JP2005307074A - Thermoplastic resin composition and molded artice - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition having excellent surface impact characteristics, weatherability and a lusterless property, and also to provide a molded article of the same. <P>SOLUTION: The thermoplastic resin composition comprises 1-99.9 pts.mass of the 1st graft copolymer (A), which is prepared by grafting a vinyl-base polymer to a composite rubber form polymer(R) consisting of a polyorganosiloxane(S) and a poly(meth)acrylate (M) containing a (meth)acrylate-based monomer unit and a crosslinking agent and/or a graft decussation agent, 99-0.1 pts.mass of the 2nd graft copolymer (B), which is prepared by grafting a vinyl-based polymer to a rubbery polymer (G) having weight average particle diameter of above 0.6 μm to 30 μm, and 0-80 pts.mass of other thermoplastic resin (C). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a thermoplastic resin composition and a molded article that can be used as various industrial materials, and relates to a thermoplastic resin composition and a molded article having a matte appearance excellent in weather resistance and impact resistance, particularly surface impact characteristics at low temperatures. .

Improving the impact resistance of the resin material is very useful industrially, for example, not only expanding the application of the resin material, but also making it possible to cope with the reduction in thickness and size of the molded product. For this reason, various techniques have been proposed so far for improving the impact resistance of resin materials.
Among these, a technique for increasing the impact resistance of a material by combining a rubbery polymer and a hard resin has already been industrialized. Materials using such a method include acrylonitrile-butadiene-styrene (ABS) resin, high impact polystyrene (HIPS) resin, acrylonitrile-styrene-acrylic acid ester (ASA) resin, modified PPE resin, methyl methacrylate-butadiene- Examples thereof include thermoplastic resin compositions such as styrene (MBS) resin-reinforced polyvinyl chloride resin.
Among thermoplastic resin compositions, as a rubbery polymer, an ASA resin using a component such as an alkyl (meth) acrylate rubber which is a saturated rubber, or an AES resin using an ethylene-propylene rubber component has good weather resistance. It has the characteristic of having sex.
Furthermore, for the purpose of further improving impact resistance at low temperatures, thermoplastic resin compositions using a composite rubber of polyorganosiloxane and alkyl (meth) acrylate as components have also been proposed (for example, Patent Documents 1 to 1). 3).

On the other hand, recently, there has been an increasing demand for materials with significantly reduced gloss, so-called matte materials, mainly in the fields of automotive interior parts such as dashboards and instrument panels and resin-based building materials for housing.
As a method for obtaining such a matte material, a method of blending a cross-linked hard polymer into a thermoplastic resin composition has been proposed. (For example, see Patent Documents 4 to 12)
Japanese Patent Laid-Open No. 01-190746 Japanese Patent Laid-Open No. 01-282239 Japanese Patent Laid-Open No. 06-025492 JP 53-071146 A Japanese Patent Application Laid-Open No. 56-036355 JP 59-161459 A JP 63-086756 A JP-A 63-297449 Japanese Patent Laid-Open No. 08-073686 Japanese Patent Application Laid-Open No. 08-253641 Japanese Patent Laid-Open No. 08-199027 JP 2000-212293 A

However, in recent years, the requirements for material specifications have become more and more severe, and the thermoplastic resin composition obtained by these prior arts cannot sufficiently satisfy the requirements.
Specifically, the thermoplastic resin composition containing the crosslinked hard polymer as described above has a remarkable reduction in impact resistance, and its use is limited. In particular, the low-temperature impact property in consideration of outdoor use in winter and the surface impact property close to the practical impact test of molded products were particularly insufficient.
Therefore, there has been a strong demand for a material that satisfies all of impact resistance, particularly surface impact characteristics at low temperatures, weather resistance, and matte appearance at the same time.

  This invention is made | formed in view of the said situation, and it aims at providing the thermoplastic resin composition and molded article which have the surface impact characteristic in low temperature, a weather resistance, and favorable matte property.

As a result of intensive studies to solve the above problems, the present inventors have found that a thermoplastic resin composition containing at least two specific types of graft copolymers can solve the above problems, and completed the present invention. .
That is, the first aspect of the present invention is a poly (meth) acrylic acid ester containing polyorganosiloxane (S), a (meth) acrylic acid ester monomer unit, a crosslinking agent and / or a graft crossing agent. 1 to 99.9 parts by mass of a first graft copolymer (A) obtained by grafting a vinyl polymer on the composite rubber-like polymer (R) comprising (M),
99 to 0.1 parts by mass of a second graft copolymer (B) obtained by grafting a vinyl polymer to a rubbery polymer (G) having a mass average particle diameter of more than 0.6 μm and not more than 30 μm, and other A thermoplastic resin composition comprising 0 to 80 parts by mass of a thermoplastic resin (C).
The second aspect of the present invention is a molded article comprising the thermoplastic resin composition of the first aspect.
The third aspect of the present invention is a molded product obtained by sheet-molding the thermoplastic resin composition of the first aspect.
A fourth aspect of the present invention is a molded product formed by profile extrusion molding of the thermoplastic resin composition of the first aspect.

  The thermoplastic resin composition and molded article of the present invention have surface impact characteristics at low temperatures, weather resistance, and good matting properties. These balances are at a very high level that cannot be obtained by conventional thermoplastic resin compositions, and the utility value as various industrial materials is extremely high.

Hereinafter, the present invention will be described in more detail.
≪Thermoplastic resin composition≫
The thermoplastic resin composition of the present invention comprises 1 to 99.9 parts by mass of the first graft copolymer (A), 99 to 0.1 parts by mass of the second graft copolymer (B), and other heat. It consists of 0 to 80 parts by mass of the plastic resin (C).

<Graft copolymer (A)>
First, the first graft copolymer (A) will be described in detail.
The graft copolymer (A) is obtained by grafting a vinyl polymer onto a composite rubber-like polymer (R) composed of a polyorganosiloxane (S) and a poly (meth) acrylic acid ester (M).

[Polyorganosiloxane (S)]
Although there is no restriction | limiting in particular as polyorganosiloxane (S) which comprises the composite rubber-like polymer (R) of a graft copolymer (A), The polyorganosiloxane containing a vinyl polymerizable functional group is preferable.
Here, the “vinyl polymerizable functional group” means a functional group having a double bond and copolymerizable with other vinyl monomers, such as a vinyl group, an acryloxy group, a methacryloxy group, a styryl group, and the like. Can be mentioned.
As the polyorganosiloxane containing a vinyl polymerizable functional group, a polyorganosiloxane containing a vinyl polymerizable functional group-containing siloxane unit is preferable because it can be easily combined with the vinyl polymer (B1). A silicon atom having 0.3 to 3 mol% of a group-containing siloxane unit and 97 to 99.7 mol% of a dimethylsiloxane unit and having 3 or more siloxane bonds is 1 mol with respect to all silicon atoms in the polyorganosiloxane. % Or less is preferable because both the impact resistance and the colorability of the resulting thermoplastic resin composition are excellent.

  The vinyl polymerizable functional group-containing siloxane constituting the vinyl polymerizable functional group-containing siloxane unit is not limited as long as it contains a vinyl polymerizable functional group and can be bonded to dimethylsiloxane via a siloxane bond, In consideration of reactivity with dimethylsiloxane, various alkoxysilane compounds containing a vinyl polymerizable functional group are preferred. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, methacryloyloxysiloxanes such as γ-methacryloyloxypropyldiethoxymethylsilane and ∂-methacryloyloxybutyldiethoxymethylsilane, vinylsiloxanes such as tetramethyltetravinylcyclotetrasiloxane, p-vinylphenyldimethoxymethylsilane, and γ-mer Examples include mercaptosiloxanes such as cabtopropyldimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane. . These vinyl polymerizable functional group-containing siloxanes can be used singly or in combination of two or more.

  As the dimethylsiloxane constituting the dimethylsiloxane unit, for example, a cyclic dimethylsiloxane having 3 or more members is preferable, and among them, those having 3 to 7 members are particularly preferable. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These can be used alone or in combination of two or more.

The polyorganosiloxane (S) may contain a siloxane crosslinking agent as a constituent component. Thereby, the impact resistance of the thermoplastic resin composition obtained improves.
Examples of the siloxane crosslinking agent include trifunctional or tetrafunctional silane crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane.

The polyorganosiloxane (S) can be produced, for example, as follows.
First, a siloxane-based crosslinking agent is added to a siloxane mixture composed of a vinyl-polymerizable functional group-containing siloxane and dimethylsiloxane as necessary, and then emulsified using an emulsifier and water to obtain a siloxane mixture latex.
Next, the siloxane mixture latex is made into fine particles by using a homomixer that makes fine particles by a shearing force generated by high-speed rotation, a homogenizer that makes fine particles by jetting power from a high-pressure generator, or the like. Here, it is preferable to use a high-pressure emulsifier such as a modifier because the particle size distribution of the siloxane mixture latex can be reduced.
Next, the finely divided siloxane mixture latex is added to an acid aqueous solution containing an acid catalyst and polymerized at a high temperature. Then, the reaction solution is cooled and further neutralized with an alkaline substance such as caustic soda, caustic potash or sodium carbonate to stop the polymerization, thereby obtaining polyorganosiloxane (S).

In the production of the polyorganosiloxane (S), examples of the emulsifier include an anionic emulsifier. Examples of the anionic emulsifier include sodium alkylbenzene sulfonate and sodium polyoxyethylene nonylphenyl ether sulfate. Among these, sulfonic acid-based emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate are particularly preferable.
These emulsifiers are used in the range of about 0.05 to 5 parts by mass with respect to 100 parts by mass of the siloxane mixture.

Examples of the acid catalyst used for the polymerization of the polyorganosiloxane (S) include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. It is done. These acid catalysts are used alone or in combination of two or more. Among these, aliphatic substituted benzene sulfonic acid is preferable, and n-dodecyl benzene sulfonic acid is particularly preferable because of excellent stability of the polyorganosiloxane (S) latex.
Further, when n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used in combination, the emulsifier used in the polyorganosiloxane (S) latex can be suppressed as much as possible from affecting the color of the molded product.

The mass average particle diameter of the polyorganosiloxane (S) is not particularly limited, but the mass average particle diameter is preferably less than 100 nm for the purpose of improving the pigment colorability of the resulting thermoplastic resin composition. More preferably, it is less than 90 nm, More preferably, it is less than 80 nm. On the other hand, the lower limit of the mass average particle diameter is preferably 10 nm, more preferably 20 nm, and even more preferably 30 nm because it can prevent an increase in latex viscosity and coagulum (coagulum) generation during production.
In addition, as a method of controlling the particle diameter of polyorganosiloxane (S), the method described in Unexamined-Japanese-Patent No. 5-279434 is employable, for example.

  The polyorganosiloxane (S) content in the composite rubbery polymer (R) is preferably 1% by mass to 99% by mass, more preferably 2% by mass to 80% by mass, and particularly preferably 3% by mass to 50% by mass. %. When the polyorganosiloxane (S) is within this range, the resulting thermoplastic resin composition is more excellent in impact resistance and molded appearance.

[Poly (meth) acrylic acid ester (M)]
The poly (meth) acrylic acid ester (M) constituting the composite rubber polymer (R) together with the polyorganosiloxane (S) is composed of a (meth) acrylic acid ester monomer unit, a crosslinking agent and / or a graft. It contains a crossing agent as an essential component. By containing a (meth) acrylic acid ester monomer and a crosslinking agent and / or a graft crossing agent, the pigment colorability of the thermoplastic resin composition of the present invention can be improved.

Examples of (meth) acrylic acid ester monomers include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate; and methacrylic acid Examples include methacrylic acid alkyl esters such as hexyl, 2-ethylhexyl methacrylate, and n-lauryl methacrylate. Among these, n-butyl acrylate is particularly preferable.
Examples of the cross-linking agent include dimethacrylate compounds, and specific examples thereof include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate. .
Examples of the graft crossing agent include allyl compounds, and specific examples thereof include allyl methacrylate, triallyl cyanurate and triallyl isocyanurate.

  The lower limit of the total amount of the crosslinking agent and / or grafting agent is 0.1% by mass of the (meth) acrylic acid ester monomer unit, preferably because the pigment colorability of the thermoplastic resin composition is more excellent, preferably 0.2% by mass, more preferably 0.5% by mass. Further, the upper limit is that the amount of coagulum (coagulum) during the production of the composite rubber-like polymer (R) and the second graft copolymer (B) is reduced, so that the (meth) acrylic acid ester monomer It is 5% by mass of the unit, preferably 3% by mass, and more preferably 2% by mass.

[Production method of composite rubber-like polymer (R)]
It does not restrict | limit especially as a manufacturing method of a composite rubber-like polymer (R). For example, polyorganosiloxane (S) latex and poly (meth) acrylic acid ester (M) latex produced separately are hetero-coagulated or co-enlarged, polyorganosiloxane (S) latex and poly (meth) acrylic acid Examples thereof include a method in which the other polymer is formed in the presence of either one of the ester (M) latexes to be combined. Among them, since the impact resistance and pigment colorability of the obtained thermoplastic resin composition are more excellent, in the presence of the polyorganosiloxane (S) latex, the (meth) acrylate monomer and the crosslinking agent and / or A method of emulsion polymerization of a monomer mixture containing a graft crossing agent is preferred.

Preferable specific examples of the emulsifier used in the method for producing the composite rubber polymer (R) include sodium or potassium salts of fatty acids such as oleic acid, stearic acid, myristic acid, stearic acid and palmitic acid, or lauryl sulfate. Examples thereof include sodium, sodium N-lauroyl sarcosinate, dipotassium alkenyl succinate, sodium alkyldiphenyl ether disulfonate, and the like. Among these, an acid emulsifier having two or more functional groups in one molecule or a salt thereof is preferable because it can further suppress gas generation during molding of the thermoplastic resin composition. Furthermore, among the acid type emulsifiers having two functional groups in one molecule, dipotassium alkenyl succinate or sodium alkyldiphenyl ether disulfonate is preferable, and in particular, the composite rubber polymer (R) is coagulated from the latex by adding sulfuric acid. From the viewpoint of easy recovery, dipotassium alkenyl succinate is more preferable.
Specific examples of dipotassium alkenyl succinate include dipotassium octadecenyl succinate, dipotassium heptadecenyl succinate, and dipotassium hexadecenyl succinate. These can be used alone or in combination of two or more.

The vinyl polymer that forms the graft portion of the graft copolymer (A) is not particularly limited as long as it is a hard polymer at room temperature, but a vinyl cyanide monomer, an aromatic vinyl monomer, ) It is preferably composed of one or more monomer units selected from acrylic ester monomers.
In the present invention, “vinyl” means having a substituted or unsubstituted vinyl group (CH ₂ ═CH—) in the monomer molecule as the raw material.

Specific examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile.
Specific examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene and the like.
Specific examples of the (meth) acrylic acid ester monomer include methacrylate monomers such as methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate; methyl acrylate, ethyl acrylate, acrylic acid n -Acrylic acid ester monomers such as butyl.
Of these, it is particularly preferable that the first graft copolymer (A) to be obtained is composed of monomer units containing styrene and acrylonitrile because of excellent thermal stability.

  In the graft copolymer (A), the content of the composite rubber-like polymer (R) and the vinyl polymer forming the graft portion is not particularly limited, but the thermoplasticity including the graft copolymer (A) is not limited. Since the impact resistance and pigment colorability of the resin composition are more excellent, the composite rubber-like polymer (R) is preferably 20% by mass to 80% by mass, and the vinyl polymer is 80% by mass to 20% by mass. More preferably, the composite rubber-like polymer (R) is 25 mass% to 75 mass%, the vinyl polymer is 75 mass% to 25 mass%, and more preferably, the composite rubber-like polymer (R) is 30 mass%. % To 70% by mass, and the vinyl polymer is 70% to 30% by mass.

[Production Method of Graft Copolymer (A)]
The graft copolymer (A) is obtained by grafting a vinyl polymer to the composite rubber-like polymer (R).
The graft copolymer (A) is produced, for example, by emulsion graft polymerization. Specifically, the composite rubber-like polymer (R) latex, at least one selected from a vinyl cyanide monomer, an aromatic vinyl monomer, a (meth) acrylic acid ester monomer, and the like It is produced by a known radical polymerization technique in the presence of an emulsifier.
At this time, various chain transfer agents for controlling the graft ratio and the molecular weight of the graft component can be added to the monomer component.

  As the radical polymerization initiator added during the polymerization, a peroxide, an azo initiator, and a redox initiator obtained by further combining an oxidizing agent / reducing agent with these are used. Of these, redox initiators are preferable, and redox initiators that combine ferrous sulfate, sodium pyrophosphate, glucose, hydroperoxide, ferrous sulfate, disodium ethylenediaminetetraacetate, longalite, hydroperoxide are particularly preferred. Agents are preferred.

  Moreover, the emulsifier used in the polymerization may not be added at all before the graft polymerization step by using the emulsifier used in the production of the composite rubber-like polymer (R) as it is. May be added. There is no restriction | limiting in particular as an emulsifier added here, For example, the emulsifier used in the case of composite rubber-like polymer (R) manufacture can be utilized.

  As a method of recovering the graft copolymer (A) from the graft copolymer (A) latex obtained by emulsion graft polymerization, the latex is put into hot water in which a coagulant is dissolved, and the slurry state A method of coagulating and recovering (wet method), a method of spraying the latex in a heated atmosphere to recover the graft copolymer (A) semi-directly (spray drying method), and the like.

Examples of the coagulant used in the wet method include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid, and metal salts such as calcium chloride, calcium acetate, and aluminum sulfate. The coagulant is selected in consideration of the emulsifier used in the polymerization. That is, when only a carboxylic acid soap such as a fatty acid soap or a rosin acid soap is used, the graft copolymer (A) can be recovered by using any coagulant. When an emulsifier exhibiting a stable emulsifying power is contained even in the acidic region, the inorganic acid cannot be sufficiently recovered, so that it is necessary to use a metal salt as a coagulant.
In the wet method, in order to obtain a dry graft copolymer (A) from the slurry of the graft copolymer (A), first, the emulsifier residue remaining in the graft copolymer (A) is eluted in water and washed. Then, this slurry is dehydrated with a centrifugal or press dehydrator, and then dried with an air dryer or the like to obtain a powder or particulate graft copolymer (A). At this time, dehydration and drying may be performed simultaneously with a press dehydrator or an extruder. Furthermore, the graft copolymer discharged from the press dehydrator or the extruder can be directly supplied to the extruder or the molding machine for producing the thermoplastic resin composition of the present invention to produce a molded product.

<Second Graft Copolymer (B)>
Next, the second graft copolymer (B) will be described in detail.
The graft copolymer (B) is obtained by grafting a vinyl polymer onto a rubber-like polymer (G) having a mass average particle diameter of more than 0.6 μm and not more than 30 μm.

[Rubber polymer (G)]
The rubbery polymer (G) is not particularly limited as long as the mass average particle diameter is more than 0.6 μm and not more than 30 μm, but it is excellent in the balance between the weather resistance and the matte property of the resulting thermoplastic resin composition. It is preferable that it is a (meth) acrylic ester rubber-like polymer (G1) containing a (meth) acrylic ester monomer unit.
In addition to this, since the thermoplastic resin composition is excellent in impact resistance, particularly surface impact, polyorganosiloxane, (meth) acrylic acid ester monomer units, crosslinking agents and / or grafts are used. More preferably, it is a composite rubber-like polymer (G2) comprising a poly (meth) acrylic acid ester containing a cross-linking agent.
Here, the “composite rubber-like polymer” refers to a state in which two or more rubber-like polymers are entangled in whole or in part at a micro level or chemically bonded. However, it is not defined as a completely uniform state, and independent domains may be formed in submicron or nano order.

The (meth) acrylic acid ester-based monomer unit constituting the poly (meth) acrylic acid ester of the (meth) acrylic acid ester-based rubbery polymer (G1) and the composite rubber-like polymer (G2) is described above. The thing similar to what was mentioned in the poly (meth) acrylic acid ester (M) of this can be used.
Moreover, as polyorganosiloxane which comprises a composite rubber-like polymer (G2), the thing similar to the above-mentioned polyorganosiloxane (S) can be used.

  When the rubber-like polymer (G) is a composite rubber-like polymer (G2), the preferred ratio of the polyorganosiloxane and the poly (meth) acrylate is the matte property of the thermoplastic resin composition of the present invention. Since both the impact resistance is excellent, the polyorganosiloxane is 1% by mass to 99% by mass, and the poly (meth) acrylic acid ester is 99% by mass to 1% by mass (total 100% by mass), preferably the polyorganosiloxane 2 Mass% to 90 mass%, poly (meth) acrylic acid ester 98 mass% to 10 mass% (total 100 mass%), more preferably polyorganosiloxane 3 mass% to 80 mass%, poly (meth) acrylic acid ester 97 Mass% to 20 mass% (total 100 mass%).

The method for producing the composite rubber-like polymer (G2) is not particularly limited. For example, a method of heteroaggregating or co-enlarging each particle of individually produced polyorganosiloxane and poly (meth) acrylate, Examples thereof include a method of forming the other polymer in the presence of one of polyorganosiloxane and poly (meth) acrylic acid ester.
In particular, in the production of the composite rubber-like polymer (G2), since it is stable and less agglomerated, and it has excellent controllability to the desired particle size, poly (meth) is present in the presence of polyorganosiloxane. A method of polymerizing a mixture containing a (meth) acrylic acid ester monomer or a (meth) acrylic acid ester monomer mixture constituting an acrylic ester and a crosslinking agent and / or a graft crossing agent is preferable.
Specifically, as a preferable specific production example of the composite rubber-like polymer (G2), polyorganosiloxane is dissolved uniformly in the monomer mixture constituting the poly (meth) acrylate. The composite rubber-like polymer (G2) can be obtained by suspension polymerization of the mixture.

  The rubbery polymer (G) needs to have a mass average particle diameter of more than 0.6 μm and 30 μm or less in order to develop the excellent matte appearance and impact resistance which are the objects of the present invention. It is preferably more than 3 μm and not more than 20 μm, more preferably more than 5 μm and not more than 10 μm. When the particle diameter of the graft copolymer is 0.6 μm or less, the matte appearance that is the object of the present invention cannot be expressed in the resin composition containing the graft copolymer. Both matte appearance and impact resistance cannot be expressed.

The method for controlling the mass average particle diameter of the rubber-like polymer (G) within the above range is not particularly limited. For example, the raw material constituting the (meth) acrylate rubber-like polymer (G1), That is, the raw material constituting the (meth) acrylic acid ester monomer or the monomer mixture or the composite rubber-like polymer (G2), that is, the (meth) acrylic acid ester monomer and the crosslinking agent and / or graft By changing the mixture and the polyorganosiloxane mixture in an aqueous medium such as water to form a (mixed) emulsion, and the type and amount of the dispersant used during suspension polymerization. It becomes possible.
More specifically, for example, when a mixture such as that described above is dispersed in an aqueous medium, a high-speed stirrer, a homomixer, a homogenizer or the like is used to control the shearing force or loading time. (Mixed) control the dispersed particle size of the emulsion. By subjecting this (mixed) emulsion to suspension polymerization, it becomes possible to obtain a rubber-like polymer (G) having a target mass average particle diameter as an aqueous dispersion.

  The polymerization initiator that can be used in the suspension polymerization is not particularly limited, and known ones can be used, and a polymerization initiator having a half-life temperature appropriate for the polymerization temperature condition of the monomer to be used is used. Just do it. For example, peroxides such as potassium peroxide, lauroyl peroxide and benzoyl peroxide, and azo compounds such as azobisisobutyronitrile can be used. These polymerization initiators are dissolved at the same time when preparing (mixed) emulsion of raw materials constituting the (meth) acrylic acid ester-based rubbery polymer (G1) and the composite rubbery polymer (G2) ( Mixing) It is preferable to encapsulate it in emulsion particles because suspension polymerization can be carried out quickly only by heating the (mixed) emulsion having a controlled particle size.

In the suspension polymerization, it is preferable to use a dispersant. Examples of suitable dispersants include sodium or potassium salts of fatty acids such as oleic acid, stearic acid, myristic acid, and palmitic acid, or sodium lauryl sulfate, Emulsifiers such as sodium N-lauroyl sarcosinate, dipotassium alkenyl succinate, sodium alkyldiphenyl ether disulfonate, organic colloidal dispersants such as polyacrylic acid, polyvinyl alcohol, carboxymethylcellulose, gelatin, tragacanth, barium sulfate, magnesium carbonate, calcium phosphate One or more inorganic colloidal dispersants such as the above can be used.
The amount of these dispersants varies depending on the type of dispersant and the desired particle size, but is generally in the range of 0.01 to 10 parts by mass.

[Production method of graft copolymer (B)]
The second graft copolymer (B) can be obtained by graft polymerization of a vinyl polymer to the rubber-like polymer (G) produced as described above.
The vinyl monomer used for graft polymerization is not particularly limited, but the glass transition temperature of the vinyl polymer constituting the graft portion is the ambient temperature because it is excellent in handleability when blended with other resin materials. It is preferable to select a monomer or a monomer mixture as described above. More preferably, the vinyl monomer is selected so that the glass transition temperature of the vinyl polymer is 50 ° C. or higher, more preferably 70 ° C. or higher. It is preferable to select.
Specific examples of vinyl monomers that can be used include (meth) acrylic acid ester monomers, aromatic vinyl monomers, vinyl cyanide monomers, and the like. Can use those described in the graft copolymer (A).

  In the graft copolymer (B), the ratio of the rubber-like polymer (G) to the vinyl polymer constituting the graft portion is not particularly limited, but the powder properties of the graft copolymer (B) and For reasons such as excellent impact resistance of the blended resin composition, 1 to 200 parts by weight, preferably 5 to 150 parts by weight, and more preferably 5 to 150 parts by weight, based on 100 parts by weight of the rubber-like polymer (G). 10 to 100 parts by mass.

The method for graft polymerization of the vinyl polymer to the rubber polymer (G) is not particularly limited, but since the rubber polymer (G) can be prepared by suspension polymerization, the rubber polymer (G) is continuously produced. Graft polymerization can be performed by supplying a vinyl monomer or vinyl monomer mixture to be used for graft polymerization to the aqueous dispersion.
At that time, as the emulsifier (dispersant) and the polymerization initiator used in the graft polymerization, the residue used in the production of the rubber-like polymer (G) may be used, and the same or different kinds of emulsifiers as necessary. (Dispersant), a polymerization initiator, and a chain transfer agent may be additionally used.

  The method of recovering the second graft copolymer (B) from the aqueous dispersion thus obtained may be recovered, for example, by washing and drying after standing separation as it is, or dissolving the coagulant. It is granulated by throwing it into the heated hot water and recovered by a wet method of coagulating into a slurry state, or by spraying the aqueous dispersion in a heated atmosphere, and recovered semi-directly as a powder. The second graft copolymer (B) can be recovered by a method such as spray drying.

As the coagulant used in the wet method, inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid, and metal salts such as calcium chloride, calcium acetate, and aluminum sulfate can be used. The coagulant is selected in combination with the emulsifier used in the polymerization. That is, when only carboxylic acid soaps such as fatty acid soaps and rosin acid soaps are used, they can be recovered using any coagulant, but stable emulsification is possible even in acidic regions such as sodium alkylbenzene sulfonate. When an emulsifier exhibiting power is contained, the above inorganic acid is insufficient, and a metal salt must be used.
In order to obtain a dried powder or granular second graft copolymer (B) from the slurry obtained by the wet method, first, the remaining emulsifier residue is eluted in water, washed, and then the slurry is centrifuged. Alternatively, the second graft copolymer dried after passing through a process such as a method of drying with an air dryer after dehydrating with a press dehydrator, a method of simultaneously performing dehydration and drying with a press dehydrator or an extruder, etc. B) can be obtained in powder or particulate form. At this time, it is also possible to directly send the product discharged from the press dehydrator or the extruder to an extruder or a molding machine for producing the resin composition to obtain a pellet or a molded product.

<Other thermoplastic resin (C)>
Other thermoplastic resins (C) that can be used in the present invention are not particularly limited. For example, polymethyl methacrylate, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-N-substituted maleimide Terpolymer, styrene-maleic anhydride copolymer, styrene-maleic anhydride-N-substituted maleimide terpolymer, polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin), polychlorinated Polyolefins such as vinyl, polyethylene and polypropylene, styrene elastomers such as styrene-butadiene-styrene (SBS), styrene-butadiene (SBR), hydrogenated SBS, styrene-isoprene-styrene (SIS), various olefin elastomers, etc. Polyester elastomer, polystyrene, methyl methacrylate - styrene copolymer (MS resin), acrylonitrile - styrene - methyl methacrylate terpolymer, polyacetal resins, modified polyphenylene ether (modified PPE resin), ethylene - vinyl acetate copolymer Weight Examples thereof include polyphenylene sulfide (PPS resin), polyethersulfone (PES resin), polyetheretherketone (PEEK resin), polyarylate, liquid crystal polyester resin, and polyamide (nylon).
Among these, polymethyl methacrylate, AS resin, acrylonitrile-styrene-N-substituted maleimide terpolymer, styrene-maleic anhydride-N-substituted maleimide terpolymer, polycarbonate resin, PBT resin are preferable. , PET resins, polyvinyl chloride, polystyrene, MS resin, acrylonitrile - styrene - methyl methacrylate terpolymer, is modified PPE resin, at least one element selected from the group consisting of polyamide.
These thermoplastic resins (C) can be used alone or in combination of two or more depending on the purpose.
The thermoplastic resin (C) can be used within a range of 0 to 80 parts by mass in 100 parts by mass of the thermoplastic resin composition.

  The thermoplastic resin composition of the present invention comprises a first graft copolymer (A), a second graft copolymer (B), and, if necessary, another thermoplastic resin (C), V It is manufactured by mixing with a mold blender or Henschel mixer, and melt-kneading the mixture. In the melt-kneading, an extruder or a kneader such as a Banbury mixer, a heating kneader, or a roll can be used.

  The thermoplastic resin composition thus obtained can be directly used as a raw material for producing molded products. If necessary, this thermoplastic resin composition may be added to a colorant such as a pigment or dye, a heat stabilizer, a light stabilizer, a reinforcing agent, a filler, a flame retardant, a foaming agent, a lubricant, a plasticizer, or an antistatic agent. Agents, processing aids, etc. can be blended.

≪Molded product≫
The molded product of the present invention was formed by molding the above-described thermoplastic resin composition of the present invention by various molding methods such as an injection molding method, an extrusion molding method, a blow molding method, a compression molding method, a calendar molding method, and an inflation molding method. Is.
The molded product of the present invention may be a molded product composed only of the above-described thermoplastic resin composition of the present invention. In some cases, the above-described thermoplastic resin composition of the present invention may be replaced with other resins or metals. It is also possible to use it as a molded article coated with the like. Here, other resins that can be coated are not particularly limited, but those described with the other thermoplastic resins (C) described above, rubber modified such as ABS resin and high impact polystyrene resin (HIPS), etc. Thermosetting resins such as thermoplastic resins, phenol resins and melamine resins can be widely used.
The thermoplastic resin composition of the present invention can be formed into a molded product subjected to primary processing by profile extrusion molding, sheet molding, or multilayer sheet molding with the above-mentioned other materials by the molding method. The molded product subjected to primary processing in this way can be a material that can be used in a wide range of industrial fields by thermoforming, vacuum forming, or the like depending on the application.

  The molded article of the present invention is used in various applications. For example, as industrial applications, vehicle parts, especially various exterior / interior parts used without painting, wall materials, building material parts such as window frames, tableware, toys, It is suitable for electric appliance housings such as household appliance parts such as vacuum cleaner housings, television housings, air conditioner housings, interior members, marine members and communication equipment housings, notebook personal computer housings, PDA housings, liquid crystal projector housings and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to a following example. Hereinafter, “%” and “part” are based on mass unless otherwise specified.

In the following examples, the average particle size of the composite rubbery polymer (R) and the rubbery polymer (G) was measured by the following method.
(1) Measurement of average particle diameter of composite rubber-like polymer (R) The average particle diameter was measured using a submicron particle size distribution analyzer CHDF-2000 manufactured by MATEC APPLIED SCIENCE.
(2) Measurement of average particle diameter of rubbery polymer (G) The average particle diameter was measured using a particle size distribution measuring device LS230 manufactured by BECKMAN COULTER.

[Production Example 1] Production of polyorganosiloxane (S-1) 98 parts of octamethylcyclotetrasiloxane and 2 parts of γ-methacryloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of a siloxane-based mixture.
After adding 100 parts of a siloxane-based mixture to 300 parts of ion-exchanged water in which 0.67 parts of sodium dodecylbenzenesulfonate is dissolved, the mixture is stirred for 2 minutes at 10,000 rpm with a homomixer, and then at a pressure of 30 MPa with a homogenizer. A stable premixed organosiloxane latex was obtained through one pass.
10 parts of dodecylbenzenesulfonic acid and 90 parts of ion-exchanged water were injected into a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer to prepare a 10% by mass aqueous solution of dodecylbenzenesulfonic acid. . This aqueous solution was heated to 85 ° C. with stirring, and the above premixed organosiloxane latex was dropped and polymerized over 4 hours. After completion of the dropping, the solution was maintained at 85 ° C. for 1 hour, and then cooled. Next, this reaction product was neutralized with an aqueous sodium hydroxide solution to obtain a polyorganosiloxane (S-1) latex having a solid content of 18.9% by mass and a mass average particle size of 60 nm.

[Production Example 2] Production of polyorganosiloxane (S-2) 97.5 parts of octamethylcyclotetrasiloxane, 0.5 part of γ-methacryloxypropyldimethoxymethylsilane, and 2.0 parts of tetraethoxysilane were mixed. As a result, 100 parts of a siloxane-based mixture was obtained.
100 parts of the siloxane-based mixture was added to 200 parts of ion-exchanged water in which 1.0 part of sodium dodecylbenzenesulfonate and 1.0 part of dodecylbenzenesulfonic acid were dissolved, and the mixture was stirred for 2 minutes at 10,000 rpm with a homomixer. Thereafter, it was treated once with a homogenizer at a pressure of 30 MPa to obtain a stable premixed organosiloxane latex.
The premixed organosiloxane latex was transferred to a reactor equipped with a reagent injection vessel, a cooling tube, a jacket heater and a stirrer, stirred and mixed, heated at 80 ° C. for 5 hours, and then left to cool to 20 ° C. for 48 hours. Later, it was neutralized with an aqueous sodium hydroxide solution to obtain a polyorganosiloxane (S-2) latex having a solid content of 32% by mass and a mass average particle size of 170 nm.

[Production Example 3] Production of composite rubber-like polymer (R-1) and first graft copolymer (A-1) In a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer , 8 parts (solid content) of polyorganosiloxane (S-1) latex, 0.2 part of polyoxyethylene alkylphenyl ether sulfate, 220 parts of ion exchange water (including water in polyorganosiloxane (S-1) latex) , 41.6 parts of n-butyl acrylate, 0.3 part of allyl methacrylate, 0.1 part of 1,3-butylene glycol dimethacrylate, and 0.11 part of t-butyl hydroperoxide were stirred in a nitrogen stream. While throwing.
This was heated to 60 ° C., and an aqueous solution in which 0.000075 parts of ferrous sulfate, 0.000225 parts of disodium ethylenediaminetetraacetate, and 0.2 parts of sodium formaldehyde sulfoxylate were dissolved in 5 parts of ion-exchanged water. Was added for radical polymerization. At this time, the content rose to about 80 ° C. due to polymerization of the monomer component. This temperature was maintained for 1 hour to obtain a composite rubber-like polymer (R-1) latex. The composite rubber-like polymer (R-1) had a mass average particle diameter of 110 nm.

Next, the temperature inside the reactor was set to 70 ° C., and an aqueous solution in which 0.25 parts of sodium formaldehyde sulfoxylate was dissolved in 10 parts of ion-exchanged water was added, followed by 2.5 parts of acrylonitrile, 7.5 parts of styrene. And a mixed solution of 0.05 part of t-butyl hydroperoxide was added dropwise over 30 minutes, and after completion of the dropwise addition, the temperature was maintained at 70 ° C. for 1 hour for polymerization.
Subsequently, 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.2 part of sodium formaldehyde sulfoxylate, 0.2 part of polyoxyethylene alkylphenyl ether sulfate, and ion exchange An aqueous solution comprising 5 parts of water was added, and a mixture of 10 parts of acrylonitrile, 30 parts of styrene, and 0.2 part of t-butyl hydroperoxide was added dropwise at an internal temperature of 75 ° C. over 2 hours for polymerization. I was damned. After completion of dropping, the content was cooled after maintaining the temperature at 75 ° C. for 30 minutes.
0.5 parts of alkenyl succinic acid dipotassium salt was added to this latex to obtain a first graft copolymer (A-1) latex.
Next, 150 parts of a 1% calcium acetate aqueous solution was heated to 60 ° C., and 100 parts of the graft copolymer (A-1) latex was added thereto, and further heated at 90 ° C. for 5 minutes to obtain a coagulated slurry. . Next, the precipitate was dehydrated, washed, and dried to obtain a white powdery first graft copolymer (A-1).

[Production Example 4] Production of composite rubber-like polymer (R-2) and first graft copolymer (A-2) In Production Example 3, the polyorganosiloxane (S-1) latex used is from 8 parts to 3 parts. Parts (solid content), 41.6 parts of n-butyl acrylate, 0.3 part of allyl methacrylate, 0.1 part of 1,3-butylene glycol dimethacrylate, 46.6 parts of n-butyl acrylate In the same manner as in Production Example 3, except that allyl methacrylate was changed to 0.3 part and 1,3-butylene glycol dimethacrylate was changed to 0.1 part, a composite rubber-like polymer (R- 2) and a first graft copolymer (A-2) were obtained.

[Production Example 5] Production of composite rubber-like polymer (R-3) and first graft copolymer (A-3) In Production Example 3, the polyorganosiloxane (S-1) latex used is from 8 parts to 15 parts. Parts (solid content), 41.6 parts of n-butyl acrylate, 0.3 part of allyl methacrylate, 0.1 part of 1,3-butylene glycol dimethacrylate, 44.6 parts of n-butyl acrylate In the same manner as in Production Example 3, except that allyl methacrylate was changed to 0.3 part and 1,3-butylene glycol dimethacrylate was changed to 0.1 part, a composite rubber-like polymer (R- 3) and a first graft copolymer (A-3) were obtained.

[Production Example 6] Production of composite rubber-like polymer (R-4) and first graft copolymer (A-4) In Production Example 3, instead of polyorganosiloxane (S-1) latex, polyorgano A composite rubber-like polymer (R-4) and a first graft copolymer (A-4) having a mass average particle diameter of 160 nm were obtained in the same manner except that siloxane (S-2) was used.

[Production Example 7] Production of rubber-like polymer (G-1) and second graft copolymer (B-1) Polyorganosiloxane (S-1) latex was frozen and thawed, and separated into two layers. Washing and drying were performed to obtain oily polyorganosiloxane (S-1).
8 parts of this oily polyorganosiloxane (S-1), (meth) acrylic acid ester monomer {0.7 parts of allyl methacrylate, 71.3 parts of n-butyl acrylate}, benzoyl peroxide 4 parts were mixed to obtain a premixed solution. This was mixed with 0.25 part of sodium alkyldiphenyl ether disulfonate (“PEX SS-L” manufactured by Kao Corporation, solid content) and 295 parts of deionized water, and homomixer (“HG92” manufactured by SMT Corporation). Type and the same rotor "PB-1") for 15 minutes at 10,000 rpm to obtain a premixed emulsion.
This premixed emulsion is put into a reactor equipped with a cooling tube, a jacket heater and a stirrer, and is heated to 70 ° C. while being stirred and polymerized, and heated at 75 ° C. for 1 hour after the exothermic peak is settled. And the slurry of the rubber-like polymer (G-1) whose mass mean particle diameter is 9 micrometers was obtained.

Subsequently, while maintaining the internal temperature at 75 ° C., an aqueous solution comprising 0.1 part Rongalite, 0.0001 part ferrous sulfate heptahydrate, 0.0003 part disodium ethylenediaminetetraacetate and 5 parts deionized water was added. Subsequently, a mixture consisting of 20 parts of methyl methacrylate and 0.15 part of t-butyl hydroperoxide was dropped into the aqueous dispersion of the composite rubber-like polymer over 2 hours for polymerization. After completion of the dropwise addition, heat treatment was further performed for 1 hour at 75 ° C. to obtain an aqueous dispersion of the graft copolymer (B-1).
The mixture was poured into a 1.5% calcium acetate aqueous solution at 90 ° C. in the same amount as the obtained aqueous dispersion, and further heat-treated at 98 ° C. for 5 minutes. Then, dehydration and washing were repeated. The mixture was then dried to obtain a graft copolymer (B-1) in the form of a white powder.

[Production Example 8] Rubbery polymers (G-2) to (G-10) and (g-11), second graft copolymers (B-2) to (B-10) and (b-11) In Production Example 7, the types and amounts of the polyorganosiloxane and (meth) acrylate monomer (monomer used for producing the rubbery polymer (G)) to be used, and the homomixer mixing conditions are as follows. As shown in Table 1, composite rubber-like polymers (G-2) to (G-10) and (g-11) were obtained, and vinyls whose types and amounts were listed in Table 1 were obtained in the composite rubber-like polymer. System monomers (monomers used for graft polymerization) were subjected to graft polymerization in the same manner as in Production Example 7 to obtain second graft copolymers (B-2) to (B-10) and (b-11). Obtained.

[Production Example 9] Production of rubber-like polymer (g-12) and second graft copolymer (b-12) In Production Example 7, the polyorganosiloxane (S-2) used was recovered by lyophilization. Polymerization (in this example, emulsion polymerization) and recovery treatment were performed in the same manner except that the oil-like one was changed to polyorganosiloxane (S-2) latex, and the second graft copolymer (b-12) was obtained. Obtained.

  In Production Examples 7 to 9, rubbery polymers (G-1) to (G-9) and (g-11) to (g-12) are polyorganosiloxane and (meth) acrylic monomer units. The rubber-like polymer (G-10) is a (meth) acrylic acid ester-based rubber-like polymer (G1).

The abbreviations in Table 1 have the following meanings.
BA: n-butyl acrylate AMA: allyl methacrylate MMA: methyl methacrylate EHA: 2-ethylhexyl acrylate AN: acrylonitrile St: styrene

[Production Example 9] Production of other thermoplastic resin (C-1) Composed of 99 parts of methyl methacrylate and 1 part of methyl acrylate, the reduced viscosity measured at 25 ° C from an N, N-dimethylformamide solution was 0.25 dl. A / g acrylic resin (C-1) was produced by known suspension polymerization.

[Production Example 10] Production of other thermoplastic resin (C-2) Composed of 7 parts of acrylonitrile, 23 parts of styrene and 70 parts of methyl methacrylate, the reduced viscosity measured at 25 ° C from an N, N-dimethylformamide solution was 0. An acrylonitrile-styrene-methyl methacrylate terpolymer (C-2) of .38 dl / g was produced by known suspension polymerization.

[Production Example 11] Production of other thermoplastic resin (C-3) Composed of 29 parts of acrylonitrile and 71 parts of styrene, the reduced viscosity measured at 25 ° C from an N, N-dimethylformamide solution is 0.60 dl / g. Acrylonitrile-styrene copolymer (C-3) was produced by known suspension polymerization.

[Example 1 to Example 18, Comparative Example 1 to Comparative Example 4] Production of thermoplastic resin composition First graft copolymers (A-1) to (A-4) produced in Production Examples 3 to 11 above. ), Second graft copolymers (B-1) to (B-10), (b-11), (b-12), and other thermoplastic resins (C-1) to (C-3). In addition, 0.4 parts ethylene bisstearylamide, 0.2 parts Adekastab LA-63P (Asahi Denka Kogyo Co., Ltd.), Adekastab LA-36 (Asahi Denka Kogyo Co., Ltd.) ) 0.2 part, 3 parts of titanium oxide (“CR60-2”, manufactured by Ishihara Sangyo Co., Ltd.) as a colorant were added, and then mixed using a Henschel mixer, and the mixture was heated to a barrel temperature of 230 ° C. Shaped by a degassing twin screw extruder ("PCM-30" manufactured by Ikekai Tekko Co., Ltd.) and pellets (heat A plastic resin composition) was prepared.
Using the 25 mmφ single screw extruder manufactured by Thermo Plastics Co., Ltd., the obtained pellets were discharged into a sheet from a 60 mm wide die at a barrel temperature of 190 ° C. and 250 ° C. and a cooling roll temperature of 85 ° C. A sheet-like molded product having a width of 50 mm to 60 mm and a thickness of 200 μm to 250 μm was obtained by extrusion molding to adjust the taking speed.

The pellets (thermoplastic resin composition) or molded products obtained in Examples and Comparative Examples were evaluated by the following evaluation tests. The evaluation results are shown in Table 2.
(I) Charpy impact strength After leaving a test piece for 12 hours or more in a 23 ° C. atmosphere using a notched test piece made of a sheet-like molded product obtained in Examples and Comparative Examples by a method according to ISO 179 Measurements were made.
(Ii) High-speed impact fracture energy A 40 mmφ single-screw sheet extruder was used to prepare a sheet-like test piece having a barrel temperature of 230 ° C. and a width of 25 cm and a thickness of about 3 mm. Using this sheet-shaped test piece, Shimadzu Corporation high speed impact tester HTM-1 type, striker diameter 1/2 inch, receiving diameter 3 inch, temperature 23 ° C. and −10 ° C., load 1 ton, striker speed The fracture energy was measured under the condition of 3.3 m / sec.
(Iii) Molding Glossiness In the above (ii), the glossiness of the sheet-like test piece prepared using a 40 mmφ short-axis extruder was measured as a reflectance of incident light of 60 °.
(Iv) Molding appearance About the sheet-like molded products obtained in Examples and Comparative Examples, the matteness, the appearance of fish eyes and die lines, and the fineness of the surface are judged by visual judgment, and good without problems. A sheet that was recognized as a good sheet was evaluated as ◯, a sheet that had many problems and could not be put into practical use was evaluated as ×, and the middle was evaluated as △.
(V) Weather resistance (accelerated exposure test)
A white colored sheet (containing 3 parts of titanium oxide) prepared in the same manner as in (ii) was subjected to a black panel temperature of 63 ° C. and a cycle condition of 60 minutes (rainfall: 12 minutes) with a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.). For 1,000 hours. The difference in color between the exposed test piece and the unexposed test piece was measured with a color difference meter and evaluated by the degree of color change ΔE.

From the examples and comparative examples, the following became clear.
1) The thermoplastic resin compositions of Examples 1 to 18 were both high in Charpy impact strength and high-speed impact fracture energy, had good matteness and appearance, and exhibited good weather resistance. Such a resin composition has high industrial value.
2) In particular, the thermoplastic resin compositions of Examples 1 to 4, Example 6, Example 11, Example 12, Example 15 to Example 17 showed good material properties in any items, Such a resin composition has an extremely high industrial value.
3) The thermoplastic resin composition of Comparative Example 1 that did not contain the second graft copolymer (B) had good Charpy impact strength and weather resistance, but had high-speed impact fracture energy of 23 ° C. and −10 ° C. Both of these were low, and the glossiness of the molded sheet was high. Such a resin composition has low industrial utility value.
4) The thermoplastic resin composition of Comparative Example 2 that did not contain the first graft copolymer (A) had good matteness and weather resistance, but had Charpy impact strength and high-speed impact fracture energy of 23 ° C. -10 ° C was low. Such a resin composition has low industrial utility value.
5) The thermoplastic resin composition of Comparative Example 3 having a large mass average particle diameter of 45 μm of the second graft copolymer (B) is excellent in Charpy impact strength and high-speed impact fracture energy, but has high gloss, and The surface roughness was remarkable. Such a resin composition has low industrial utility value.
6) The thermoplastic resin composition of Comparative Example 4 having a small mass average particle diameter of 0.3 μm of the second graft copolymer (B) has good Charpy impact strength and weather resistance, but high-speed impact fracture energy However, both 23 ° C. and −10 ° C. were low and the glossiness was high. Such a resin composition has low industrial utility value.
7) From the comparison between Example 1 and Example 13, when the second graft copolymer (B) containing polyorganosiloxane (S) was used, both Charpy impact strength and high-speed impact fracture energy were high. Showed a tendency to become.
8) The molded sheets produced according to Examples 1 to 18 had high Charpy impact strength and high-speed impact fracture energy, excellent matting properties, and good weather resistance. Such a molded sheet has high industrial value.

Claims (8)

Composite rubber-like polymer comprising polyorganosiloxane (S) and poly (meth) acrylate (M) containing a (meth) acrylate monomer unit and a crosslinking agent and / or graft crossing agent (R) 1 to 99.9 parts by mass of the first graft copolymer (A) grafted with a vinyl polymer,
99 to 0.1 parts by mass of a second graft copolymer (B) obtained by grafting a vinyl polymer to a rubbery polymer (G) having a mass average particle diameter of more than 0.6 μm and not more than 30 μm, and other A thermoplastic resin composition comprising 0 to 80 parts by mass of a thermoplastic resin (C).   The thermoplastic resin composition according to claim 1, wherein the composite rubber-like polymer (R) has a mass average particle diameter of 0.05 to 0.6 μm.   The thermoplastic resin composition according to claim 1 or 2, wherein the rubber-like polymer (G) is a (meth) acrylic ester-based rubber-like polymer (G1).   The rubber-like polymer (G) is a composite rubber comprising polyorganosiloxane, a (meth) acrylic acid ester monomer unit, and a poly (meth) acrylic acid ester containing a crosslinking agent and / or a graft crossing agent. The thermoplastic resin composition according to any one of claims 1 to 3, which is a polymer (G2).   Other thermoplastic resins (C) are polymethyl methacrylate, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-N-substituted maleimide terpolymer, styrene-maleic anhydride-N-substituted maleimide. Ternary copolymer, polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin), polyvinyl chloride, polystyrene, methyl methacrylate-styrene copolymer (MS resin), acrylonitrile-styrene-methyl methacrylate The thermoplastic resin composition according to any one of claims 1 to 4, wherein the thermoplastic resin composition is at least one selected from the group consisting of a terpolymer, a modified polyphenylene ether (modified PPE resin), and a polyamide.   The molded article which consists of a thermoplastic resin composition in any one of Claims 1-5.   A molded product obtained by sheet-molding the thermoplastic resin composition according to claim 1. A molded article obtained by profile-extrusion molding of the thermoplastic resin composition according to any one of claims 1 to 5.