer mixture in the presence of an acid catalyst. First, an emulsifier, an acid catalyst, and water are added to a monomer mixture containing an aryl group-containing linear organosiloxane, and further, if necessary, a vinyl polymerizable functional group-containing siloxane or a siloxane-based crosslinking agent is added. Emulsify the mixture. Examples of the emulsification method include mixing by high-speed stirring, mixing with a high-pressure emulsifying device such as a homogenizer, membrane emulsification using a porous membrane, fluid mixing using a static mixer, and the like. The use of a homogenizer is preferred because the particle size distribution of the organosiloxane (A) latex can be easily controlled. When a mixture is produced, a monomer mixture containing an aryl group-containing linear organosiloxane, a vinyl polymerizable functional group-containing siloxane, and a siloxane-based crosslinking agent are first mixed and homogenized. It is preferable to prepare a mixture of siloxane compounds in advance, then add an emulsifier and an acid catalyst to the mixture, and then mix water. Mixing by such a method enables more uniform emulsification.

Then, the emulsion prepared by the above method is heated and reacted to produce a polyorganosiloxane (A) latex. Heating temperature is 50
C. or higher, more preferably 80 C. or higher. The heating time is 2 hours or more, more preferably 5 hours.
More than an hour. During polymerization, sodium sulfate, magnesium sulfate,
An inorganic electrolyte such as calcium sulfate, sodium chloride, and aluminum chloride may be added. The amount of water used in the polymerization is not particularly limited. However, since both the stability of the polyorganosiloxane (A) latex and the productivity of the polyorganosiloxane (A) are excellent, 100 parts by mass of the siloxane compound mixture is used. Is preferably 100 to 1000 parts by mass, more preferably 150 to 500 parts by mass,
More preferably, it is in the range of 150 to 300 parts by mass.
If the amount is less than 100 parts by mass, the stability of the latex tends to be impaired. When the amount exceeds 500 parts by mass, the obtained polyorganosiloxane (A) latex becomes thin, and as a result, the subsequent step, that is, the step of compounding with the polymer (B) or the step of monomer unit (D ′) In some cases, the productivity in the graft polymerization step (2) may be significantly reduced. The polymerization reaction can be stopped by cooling the reaction solution and neutralizing by adding an alkaline substance such as caustic soda, potassium hydroxide, sodium carbonate and ammonia.
Further, the time required for cooling and neutralizing the emulsion after the reaction by heat treatment affects the molecular weight of the polyorganosiloxane (A) containing an aryl group. The molecular weight increases. Therefore, it is preferable to control the molecular weight of the polyorganosiloxane (A) by setting the retention time until neutralization to 1 hour or more, more preferably 10 hours or more. Preferably, the weight average molecular weight of the polyorganosiloxane (A) is 10,000 or more.

Other polymerization methods for the aryl group-containing polyorganosiloxane (A) include a monomer mixture containing an aryl group-containing linear organosiloxane, an emulsifier, water, and, if necessary, a vinyl polymerizable functional group. After emulsifying the mixture to which the group-containing siloxane and the siloxane-based crosslinking agent are added as described above, the mixture may be continuously dropped into an aqueous solution containing a heated acid catalyst to carry out polymerization.

In the production of the polyorganosiloxane (A) containing an aryl group, the siloxane containing a vinyl polymerizable functional group, which is used as required, may be other organosiloxane having a vinyl polymerizable functional group. There is no particular limitation as long as it can be bonded via a siloxane bond, but various alkoxysilane compounds containing a vinyl polymerizable functional group are preferred because of their excellent reactivity with other organosiloxanes. The use of a vinyl polymerizable functional group-containing siloxane is preferred because it functions as a graft-crosslinking agent, and the resulting polyorganosiloxane (A) and polymer (B) can be easily complexed.

Specific examples of the vinyl-polymerizable functional group-containing siloxane include β-methacryloxyethyldimethoxymethylsilane, γ-methacryloxypropyldimethoxymethylsilane, γ-methacryloxypropylmethoxydimethylsilane, and γ-methacryloxypropyltrimethoxy. Silanes, methacryloxysiloxanes such as γ-methacryloxypropyldiethoxymethylsilane and δ-methacryloxybutyldiethoxymethylsilane, vinylsiloxanes such as tetramethyltetravinylcyclotetrasiloxane, p- Vinylphenyldimethoxymethylsilane and γ-mercaptopropyldimethoxymethylsilane, γ-
Mercaptosiloxanes such as mercaptopropyltrimethoxysilane can be mentioned, and one kind can be used alone or two or more kinds can be used in combination. The preferred range of the amount of the vinyl-polymerizable functional group-containing siloxane is, when the amount of the aryl group-containing polyorganosiloxane (A) is 100 mol%, the amount of the vinyl-polymerizable functional group-containing siloxane unit is from 0.3 to 0.3%.
3 mol%, more preferably 0.5 to 2 mol%.
Mol%, more preferably 0.5 to 1 mol%.
If the amount is less than 0.3 mol%, complexation with the polymer (B) and graft polymerization of the monomer unit (D ') become insufficient, and the impact resistance of the finally obtained thermoplastic resin composition and Transparency may deteriorate. If it exceeds 3 mol%, the crosslinked structure of the rubber excessively develops, and as a result, the impact resistance of the thermoplastic resin composition may decrease.

The siloxane-based cross-linking agent optionally used in the production of the polyorganosiloxane (A) containing an aryl group may be a tri- or tetra-functional silane-based cross-linking agent such as trimethoxy. Methylsilane,
Triethoxyphenylsilane, tetramethoxysilane,
Tetraethoxysilane, tetrabutoxysilane, tetra-n-propyloxysilane and the like are used.

As the emulsifier, a usual anionic emulsifier or a nonionic emulsifier can be used. Examples of anionic emulsifiers include sodium alkylbenzene sulfonate, sodium lauryl sulfonate, sodium lauryl sulfate, sodium sulfosuccinate, sodium polyoxyethylene alkyl phenyl ether sulfate, sodium N-lauroyl sarcosine, dipotassium alkenyl succinate, rosin acid Soaps and sodium oleate. Among these, use of a sulfonate emulsifier such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate is particularly preferred. As the nonionic emulsifier, polyoxyethylene nonylphenyl ether, polyoxyethylene ethyl ether, polyoxyethylene lauryl ether, and the like can be used. These emulsifiers can be used alone or in combination of two or more. The amount of the emulsifier used is not particularly limited, but the stability of the emulsified latex during the production of the polyorganosiloxane (A) containing an aryl group is excellent, and the thermal coloring of the finally obtained thermoplastic resin composition is improved. Considering this, the amount of the emulsifier is 0.05 to 100 parts by mass of the aryl group-containing polyorganosiloxane (A).
The range of 20 parts by mass is preferable, and more preferably 0.05 part by mass.
To 5 parts by mass, more preferably 0.1 to 2 parts by mass. If the amount is less than 0.05 parts by mass, the dispersion of the aryl group-containing linear organosiloxane becomes insufficient, and the production of the aryl group-containing polyorganosiloxane (A) may be difficult. On the other hand, when the amount exceeds 20 parts by mass, the amount of the emulsifier remaining in the thermoplastic resin composition increases, and as a result, thermal coloring may be easily caused.

Examples of the acid catalyst include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid and aliphatic substituted naphthalenesulfonic acid, and sulfuric acid, hydrochloric acid, nitric acid, and the like.
Mineral acids such as phosphoric acid; Among these, aliphatic substituted benzenesulfonic acid is preferred in terms of having an effect of stabilizing the emulsified latex at the time of polymerization, and more preferably n-dodecylbenzenesulfonic acid.

The thus obtained polyorganosiloxane containing an aryl group (A) and the polymer (B) are compounded to obtain a composite rubber-like polymer (C). By graft-polymerizing the monomer unit (D ') to (C), a graft copolymer (E) is obtained. The term “composite” as used herein refers to a state in which the polymer (B) to be composited is entangled at a micro level or chemically bonded to the polyorganosiloxane (A) containing an aryl group. It refers to Therefore, it may or may not have a chemical bond.

The polymer (B) contains at least one monomer unit selected from a vinyl cyanide monomer unit, an aromatic alkenyl unit and an alkyl (meth) acrylate unit as a constituent. As the vinyl cyanide monomer used here, acrylonitrile, methacrylonitrile, fumaronitrile and the like can be used, and among these, acrylonitrile is preferable. As the aromatic alkenyl monomer, styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene and the like can be used, and among them, styrene is preferred. As the alkyl (meth) acrylate, an alkyl group having 2 to 8 carbon atoms is preferable. For example, an ester of acrylic acid and a linear or side chain alcohol having 2 to 8 carbon atoms is used. You. Specifically, methyl acrylate, ethyl acrylate, propyl acrylate, 2-butyl acrylate,
Isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, 2-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, methacrylic acid Benzyl etc. can be used,
Particularly, n-butyl acrylate is preferred. Further, the polymer (B) may have two or more polymerizable functional groups such as allyl methacrylate, polyethylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate as monomers other than these. Compounds and the like can also be used.

Here, the polymer (B) preferably has a refractive index close to that of the aryl group-containing polyorganosiloxane (A). Preferably, the difference between the refractive index of the aryl group-containing polyorganosiloxane (A) and the refractive index of the polymer (B) is 0.02 or less. As described above, as the polyorganosiloxane (A) containing the aryl group and the polymer (B), those having a small difference in refractive index are used. Further, as described later, the polymers (D) and ( The thermoplastic resin composition finally obtained by using a (co) polymer (F) having a refractive index similar to that of the polyorganosiloxane (A) or the polymer (B). Is more excellent in transparency. Since the refractive index of the polyorganosiloxane (A) containing an aryl group can be adjusted by changing the content of the aryl group in the polyorganosiloxane (A), the refractive index of the polymer (B) to be composited, etc. It is preferable to adjust the content of the aryl group according to the above. Further, the refractive index of the polymer (B) can also be adjusted by changing its composition.

The polyorganosiloxane (A) in the case where the aryl group-containing polyorganosiloxane (A) and the polymer (B) are compounded to form a composite rubbery polymer (C).
When the ratio of the composite rubber-like polymer (C) is 100% by mass, the content of the aryl group-containing polyorganosiloxane (A) is 2 to 98% by mass, and the ratio of the polymer (B) is Is preferably from 2 to 98% by mass. Such a ratio is preferable because the finally obtained thermoplastic resin composition has more excellent impact resistance. More preferably,
The polyorganosiloxane containing an aryl group (A) is 5 to 80% by mass, and the polymer (B) is 20 to 95% by mass. If the proportion of the polyorganosiloxane (A) containing an aryl group is less than 2% by mass, the impact resistance of the finally obtained thermoplastic resin composition may be insufficient.

There is no particular limitation on the method of complexing the aryl group-containing polyorganosiloxane (A) with the polymer (B). For example, the method of preparing the aryl group-containing polyorganosiloxane (A) prepared in advance may be used. In the presence
A method of polymerizing the monomer units constituting the polymer (B), or conversely, a monomer comprising the aryl-containing polyorganosiloxane (A) in the presence of the polymer (B) prepared in advance. Examples include a method of polymerizing a body component. In the polymerization method, since the polyorganosiloxane (A) containing an aryl can be easily obtained by emulsion polymerization, it is preferable that the complexation of the polymer (B) is also performed by emulsion polymerization. In this case, a radical polymerization initiator such as a peroxide, an azo-based initiator, or a redox-based initiator obtained by combining an oxidizing agent and a reducing agent is used. Among these, a redox initiator is preferable, and a sulfoxylate initiator obtained by combining ferrous sulfate, disodium ethylenediaminetetraacetate, Rongalit, and hydroperoxide is particularly preferable.

The monomer unit (D ') to be graft-polymerized to the composite rubbery polymer (C) is selected from vinyl cyanide monomer units, aromatic alkenyl units and alkyl (meth) acrylate units. At least one kind. The vinyl cyanide-based monomer unit, aromatic alkenyl unit, and alkyl (meth) acrylate unit used herein are the same as those exemplified as the monomer unit constituting the polymer (B). Can be used, but preferably,
It is preferred to use at least a methyl methacrylate unit. More preferably, the monomer unit (D ') 10
It is preferable that 50% by mass or more of methyl methacrylate is contained in 0% by mass. If it is less than 50% by mass, the transparency of the finally obtained thermoplastic resin composition may be reduced. In this case, as other components used in the range of 50% by mass or less, monomers of vinyl cyanide monomer units, aromatic alkenyl units, and alkyl (meth) acrylate units may be used alone or in combination of two or more. These can be used in combination.

The monomer unit (D ') is a polymer (D) obtained by polymerizing the monomer unit (D'), and the refractive index of the polymer (D) is a polyorgano group containing an aryl group. It is preferable that the refractive index is selected so as to be substantially the same as the refractive index of the siloxane (A) or the refractive index of the polymer (B), and the difference between these refractive indexes is adjusted to be small. Moreover,
Among these refractive indices, it is preferable that the difference between the maximum refractive index and the minimum refractive index is adjusted to be 0.02 or less. Further, as described later, it is preferable to reduce the difference in refractive index from the (co) polymer (F). The monomer unit (D ′) is preferably graft-polymerized in a range of 10 to 500 parts by mass, more preferably 30 to 150 parts by mass, based on 100 parts by mass of the composite rubbery polymer (C).
More preferably, it is 45 to 100 parts by mass. If the amount is less than 10 parts by mass, the impact strength of the finally obtained thermoplastic resin composition may decrease, while if it exceeds 500 parts by mass, the composite rubber-like polymer in the obtained graft copolymer (E) Since the amount of (C) is relatively decreased, the impact resistance of the finally obtained thermoplastic resin composition may be insufficient.

The method of graft-polymerizing the monomer unit (D ') to the composite rubbery polymer (C) is not particularly limited, but the aryl-containing polyorganosiloxane (A) is not particularly limited. In addition, since the composite rubber-like polymer (C) is easily prepared by emulsion polymerization and can be easily supplied in the form of an emulsion latex, it is preferable that the graft polymerization is also performed by emulsion polymerization. As an example of emulsion graft polymerization, in the presence of a composite rubbery polymer (C) latex,
A method in which the monomer units (D ') are added at once, continuously or intermittently to perform radical polymerization. In the graft polymerization, a known chain transfer agent for controlling the molecular weight of the polymer (D) and a graft ratio, and a known inorganic electrolyte for controlling the viscosity and pH of the latex are used. be able to. There is no particular limitation on the type and the amount of addition. In the emulsion graft polymerization, various emulsifiers can be used as needed. Specific examples of the emulsifier include the same emulsifiers as those used in the production of the above-mentioned aryl group-containing polyorganosiloxane (A). Preferred are anionic emulsifiers such as sodium N-lauroyl sarcosinate and sodium oleate. As the radical polymerization initiator to be used, a peroxide, an azo-based initiator, or a redox-based initiator obtained by combining an oxidizing agent and a reducing agent is used. Redox initiators are preferred among these,
In particular, a sulfoxylate initiator obtained by combining ferrous sulfate, disodium ethylenediaminetetraacetic acid, Rongalit, and hydroperoxide is preferable.

In order to obtain a granular graft copolymer (E) from the graft copolymer (E) latex produced as described above, this latex is put into hot water in which a coagulant is dissolved, and Coagulates and solidifies. And this coagulation,
The solidified graft copolymer (E) is re-dispersed in water or hot water to form a slurry, which is dried by a flash dryer or the like to obtain a granular graft copolymer (E).
Is obtained. As the coagulant used here, sulfuric acid,
Inorganic acids such as hydrochloric acid, phosphoric acid and nitric acid, calcium chloride,
Although metal salts such as calcium acetate and aluminum sulfate can be used, the productivity of the graft copolymer (E) is excellent, and thermal coloring during molding of the finally obtained thermoplastic resin composition is taken into consideration. Then, it is preferable to use a metal salt.

The thermoplastic resin composition of the present invention contains the graft copolymer (E) and the (co) polymer (F). The (co) polymer (F) comprises at least one monomer unit selected from an alkyl (meth) acrylate unit, an aromatic alkenyl unit, and a vinyl cyanide-based monomer unit, and optionally, It is obtained by polymerizing a copolymerizable monomer unit. The vinyl cyanide-based monomer unit, aromatic alkenyl unit, and alkyl (meth) acrylate unit used herein are the same as those exemplified as the monomer unit constituting the polymer (B). However, it is preferable to use at least a methyl methacrylate unit. More preferably, 100% by mass of the monomer unit preferably contains 50% by mass or more of methyl methacrylate. (Both)
The method for producing the polymer (F) is not particularly limited, but it can be produced by a known method such as suspension polymerization, solution polymerization, or bulk polymerization.

The content of the graft copolymer (E) in 100% by mass of the thermoplastic resin composition is preferably 10%.
To 100% by mass, more preferably 20 to 80% by mass. If it is less than 10% by mass, the amount of the aryl group-containing polyorganosiloxane (A) in the thermoplastic resin composition,
Or, the amount of the composite rubber-like polymer (C) relatively decreases,
The impact resistance of the thermoplastic resin composition may decrease.
As a method of blending the graft copolymer (E) and the (co) polymer (F), a method of melt-mixing is preferable. In this case, prior to melt mixing, known stabilizers, lubricants, plasticizers,
Dyes, pigments, fillers, antistatic agents and the like are added as necessary and mixed with a V-type blender or a Henschel mixer. And melt kneading. The thus obtained thermoplastic resin composition,
By performing thermoforming with an extruder, an injection molding machine, an extrusion molding machine, or the like, a film-shaped or sheet-shaped molded product excellent in transparency, impact resistance, and weather resistance can be manufactured. Also, by molding with an injection molding machine etc., transparency, impact resistance,
A three-dimensional molded article having excellent weather resistance can be manufactured. As molded products, automotive exterior parts such as bumpers, roof garnishes, door mirrors, tail lamps, etc. and their coating materials, and electrical equipment exterior parts such as OA equipment operation parts, display panels, air conditioner outdoor units, etc., and coating materials for these coating materials Used as an alternative.

[0031]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited by these examples. In Examples and Comparative Examples, “parts” and “%” are “parts by mass” and “% by mass” unless otherwise specified.
Means Reference Example 1 Preparation of Polyorganosiloxane (A-1) Latex Containing Aryl Group Terminal methoxydiphenyldimethylsiloxane (XF40-B6197 manufactured by Toshiba Silicone Co., Ltd .: diphenylsiloxane content = 34 mol%, viscosity at 25 ° C .: 0.04)
Pa · s) 76.3 parts, octamethylcyclotetrasiloxane (TSF-404 manufactured by Toshiba Silicone Co., Ltd.) 18.7
Were mixed with 5 parts of γ-methacryloyloxypropyldimethoxymethylsilane to obtain 100 parts of a siloxane mixture. Next, 1 part of sodium dodecylbenzenesulfonate and 1 part of dodecylbenzenesulfonate were added to the siloxane mixture, and after stirring, 200 parts of distilled water was added, and the mixture was preliminarily stirred at 10,000 rpm with a homomixer, and then pressure of 40 MPa was applied with a homogenizer. And emulsified and dispersed four times to obtain an organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, and mixed and stirred.
After heating at 0 ° C for 5 hours, it was left at 20 ° C. And 1
Six hours later, the pH of the latex was neutralized to 7.4 with a 5% aqueous sodium hydroxide solution to complete the polymerization, and an aryl group-containing polyorganosiloxane (A-1) latex was obtained. The solid content of the aryl group-containing polyorganosiloxane (A-1) latex thus obtained was 28.6%, and the absorbance was 0.31. Also,
The weight average molecular weight of the polyorganosiloxane containing an aryl group in (A-1) is 67000, and is 23 ° C.
Was 1.493.

Reference Example 2 Production of Polyorganosiloxane (A-2) Latex Containing Aryl Group Methoxydiphenyldimethylsiloxane (XF40-B6197 manufactured by Toshiba Silicone Co., Ltd.) was used in an amount of 78.7 parts.
Polyorganosiloxane (A-2) latex containing an aryl group in the same manner as in Reference Example 1 except that octamethylcyclotetrasiloxane was changed to 19.3 parts and γ-methacryloyloxypropyldimethoxymethylsilane was changed to 2 parts. I got The thus-obtained polyorganosiloxane containing an aryl group (A-
2) The latex has a solid content of 28.7% and an absorbance of 0.2.
75. The weight average molecular weight of the aryl group-containing polyorganosiloxane in (A-2) is 75.
000 and the refractive index measured at 23 ° C. was 1.495.

Reference Example 3 Production of Polyorganosiloxane (A-3) Latex Containing Aryl Group Terminal methoxydiphenyldimethylsiloxane (XF40-B6197 manufactured by Toshiba Silicone Co., Ltd.) was used in an amount of 85.5 parts.
An aryl group-containing polyorganosiloxane (A-3) latex was obtained in the same manner as in Reference Example 1, except that octamethylcyclotetrasiloxane was changed to 9.5 parts.
The solid content of the aryl group-containing polyorganosiloxane (A-3) latex thus obtained was 29.
The absorbance was 1% and the absorbance was 0.28. The weight average molecular weight of the aryl group-containing polyorganosiloxane in (A-3) was 53,000, and the refractive index measured at 23 ° C. was 1.501.

Reference Example 4 Polyorganosiloxane (A
-4) Production of Latex 98 parts of octamethylcyclotetrasiloxane and 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of a siloxane mixture. Next, 1 part of sodium dodecylbenzenesulfonate and 1 part of dodecylbenzenesulfonate were added to the siloxane mixture, and after stirring, 200 parts of distilled water was added, and the mixture was preliminarily stirred at 10,000 rpm with a homomixer, and then pressure of 40 MPa was applied with a homogenizer. And emulsified and dispersed four times to obtain an organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours while mixing and stirring, and then left at 20 ° C. After 16 hours, the pH of this latex was neutralized to 7.4 with a 5% aqueous sodium hydroxide solution to complete the polymerization, and the polyorganosiloxane (A
-4) A latex was obtained. The solid content of the polyorganosiloxane (A-4) latex thus obtained was 2%.
The absorbance was 9.1% and the absorbance was 0.130. The weight average molecular weight of the polyorganosiloxane (A-4) is 220.
The refractive index measured at 23 ° C. was 1.407.

Reference Example 5 Production of Copolymer (F-2) 150 parts of water, 2.5 parts of acrylonitrile were placed in a pressure-resistant reactor equipped with a cooling pipe, a jacket heater and a stirrer.
7.5 parts of styrene, 90 parts of methyl methacrylate, 0.20 part of azobisisobutyronitrile, 0.4 part of tertiary decyl mercaptan and 0.7 part of polyvinyl alcohol are charged, and 400 revolutions are performed using an anchor-type stirring bar. The mixture was stirred under the condition of every minute. Next, the internal temperature was raised to 75 ° C. by a jacket heater, and a polymerization reaction was performed for 2 hours. Next, the internal temperature was again raised to 110 ° C. by the jacket heater and maintained for 20 minutes to complete the reaction. After cooling the content, washing and dehydration were repeated using a centrifugal dehydrator, and the resulting solid was dried to obtain a white granular copolymer (F-2). Reduced viscosity of this polymer (F-2) measured in dimethylformamide at 25 ° C. (ηsp /
C) was 0.50 dl / g, and the refractive index measured at 23 ° C. was 1.501.

Example 1 Graft Copolymer (E-1)
The aryl group-containing polyorganosiloxane (A-1) latex was placed in a reactor equipped with a nitrogen gas inlet pipe, a reagent injection vessel, a cooling pipe, a jacket heater and a stirrer.
5.0 parts (10 parts as solids), Emar NC-35
(Polyoxyethylene alkylphenyl sulfate;
After adding and mixing 0.2 part of Kao Corporation and 150 parts of distilled water, 49.2 parts of butyl acrylate, 10.8 parts of styrene and allyl methacrylate 0.9 constituting the polymer (B-1) were mixed. And an aqueous solution obtained by dissolving 0.3 part of t-butyl hydroperoxide, 0.00001 part of ferrous sulfate, 0.00003 part of disodium ethylenediaminetetraacetate and 0.3 part of Rongalit in 10 parts of distilled water. 320 parts of distilled water were added. The above polymer (B-1) (81 parts of butyl acrylate, 17.5 parts of styrene, 1.5 parts of allyl methacrylate, 0.5 part of t-butyl hydroperoxide separately prepared by emulsion polymerization)
Part) at 23 ° C. had a refractive index of 1.489. The liquid temperature after one hour increased to 75 ° C. due to polymerization by complexing polyorganosiloxane (A-1) and polymer (B-1). This state is maintained for 1 hour, and the composite rubbery polymer (C)
Latex was obtained. The atmosphere was replaced with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the internal liquid temperature reached 60 ° C., an aqueous solution in which 0.25 part of Rongalite was dissolved in 10 parts of distilled water was added, and 28.5 parts of methyl methacrylate and 1.85 parts of methacrylic acid were added.
A mixture of 5 parts and 0.12 parts of t-butyl hydroperoxide was added dropwise over 2 hours, and a monomer unit (D ′) was added.
Radical polymerization for graft polymerization of -1) was started. In addition, separately prepared polymer (D-
1) (95 parts of methyl methacrylate, 5 parts of methacrylic acid)
Had a refractive index at 23 ° C. of 1.490. After completion of the dropwise addition, the mixture was kept for 2 hours and cooled. Solid content of the graft copolymer (E-1) in the latex determined by the dynamic light scattering method,
The weight average particle diameters are 22.5% and 0.270 μ, respectively.
m. Then, the graft copolymer (E-1) latex was heated to 65 ° C. and a 5% calcium acetate aqueous solution 15 was added.
The mixture was dropped into 0 parts and solidified. The obtained powdery graft copolymer was dried at 85 ° C. for 24 hours to obtain a graft copolymer (E-1). The acetone insoluble content in this graft copolymer (E-1) was 78%. The used aryl group-containing polyorganosiloxane (A-1), polymer (B-1) and polymer (D-1) are shown in Table 1 together with their refractive indices.

Example 2 Graft Copolymer (E-2)
Example 1 was repeated except that the aryl group-containing polyorganosiloxane (A-1) latex was changed to 104.9 parts (30 parts as solid content), butyl acrylate was changed to 32.8 parts, and styrene was changed to 7.2 parts. Similarly, the graft copolymer (E
-2) was obtained. The solid content and the weight average particle diameter of the graft copolymer (E-2) in the latex determined by the dynamic light scattering method were 23.1% and 0.217 μm, respectively.
Subsequently, the polymerization latex of the graft copolymer (E-2) was dropped into 150 parts of a 5% calcium acetate aqueous solution heated to 65 ° C. to coagulate. The obtained powdery graft copolymer was dried at 85 ° C. for 24 hours to obtain a graft copolymer (E-
2) was obtained. The acetone insoluble content in this graft copolymer (E-2) was 79%. The used aryl group-containing polyorganosiloxane (A-1) and polymer (B-
1) and the polymer (D-1) are shown in Table 1 together with the refractive index.

Example 3 Graft Copolymer (E-3)
Example 1 was repeated except that the aryl group-containing polyorganosiloxane (A-1) latex was changed to 175.0 parts (50 parts as solid content), butyl acrylate was changed to 16.4 parts, and styrene was changed to 3.6 parts. Similarly, the graft copolymer (E
-3) was obtained. The solid content and the weight average particle diameter of the graft copolymer (E-4) in the latex determined by the dynamic light scattering method were 23.5% and 0.231 μm, respectively.
Then, a polymerization latex of the graft copolymer (E-3) was dropped into 150 parts of a 5% calcium acetate aqueous solution heated to 65 ° C. to coagulate. The obtained powdery graft copolymer was dried at 85 ° C. for 24 hours to obtain a graft copolymer (E-
3) was obtained. The content of acetone insoluble in this graft copolymer (E-3) was 79%. The used aryl group-containing polyorganosiloxane (A-1) and polymer (B-
1) and the polymer (D-1) are shown in Table 1 together with the refractive index.

Example 4 Graft Copolymer (E-4)
A graft copolymer (E-4) was obtained in the same manner as in Example 2 except that the aryl group-containing polyorganosiloxane latex used was changed from (A-1) to (A-2).
The solid content and the weight average particle diameter of the graft copolymer (E-4) in the latex determined by the dynamic light scattering method were 23.7% and 0.231 μm, respectively. Then, a polymerization latex of the graft copolymer (E-4) was dropped into 150 parts of a 5% calcium acetate aqueous solution heated to 65 ° C. to coagulate. The obtained powdery graft copolymer was heated at 85 ° C for 24 hours.
After drying for an hour, a graft copolymer (E-4) was obtained. The acetone insoluble content in this graft copolymer (E-4) was 78.
%Met. The used aryl group-containing polyorganosiloxane (A-2), polymer (B-1), and polymer (D
-1) is shown in Table 1 together with the refractive index.

Example 5 Graft Copolymer (E-5)
The aryl-containing polyorganosiloxane latex to be used was changed from (A-1) to (A-3), and instead of 28.5 parts of graft-polymerized methyl methacrylate and 1.5 parts of methacrylic acid, A graft copolymer (E-5) was obtained in the same manner as in Example 2, except that 27.0 parts of methyl methacrylate, 2.25 parts of acrylonitrile, and 6.75 parts of styrene were used as a body unit. The monomer unit used here is designated as (D'-2). The refractive index at 23 ° C. of the polymer (D-2) (90 parts of methyl methacrylate, 2.5 parts of acrylonitrile, 7.5 parts of styrene) separately prepared by suspension polymerization was 1.501.
The solid content and the weight average particle diameter of the graft copolymer (E-5) in the latex determined by the dynamic light scattering method were 23.7% and 0.241 μm, respectively. Then, a polymerization latex of the graft copolymer (E-5) was dropped into 150 parts of a 5% calcium acetate aqueous solution heated to 65 ° C. to coagulate. The obtained powdery graft copolymer was heated at 85 ° C for 24 hours.
After drying for an hour, a graft copolymer (E-5) was obtained. The acetone insoluble content in this graft copolymer (E-5) was 78.
%Met. The used aryl group-containing polyorganosiloxane (A-3), polymer (B-1) and polymer (D
-2) are shown in Table 1 together with the refractive index.

Comparative Example 1 Graft Copolymer (E-6)
The polymerization was carried out in the same manner as in Example 2 except that polydimethylorganosiloxane (A-4) was used in place of the aryl group-containing polyorganosiloxane (A-1), and the amount of water was adjusted. E-6) was obtained. The refractive index of this graft copolymer (E-6) measured at 23 ° C. was 1.
411. The solid content and the weight average particle size of the graft copolymer (E-6) in the latex determined by the dynamic light scattering method were 23.2% and 0.159 μm, respectively. The acetone insoluble content in this graft copolymer (E-6) was 76%. The used polyorganosiloxane, polymer (B-1) and polymer (D-1) were
The refractive index is shown in Table 1.

Comparative Example 2 Graft Copolymer (E-7)
In the same manner as in Example 2 except that the aryl group-containing polyorganosiloxane (A-1) was not used, the ratio of butyl acrylate / styrene was changed to 70/30 by mass, and the amount of water was adjusted. A graft copolymer (E-7) was obtained. Here, the butyl acrylate / styrene copolymer is referred to as a polymer (B-2). The refractive index of the polymer (B-2) was 1.490. The solid content and the weight average particle size of the graft copolymer in the latex determined by the dynamic light scattering method were 23.9% and 0.243 μm, respectively. Also,
Acetone insoluble content in this graft copolymer (E-7) was 73%. The used polyorganosiloxane, polymer (B-2) and polymer (D-1) are shown in Table 1 together with the refractive index.

(Examples 6 to 10, Comparative Examples 3 to 5) Production of Thermoplastic Resin Compositions Graft copolymers (E-1 to 7) produced in Examples 1 to 5 and Comparative Examples 1 and 2, (Co) polymer (Acripet VHS manufactured by Mitsubishi Rayon Co., Ltd., refractive index 1.489)
(F-1) and the copolymer (F-2) produced in Reference Example 5
Are mixed at the ratio shown in Table 2, 0.2 parts of ADK STAB AO-50 (manufactured by Asahi Denka Kogyo KK) as an antioxidant, and ADEKA STAB 329K (manufactured by Asahi Denka Kogyo KK) as a heat stabilizer. ) As a modifier and a release agent, silicone L-45-100 (Shin-Etsu Chemical Co., Ltd.)
Manufactured by Adekastab LA- as a light stabilizer.
77Y (made by Asahi Denka Kogyo Co., Ltd.) and ADK STAB 32P
(Asahi Denka Kogyo KK) 0.25 parts, 0.1
Five parts were added and mixed with a Henschel mixer for 3 minutes.
Each thermoplastic resin composition (1) thus obtained
Table 3 shows the refractive index of each component in (8). Table 3 shows the difference between the maximum refractive index and the minimum refractive index.

(Examples 11 to 15 and Comparative Examples 6 to 8) The thermoplastic resin compositions obtained in Examples 6 to 10 and Comparative Examples 3 to 5 were prepared using PCM-30 set at a barrel temperature of 230 ° C.
(Twin screw extruder; manufactured by Ikegai Iron Works Co., Ltd.) to produce resin pellets. Then, the obtained pellets were subjected to SAV-60 injection molding machine (vertical injection molding machine; manufactured by Yamashiro Seiki Co., Ltd.) at a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C. for 1 hour.
It was formed into a flat plate of 00 mm × 100 mm × 3 mmt. The impact resistance at room temperature and low temperature was measured using this molded plate. In addition, the obtained pellets were 70 mm in width and 1.
Screw diameter 25 m with 0, 3.0 mm T die
extruder using a single-screw extruder (manufactured by Thermoplastics Co., Ltd.), a transfer roll, and an extruder comprising a winding device at a barrel temperature of 230 ° C., a roll temperature of 80 ° C., and a screw rotation speed of 40 revolutions / minute. A film having a width of 70 mm and a thickness of 0.5 mm and a sheet molded product having a thickness of 2.0 mm were obtained. Then, the molded appearance characteristics and weather resistance of the sheet molded product were evaluated, and the tensile strength, molded appearance characteristics, and weather resistance of the film at ordinary temperature and low temperature were evaluated. Table 4 shows the evaluation results.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

[Table 4]

[Evaluation Methods] Various physical properties and the like in the above Reference Examples, Examples and Comparative Examples were measured and evaluated by the following methods. (1) Absorbance of Polyorganosiloxane Latex Latex The absorbance of the aryl group-containing polyorganosiloxane (A) and the polyorganosiloxane latex in Examples and Comparative Examples was determined by measuring the latex prepared at a solid content concentration of 0.5 g / L using an ultraviolet-visible spectrophotometer. The measurement was performed under the condition of a wavelength of 700 nm using a total meter (“UV-160”, Shimadzu Corporation). (2) Molecular weight of polyorganosiloxane The weight-average molecular weight of the polyorganosiloxane (A) containing an aryl group and the polyorganosiloxane latex was determined by precipitating and recovering the latex with isopropyl alcohol, drying the latex under vacuum at room temperature, and then adding tetrahydrofuran. Was measured using GPC (manufactured by WATERS), and determined from the retention time in terms of standard polystyrene. (3) Refractive index of polyorganosiloxane The refractive index of the polyorganosiloxane (A) containing an aryl group and the polyorganosiloxane is determined by precipitating and recovering a latex with isopropyl alcohol, drying it in a vacuum at room temperature, and then subjecting it to Abbe refraction. Rate meter (Shimadzu Corporation)
Manufactured at 23 ° C. (4) Refractive index of polymer (B), polymer (D), (co) polymer (F) Polymer (B), polymer (D), (co) polymer (Example) and Comparative Example The measurement of the refractive index of F) is performed separately.
The resin composition obtained by emulsion polymerization and suspension polymerization was extruded, and the obtained sheet-like specimen was cut out and measured at 23 ° C. using an Abbe refractometer (manufactured by Shimadzu Corporation). . (5) Weight average particle diameter of graft copolymer (E)
The particle sizes of 00 to 300 particles were measured, and their average particle sizes were determined. (6) Izod impact strength Using an injection molded product in accordance with ASTM D256, 23
It measured under the conditions of ° C and -30 ° C. (7) Tensile strength A JIS No. 2 dumbbell was prepared from a 0.5 mm thick film molded product prepared by extrusion molding by punching, and this was used as a test piece by a tensile tester (Strograph T, Toyo Seiki (product)). Crosshead speed 500mm /
In seconds, it was measured at 23 ° C and -30 ° C. And the strength which the test piece fractured was calculated | required. (8) Evaluation of molding appearance characteristics The evaluation of molding appearance characteristics (total light transmittance, haze (haze value)) was performed by cutting out a sheet molded product obtained by extrusion molding.
It was measured by a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd.). (9) Evaluation of Weather Resistance The weather resistance of the resin composition (white colored product) was determined by cutting a sheet molded product or film obtained by extrusion molding into a size of 50 mm × 50 mm, and using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.). ) For 1000 hours, and was evaluated based on the degree of discoloration (ΔE) and the gloss retention rate calculated by the following equation (1). The degree of discoloration was measured with a color difference meter. Gloss retention (%) = (gloss after exposure for 1000 hours / gloss before exposure) × 100 (1)

From the examples and comparative examples, the following became clear. (1) An aryl group-containing polyorganosiloxane (A) and a polymer (B) are used as a graft copolymer containing a composite rubbery polymer (C). The refractive index is higher than that of the graft copolymer. By blending such a graft copolymer with a resin and molding, a sheet and a film having good transparency could be obtained. (2) When a graft copolymer containing a composite rubbery polymer (C) in which a polyorganosiloxane (A) containing an aryl group and a polymer (B) are compounded is blended with a thermoplastic resin and molded, the mixture is molded at room temperature. A molded article having excellent mechanical properties at low temperatures, excellent weather resistance, high transparency, and good molded appearance properties was obtained. Note that the characteristics at low temperatures are derived from low Tg. (3) On the other hand, when a graft copolymer containing a polyorganosiloxane containing no aryl group was blended with a thermoplastic resin and molded, a molded article with poor transparency and poor molded appearance was obtained. (4) When a thermoplastic resin is blended with a graft copolymer containing alkyl (meth) acrylate / styrene, which does not contain polyorganosiloxane, and molded, the transparency and the impact resistance at room temperature are excellent, but the temperature is low. A molded article having slightly poor impact resistance and low weather resistance under the conditions was obtained.

[0051]

As described above, the graft copolymer (E) of the present invention comprises a polyorganosiloxane (A) having an aryl group, a vinyl cyanide monomer unit, an aromatic alkenyl unit and an alkyl group. As a rubber source, a composite rubbery polymer (C) obtained by complexing with a polymer (B) having at least one monomer unit selected from (meth) acrylate units as a constituent is included as a rubber source. By blending the polymer (E) with the resin, it is possible to obtain a thermoplastic resin composition having excellent impact resistance and weather resistance and excellent transparency even at normal temperature or low temperature environment. The thermoplastic resin composition of the present invention is suitable for a sheet or a film, and also suitable for use as an automotive exterior material or a building material.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 33/18 C08L 33/18 51/06 51/06 51/08 51/08 // B29K 21:00 B29K 21:00 B29L 7:00 B29L 7:00 (72) Inventor Hideyuki Fujii 20-1 Miyukicho, Otake City, Hiroshima Prefecture Inside Mitsubishi Rayon Co., Ltd.'s Otake Works (72) Inventor Hideyuki Shigemitsu 20 Miyukicho, Otake City, Hiroshima Prefecture No. 1 Mitsubishi Rayon Co., Ltd. Otake Works F-term (reference) 4F071 AA22 AA33 AA34 AA67 AA77 AF31Y AH07 AH12 BB05 BB06 BC01 BC07 4F206 AA45G JA07 JF01 JL02 4F208 AA45G AG01 MG01 MG11 4J002 BG06YBGN BG10 BG06YBN10G AA17 AA45 AA56 AB44 AC15 BA05 BA08 BA27 BA28 BA31 BA40 BB04 BB10 DB04 DB08 DB12 DB13 DB16 FA04 GA01 GA08

Claims (8)

[Claims] 1. An aryl group-containing polyorganosiloxane (A) and at least one monomer unit selected from a vinyl cyanide monomer unit, an aromatic alkenyl unit and an alkyl (meth) acrylate unit. Rubber-like polymer (C) in which a polymer (B) having the following constituents has been compounded:
With respect to a vinyl cyanide monomer unit, an aromatic alkenyl unit,
A graft copolymer (E), wherein at least one monomer unit (D ′) selected from alkyl (meth) acrylate units is graft-polymerized. 2. The graft copolymer (E) according to claim 1, wherein the monomer unit (D ′) contains a methyl methacrylate unit. 3. The refractive index of the polyorganosiloxane (A) containing an aryl group, the refractive index of the polymer (B), and the refractive index of the polymer (D) composed of the monomer unit (D ′). The graft copolymer (E) according to claim 1 or 2, wherein a difference between a maximum refractive index and a minimum refractive index is 0.02 or less. 4. The graft copolymer (E) according to claim 1, and at least one selected from vinyl cyanide monomer units, aromatic alkenyl units, and alkyl (meth) acrylate units. A (co) polymer (F) containing one type of monomer unit as a constituent component, which is a thermoplastic resin composition. 5. The constituent components of the (co) polymer (F) include:
The thermoplastic resin composition according to claim 4, comprising a methyl methacrylate unit. 6. The refractive index of an aryl group-containing polyorganosiloxane (A), the refractive index of a polymer (B), and the refractive index of a polymer (D) comprising a monomer unit (D ′). ,
6. The thermoplastic resin according to claim 4, wherein a difference between a maximum refractive index and a minimum refractive index of the (co) polymer (F) is 0.02 or less. Resin composition. 7. A film-shaped or sheet-shaped molded product obtained by thermoforming the thermoplastic resin composition according to claim 4. 8. A molded product obtained by injection molding the thermoplastic resin composition according to claim 4.