JP2005132988A - Thermoplastic resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in impact resistance, weatherability, and moldability. <P>SOLUTION: The thermoplastic resin composition comprises 1-99 pts. mass graft copolymer (A) obtained by grafting a vinyl polymer on to a composite rubbery polymer (R) comprising a polyorganosiloxane (S) and a poly(meth)acrylic ester (M) comprising a (meth)acrylic ester monomer unit, 99-1 pt. mass vinyl copolymer (B) (provided that the sum of the graft copolymer (A) and the vinyl copolymer (B) is taken as 100 pts. mass), and 0-80 pts. mass another thermoplastic resin (F), and furthermore 0.1-10 pts. mass, based on 100 pts. mass sum of the graft copolymer (A), the vinyl copolymer (B), and the another thermoplastic resin (F), polyalkylene glycol (C). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a thermoplastic resin composition excellent in impact resistance, weather resistance and molding processability, and a molded article thereof.

Improving the impact resistance of a resin material is industrially very useful because it enables expansion of applications and reduction in thickness and size of molded products, and various studies have been made heretofore.
For example, acrylonitrile-butadiene-styrene (ABS) resin, high-impact polystyrene (HIPS) resin, acrylonitrile-styrene-acrylic acid ester can be used to improve the impact resistance of the material by combining a rubbery polymer and a hard resin. (ASA) resin, modified PPE resin, MBS resin, reinforced polyvinyl chloride resin and the like are known. An ASA resin using an alkyl (meth) acrylate rubber which is a saturated rubber as a rubbery polymer or an AES resin using an ethylene-propylene rubber has good weather resistance in addition to impact resistance.
Further, as means for improving impact resistance at low temperatures, it has been proposed to use a composite rubber of polyorganosiloxane and alkyl (meth) acrylate as a rubbery polymer (see, for example, Patent Documents 1 to 3). ). Furthermore, as a means to improve weather resistance and pigment colorability, it has also been proposed to blend a graft polymer containing a composite rubber of polyorganosiloxane and alkyl (meth) acrylate and a (meth) acrylic ester polymer. (For example, see Patent Documents 4 to 6).
Japanese Patent Laid-Open No. 01-190746 Japanese Patent Laid-Open No. 01-282239 Japanese Patent Laid-Open No. 06-025492 Japanese Patent Laid-Open No. 08-283524 JP 2000-186182 A JP 2001-316559 A

However, although the above-described thermoplastic resin composition is excellent in impact resistance and weather resistance (weather discoloration), molding processability may be insufficient depending on molding conditions.
Specifically, when the thermoplastic resin composition described in Patent Documents 1 to 6 is subjected to coextrusion molding as a coating material such as ABS resin or vinyl chloride resin, it is coextruded depending on the shape of the molded product. In some cases, the slipperiness of the mold is not sufficient, and chattering marks, sliding scratches, and the like may be attached to the obtained molded product.
The present invention has been made in view of such circumstances, and an object of the present invention is to provide a thermoplastic resin composition having improved moldability while having impact resistance and weather resistance, and a molded product thereof.

As a result of intensive studies on a thermoplastic resin composition containing a composite rubber of polyorganosiloxane and alkyl (meth) acrylate, the present inventors have ensured impact resistance and weather resistance by blending polyalkylene glycol. However, the present inventors have found that molding processability can be improved and completed the present invention.
That is, the thermoplastic resin composition of the present invention is a composite rubber-like polymer containing polyorganosiloxane (S) and poly (meth) acrylate (M) containing a (meth) acrylate monomer unit. (R) 1 to 99 parts by mass of a graft copolymer (A) grafted with a vinyl polymer, and 99 to 1 part by mass of a vinyl copolymer (B) (provided that the graft copolymer (A) And the vinyl copolymer (B) is 100 parts by mass) and other thermoplastic resins (F) 0 to 80 parts by mass, and the graft copolymer (A) and the vinyl copolymer It is characterized by further containing 0.1 to 10 parts by mass of polyalkylene glycol (C) with respect to 100 parts by mass in total of the copolymer (B) and the other thermoplastic resin (F).

In the present invention, the vinyl copolymer (B) is selected from the group consisting of vinyl cyanide monomer units, aromatic vinyl monomer units, and (meth) acrylic acid ester monomer units. Those containing at least one monomer unit are preferred, and those containing 40% by mass or more of (meth) acrylic acid ester monomer units are particularly preferred.
Moreover, it is preferable that the polystyrene conversion mass mean molecular weight of polyalkylene glycol (C) is 500-3,000,000.
Other thermoplastic resins (F) include acrylonitrile-styrene-N-substituted maleimide terpolymer, styrene-maleic anhydride-N-substituted maleimide terpolymer, polycarbonate resin, polybutylene terephthalate ( PBT resin), polyethylene terephthalate (PET resin), polyvinyl chloride, modified polyphenylene ether (modified PPE resin), and at least one selected from the group consisting of polyamide are preferred.

  The molded article of the present invention is formed by molding the above-described thermoplastic resin composition of the present invention, and examples thereof include those extruded into a sheet and those formed by profile extrusion.

  According to the present invention, it is possible to provide a thermoplastic resin composition having improved impact resistance and weather resistance and improved molding processability. The balance of impact resistance, weather resistance, and moldability in the thermoplastic resin composition of the present invention is at a very high level that could not be achieved by a conventionally known thermoplastic resin composition, and the thermoplastic resin of the present invention. The utility value of the composition and its molded product as various industrial materials, particularly as a weather resistant material, is extremely high.

Hereinafter, the present invention will be described in detail.
"Thermoplastic resin composition"
The thermoplastic resin composition of the present invention is obtained by blending a polyalkylene glycol (C) with a resin composition containing a specific graft copolymer (A) and a vinyl copolymer (B).

{Graft Copolymer (A)}
The graft copolymer (A) is a composite rubber-like polymer (R) containing a polyorganosiloxane (S) and a poly (meth) acrylate ester (M) containing a (meth) acrylate monomer unit. In addition, a vinyl polymer is grafted.

<Polyorganosiloxane (S)>
Although there is no restriction | limiting in particular as polyorganosiloxane (S), The polyorganosiloxane containing a vinyl polymerizable functional group is preferable, and especially dimethylsiloxane unit 97-99.7 mol% and vinyl polymerizable functional group containing siloxane unit 0 A polyorganosiloxane comprising 3 to 3 mol% and having 3 or more siloxane bonds in an amount of 1 mol% or less with respect to all silicon atoms in the polyorganosiloxane is preferred.

  The dimethylsiloxane unit constituting the polyorganosiloxane (S) is preferably a three-membered or higher dimethylsiloxane-based cyclic body, and particularly preferably a 3- to 7-membered ring. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These can be used alone or in combination of two or more.

  The vinyl polymerizable functional group-containing siloxane unit is not particularly limited as long as it contains a vinyl polymerizable functional group and can be bonded to dimethyl siloxane via a siloxane bond, but the reactivity with dimethyl siloxane is considered. Then, the various alkoxysilane compounds containing a vinyl polymerizable functional group are preferable. 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 mercaptosiloxanes such as methylsilane and γ-mercaptopropyltrimethoxysilane. . These vinyl polymerizable functional group-containing siloxanes can be used alone or in combination of two or more.

  The polyorganosiloxane (S) may contain a siloxane-based crosslinking agent as a constituent component. 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 dimethylsiloxane and vinyl polymerizable functional group-containing siloxane 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 a jet output from a high-pressure generator, or the like. In this step, since the particle size distribution of the polyorganosiloxane (S) latex can be reduced, it is particularly preferable to use a high-pressure emulsifier such as a homogenizer.
Next, the finely divided siloxane mixture latex is put into an acid aqueous solution containing an acid catalyst and polymerized at a high temperature. After the polymerization reaction has sufficiently progressed, the reaction solution is cooled, and further neutralized with an alkaline substance such as caustic soda, caustic potash, sodium carbonate or the like to stop the polymerization, and polyorganosiloxane (S) is obtained.

  Examples of emulsifiers suitable for use in the production of polyorganosiloxane (S) include anionic emulsifiers. 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 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. These acid catalysts can be 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 its excellent stabilizing effect on the polyorganosiloxane (S) latex. Further, when n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used in combination, the effect of the emulsifier used in the polyorganosiloxane (S) latex on the color and the like of the molded product can be minimized. .

The mass average particle diameter of the polyorganosiloxane (S) is not particularly limited, but is preferably less than 100 nm, more preferably less than 90 nm, from the viewpoint of improving pigment colorability of the resulting thermoplastic resin composition. Particularly preferred is less than 80 nm. Further, in the production process, it is possible to prevent an increase in the viscosity of latex and generation of agglomerates (coagulum), so that the mass average particle diameter is preferably 10 nm or more, more preferably 20 nm or more, and 30 nm or more. Is particularly preferred.
In addition, the particle diameter of polyorganosiloxane (S) can be controlled by the method described in Unexamined-Japanese-Patent No. 5-279434, for example.

  The content of the polyorganosiloxane (S) in the composite rubbery polymer (R) is not particularly limited, but is preferably 1 to 99% by mass, more preferably 2 to 80% by mass, It is especially preferable that it is 50 mass%. By setting the polyorganosiloxane (S) content within such a range, a thermoplastic resin composition having more excellent impact resistance and molded appearance can be obtained.

<Poly (meth) acrylic acid ester (M)>
The poly (meth) acrylic acid ester (M) constituting the composite rubber-like polymer (R) contains a (meth) acrylic acid ester monomer unit, a crosslinking agent and / or a graft crossing agent. is there.

  Examples of (meth) acrylic acid ester monomers include methyl acrylate, ethyl acrylate, acrylic acid n-propyl, acrylic acid n-butyl, acrylic acid alkyl esters such as 2-ethylhexyl acrylate, and methacrylic acid. And methacrylic acid alkyl esters such as hexyl, 2-ethylhexyl methacrylate, and n-lauryl methacrylate. Among these, n-butyl acrylate is preferable because the resulting resin composition has excellent impact resistance.

Examples of the graft crossing agent include allyl compounds, and specific examples thereof include allyl methacrylate, triallyl cyanurate and triallyl isocyanurate. 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. . By using such a crosslinking agent and / or graft crossing agent, the pigment colorability of the resulting thermoplastic resin composition can be improved.
The lower limit of the total amount of the crosslinking agent and / or the grafting agent is preferably from the viewpoint of pigment colorability of the thermoplastic resin composition with respect to 100% by mass of the (meth) acrylic acid ester monomer unit. 1% by mass, more preferably 0.2% by mass, and particularly preferably 0.5% by mass. In addition, the upper limit is set to 100% by mass of (meth) acrylic acid ester monomer units from the viewpoint of reducing agglomerates (coagulum) during the production of the composite rubber-like polymer (R) and the graft copolymer (A). On the other hand, it is preferably 5% by mass, more preferably 3% by mass, and particularly preferably 2% by mass.

<Composite rubbery polymer (R)>
The production method of the composite rubber polymer (R) is not particularly limited. For example, the polyorganosiloxane (S) latex and the poly (meth) acrylate (M) latex produced individually are hetero-aggregated or co- enlarged. And a method in which the other polymer is produced and combined in the presence of either one of a polyorganosiloxane (S) latex and a poly (meth) acrylate (M) latex.
Among them, since the resulting thermoplastic resin composition is more excellent in impact resistance and pigment colorability, in the presence of the polyorganosiloxane (S) latex, a (meth) acrylate monomer and a crosslinking agent and / or Or the method of carrying out emulsion polymerization of the monomer mixture containing a graft crossing agent is preferable.

Suitable emulsifiers used in the above production method include, for example, sodium or potassium salts of fatty acids such as oleic acid, stearic acid, myristic acid, palmitic acid, or sodium lauryl sulfate, sodium N-lauroyl sarcosinate, dipotassium alkenyl succinate. And sodium alkyldiphenyl ether disulfonate. 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. Particularly, sulfuric acid is added to coagulate the composite rubber polymer (R) from the latex. 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.

<Graft part>
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 the resulting resin composition has impact resistance, rigidity, heat resistance, and weather resistance. And at least one selected from a vinyl cyanide monomer, an aromatic vinyl monomer, and a (meth) acrylate monomer because it is excellent in one or more items of molding processability and dimensional stability. Those composed of one kind of monomer are preferred.
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 methacrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate and the like. Specific examples of the acrylate monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, and the like. Among these monomers, those composed of monomers containing styrene and acrylonitrile are particularly preferred because the resulting graft copolymer (A) has excellent thermal stability.

  In the graft copolymer (A), the content ratio of the composite rubber-like polymer (R) and the vinyl polymer forming the graft portion is not particularly limited, but is excellent in impact resistance and pigment colorability. Since the composition is obtained, the former content is preferably 20 to 80% by mass, and the latter content is preferably 80 to 20% by mass, and the former content is 25 to 75% by mass and the latter content. Is more preferably 75 to 25% by mass, particularly preferably the former content is 30 to 70% by mass and the latter content is 70 to 30% by mass.

<Production of graft copolymer (A)>
The graft copolymer (A) can be produced, for example, by emulsion graft polymerization. Specifically, it can be produced by a known radical polymerization technique in the presence of an emulsifier in the presence of an emulsifier by adding a monomer constituting the graft portion to the composite rubber-like polymer (R) latex. At this time, various chain transfer agents may be added to the monomer solution to be added in order to control the graft ratio and the molecular weight of the graft component.

Suitable radical polymerization initiators for use in the polymerization include peroxides, azo initiators, redox initiators in which these are further combined with an oxidizing agent / reducing agent, and the like. Among 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.
There is no restriction | limiting in particular as an emulsifier, The emulsifier illustrated for manufacture of a composite rubber-like polymer (R) can be used. In addition, it is also possible to use the emulsifier used for manufacture of composite rubber-like polymer (R) as it is, without adding an emulsifier before a graft polymerization process.

  As a method for 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 then in a 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 fatty acid soap or rosin acid soap is used as the emulsifier, the graft copolymer (A) can be recovered using any coagulant, but sodium alkylbenzene sulfonate, etc. In the case where an emulsifier exhibiting a stable emulsifying power is contained even in the acidic region, it is necessary to use a metal salt as a coagulant because the inorganic acid cannot be sufficiently recovered.
In the wet method, in order to obtain a dry graft copolymer (A) from the slurry of the graft copolymer (A), for example, the emulsifier residue remaining in the graft copolymer (A) is eluted in water and washed. Then, the slurry may be dehydrated with a centrifugal or press dehydrator, and then dried with an air dryer or the like. By such a method, a powder or particulate dry graft copolymer (A) is obtained. In addition, dehydration and drying can be simultaneously performed using a press dehydrator or an extruder. Moreover, without recovering the graft copolymer (A) discharged from the press dehydrator or the extruder, the graft copolymer (A) is directly supplied to an extruder or a molding machine for producing the thermoplastic resin composition to produce a molded product. Is also possible.

{Vinyl copolymer (B)}
The vinyl copolymer (B) is not particularly limited as long as it is composed of vinyl monomer units, but the resulting resin composition has impact resistance, rigidity, heat resistance, weather resistance, molding processing, and the like. From the group consisting of vinyl cyanide monomer units, aromatic vinyl monomer units, and (meth) acrylic acid ester monomer units. What contains at least 1 sort (s) chosen is suitable. The vinyl cyanide monomer, aromatic vinyl monomer, and (meth) acrylic acid ester monomer are the same as those exemplified for the production of the graft copolymer (A). Can be used (see paragraph [0024]).

Preferable specific examples of the vinyl copolymer (B) include polystyrene, acrylonitrile-styrene copolymer (SAN resin), acrylonitrile-α-methylstyrene copolymer (αSAN resin), and styrene-methyl methacrylate copolymer ( MS resin), polymethyl methacrylate (PMMA resin), methyl methacrylate-methyl acrylate copolymer, acrylonitrile-styrene-α-methylstyrene terpolymer, acrylonitrile-methyl methacrylate copolymer, acrylonitrile-styrene- Examples thereof include a methyl methacrylate terpolymer and an acrylonitrile-styrene-α-methylstyrene-methyl methacrylate quaternary copolymer. These can be used alone or in combination of two or more.
Above all, the resin composition obtained satisfies at least two items of impact resistance, rigidity, heat resistance, weather resistance, molding processability and dimensional stability at the same time. Resins containing monomer units, specifically styrene-methyl methacrylate copolymer (MS resin), polymethyl methacrylate (PMMA resin), methyl methacrylate-methyl acrylate copolymer, acrylonitrile-styrene-methacrylic acid A methyl terpolymer or the like is preferred. In particular, those containing 40% by mass or more of (meth) acrylic acid ester monomer units are preferred, and those containing 80% by mass or more are more preferred.

  In the present invention, since the resin composition obtained has an excellent balance between impact resistance and molding processing characteristics, the total amount of the graft copolymer (A) and the vinyl copolymer (B) is 100 parts by mass. The blending amount of the graft copolymer (A) is 1 to 99 parts by mass, and the blending amount of the vinyl copolymer (B) is 99 to 1 part by mass.

{Other thermoplastic resins (F)}
In addition to the above graft copolymer (A) and vinyl copolymer (B), the thermoplastic resin composition of the present invention contains other thermoplastic resin (F) as necessary. May be.
The thermoplastic resin (F) is not particularly limited, and examples thereof include acrylonitrile-styrene-N-substituted maleimide terpolymer, styrene-maleic anhydride-N-substituted maleimide terpolymer, polycarbonate resin, and polybutylene. Polyolefin such as terephthalate (PBT resin), polyethylene terephthalate (PET resin), polyvinyl chloride, modified polyphenylene ether (modified PPE resin), polyamide, polyethylene, polypropylene, styrene-butadiene-styrene (SBS), styrene-butadiene (SBR) , Hydrogenated SBS, styrene elastomers such as styrene-isoprene-styrene (SIS), various olefin elastomers, various polyester elastomers, polyacetal resins, ethylene-vinyl acetate copolymers, PS resin, PES resin, PEEK resin, polyarylate, liquid crystal polyester resins. These can be used alone or in combination of two or more.
Among them, acrylonitrile-styrene-N-substituted maleimide terpolymer, styrene-maleic anhydride-N— can be imparted with other characteristics such as heat resistance and chemical resistance as long as the object of the present invention is not greatly impaired. A substituted maleimide terpolymer, polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin), polyvinyl chloride, modified polyphenylene ether (modified PPE resin), polyamide and the like are preferable.

In order to fully exhibit the effects of the present invention, the amount of the other thermoplastic resin (F) is 0 with respect to 100 parts by mass in total of the graft copolymer (A) and the vinyl copolymer (B). -80 mass parts. Moreover, it is preferable that the compounding quantity of a thermoplastic resin (F) shall be 0-70 mass parts.
If the blending amount of the other thermoplastic resin (F) is more than 80 parts by mass, the impact resistance, weather resistance and molding process characteristics which are the objects of the present invention cannot be satisfied at the same time, which is not preferable.

{Polyalkylene glycol (C)}
In the present invention, in order to improve molding processability while ensuring good impact resistance and weather resistance, a composition containing the graft copolymer (A) and the vinyl copolymer (B) is used. Polyalkylene glycol (C) is blended.

  Although the kind of polyalkylene glycol (C) to be used is not specifically limited, For example, polyethylene glycol, polypropylene glycol, an ethylene oxide propylene oxide copolymer etc. are mentioned. Polyalkylene glycol (C) may be used individually by 1 type, and can also use 2 or more types together.

  The molecular weight of the polyalkylene glycol (C) is not particularly limited, but the resulting thermoplastic resin composition is excellent in molding processability and impact resistance, and fish eyes are not seen on the surface of the molded product. The molecular weight is preferably 100 to 3,000,000, more preferably 500 to 1,000,000, and particularly preferably 1,000 to 500,000. If the polystyrene-equivalent mass average molecular weight is less than 100, the impact resistance of the resulting thermoplastic resin composition may be reduced, or bleeding out may occur during molding. On the other hand, when the polystyrene-equivalent mass average molecular weight exceeds 3,000,000, the dispersibility in the resin composition is lowered, and as a result, fish eyes are generated on the surface of the molded product, and sufficient molding processability is improved. May not be obtained.

The blending amount of the polyalkylene glycol (C) is excellent in impact resistance, fluidity, molding processability and appearance of the molded product of the resulting thermoplastic resin composition. Therefore, the graft copolymer (A) and the vinyl-based copolymer are used. It is 0.1-10 mass parts with respect to a total of 100 mass parts of a polymer (B) and the other thermoplastic resin (F) mix | blended as needed, Preferably 0.2-7 mass parts Especially preferably, it is 0.5-5 mass parts.
If the blending amount of the polyalkylene glycol (C) is less than 0.1 parts by mass, the resulting thermoplastic resin composition may have insufficient fluidity and molding processability (such as mold slipping during molding). Yes, if the amount exceeds 10 parts by mass, the impact resistance and heat resistance of the resulting thermoplastic resin composition may be reduced.

{Other ingredients}
The thermoplastic resin composition of the present invention includes the above components (graft copolymer (A), vinyl copolymer (B), other thermoplastic resins (F), and polyalkylene glycol (C)). In addition, various additives can be blended as necessary within a range not departing from the gist of the present invention.
Other additives specifically include dyes, pigments, stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, lubricants, plasticizers, antistatic agents and the like.

{Preparation of thermoplastic resin composition}
The thermoplastic resin composition of the present invention includes, for example, a graft copolymer (A), a vinyl copolymer (B), other thermoplastic resin (F) as necessary, and a polyalkylene glycol (C ) And various additives as necessary, and the resulting mixture can be prepared by melt-kneading using a kneader such as an extruder, a Banbury mixer, a pressure kneader, or a roll.

"Molding"
By molding the thermoplastic resin composition of the present invention, the molded article of the present invention is obtained.
Examples of the molding method include various known 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. Further, the thermoplastic resin composition of the present invention and other materials can be combined to form a molded product by coating the thermoplastic resin composition of the present invention with another resin or metal. By these molding methods, a molded product subjected to primary processing (a profile extrusion molded product, a sheet-like extrusion molded product, a multilayer sheet molded product with other resin or metal, etc.) can be obtained.

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

Production Example 1 Production of Polyorganosiloxane (S-1) Latex 98 parts of octamethylcyclotetrasiloxane and 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of a siloxane mixture. To this, an aqueous solution consisting of 0.67 parts of sodium dodecylbenzenesulfonate and 300 parts of water was added, stirred for 2 minutes at 10,000 rpm with a homomixer, and then passed once through the homogenizer at a pressure of 20 MPa, A stable premixed organosiloxane latex was obtained.
Further, 10 parts of dodecylbenzenesulfonic acid and 90 parts of water were put into another reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer, and a 10% aqueous solution of dodecylbenzenesulfonic acid was added. Prepared. While the aqueous solution was heated to 85 ° C., the previously prepared premixed organosiloxane latex was dropped and polymerized over 4 hours, and after the completion of dropping, the temperature was maintained for 1 hour and then cooled. Next, this reaction product was neutralized with an aqueous caustic soda solution to obtain a polyorganosiloxane (S-1) latex.
The obtained latex was dried at 170 ° C. for 30 minutes and the solid content was determined to be 17.7%. The mass average particle diameter of the polyorganosiloxane (S-1) particles in the latex was 50 nm.

(Production Example 2) Production of polyorganosiloxane (S-2) latex 97.5 parts of octamethylcyclotetrasiloxane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane, and 2 parts of tetraethoxysilane were mixed. As a result, 100 parts of a siloxane mixture was obtained. An aqueous solution consisting of 1 part of dodecylbenzenesulfonic acid, 1 part of sodium dodecylbenzenesulfonate, and 200 parts of water was added thereto, stirred for 2 minutes at 10,000 rpm with a homomixer, and then subjected to a pressure of 20 MPa in the homogenizer. 1 to obtain a stable premixed organosiloxane latex.
The premixed organosiloxane latex was placed in a reactor equipped with a cooling tube, a jacket heater and a stirring device, polymerized by heating at 80 ° C. for 5 hours with stirring and mixing, and then cooled to about 20 ° C. Allowed to stand for 48 hours. Next, this reaction product was neutralized to pH 7.0 with an aqueous caustic soda solution to complete the polymerization, and a polyorganosiloxane (S-2) latex was obtained.
When the solid content of the obtained latex was determined in the same manner as in Production Example 1, it was 36.5%. Moreover, the mass average particle diameter of the polyorganosiloxane (S-2) particles in the latex was 160 nm.

Production Example 3 Production of Composite Rubber Polymer (R-1) In a glass reactor equipped with a reagent injection container, a cooling tube, a jacket heater, a thermometer and a stirrer, polyorganosiloxane (S-1 ) 16 parts of latex (based on solid content), 0.4 part of polyoxyethylene alkylphenyl ether sulfate (“Emar NC-35” manufactured by Kao Corporation) and 297 parts of ion-exchanged water were added and mixed. Next, the following monomer mixture was added to the reactor.
<Monomer mixture>
N-butyl acrylate 84 parts allyl methacrylate 0.6 parts 1,3-butylene glycol dimethacrylate 0.2 parts t-butyl hydroperoxide 0.22 parts The internal temperature was raised to 60 ° C., and when the temperature reached 60 ° C., a redox aqueous solution having the following composition was added to initiate radical polymerization.
<Redox aqueous solution>
Ferrous sulfate heptahydrate 0.00015 parts
Ethylenediaminetetraacetic acid disodium salt 0.00045 parts Rongalite 0.4 parts Ion-exchanged water 20 parts Due to polymerization of the acrylate component, the liquid temperature rose to 78 ° C. This state is maintained for 1 hour to complete the polymerization of the acrylate component, and a latex of a composite rubber-like polymer (R-1) of polyorganosiloxane (S-1) having a mass average particle size of 120 nm and butyl acrylate rubber is prepared. Obtained.

(Production Example 4) Production of composite rubber-like polymer (R-2) Polyorganosiloxane (S-1) latex was changed to polyorganosiloxane (S-2) latex, and the final solid content was composite rubber-like heavy A polyorganosiloxane (S-2) having a mass average particle diameter of 190 nm, butyl acrylate rubber, and the like, except that the amount of ion-exchanged water was changed to be the same as that of the union (R-1) latex A latex of composite rubber-like polymer (R-2) was obtained.

(Production Example 5) Production of Graft Copolymer (A-1) In a glass reactor equipped with a reagent injection container, a cooling tube, a jacket heater, a thermometer and a stirring device, the following rubber mixture was stirred. After mixing, the internal temperature was raised to 70 ° C.
<Rubber mixture>
50 parts of composite rubber-like polymer (R-1) latex (based on solid content)
Ion-exchanged water (including water in (R-1) latex) 210 parts Dipotassium alkenyl succinate 0.5 part Rongalite 0.15 part Thereafter, the following first monomer mixture was added dropwise over 30 minutes. Polymerization was started and held for 15 minutes.
<First monomer mixture>
Acrylonitrile 3 parts Styrene 9 parts t-Hydroperoxide 0.1 part Furthermore, the redox aqueous solution of the following composition was added.
<Redox aqueous solution>
Rongalite 0.15 parts Ferrous sulfate heptahydrate 0.001 parts Ethylenediaminetetraacetic acid disodium salt 0.003 parts Water 5 parts Subsequently, the following second monomer mixture was added dropwise over 120 minutes to polymerize. And kept at 70 ° C. for 30 minutes.
<Second monomer mixture>
Acrylonitrile 9.5 parts Styrene 28.5 parts t-Hydroperoxide 0.3 parts Thereafter, the content was cooled to obtain a graft copolymer (A-1) latex.
The obtained latex was charged into a 1.4% amount of 1.2% aluminum sulfate aqueous solution at 50 ° C. while stirring the aqueous solution. The temperature was raised to 70 ° C. and held for 5 minutes, and further raised to 90 ° C. and held for 5 minutes. The slurry thus obtained was repeatedly dehydrated and washed, and finally dried overnight under an air stream to obtain a white powdered graft copolymer (A-1).

Production Example 6 Production of Graft Copolymer (A-2) Production Example 5 except that the composite rubber-like polymer (R-1) latex was changed to the composite rubber-like polymer (R-2) in Production Example 5. In the same manner as in No. 5, a graft copolymer (A-2) was obtained.

(Production Example 7) Production of vinyl-based copolymer (B-1) Composed of 99 parts of methyl methacrylate and 1 part of methyl acrylate, N, N-dimethylformamide solution (100ml solution of polymer 0.2g) An acrylic resin (B-1) having a reduced viscosity (measured temperature: 25 ° C.) of 0.25 dl / g was produced by a known suspension polymerization.
(Production Example 8) Production of vinyl copolymer (B-2) Composed of 7 parts of acrylonitrile, 23 parts of styrene and 70 parts of methyl methacrylate, N, N-dimethylformamide solution (concentration is the same as in Production Example 7) An acrylonitrile-styrene-methyl methacrylate terpolymer (B-2) having a reduced viscosity (measurement temperature of 25 ° C.) of 0.38 dl / g was produced by a known suspension polymerization.
(Production Example 9) Production of vinyl copolymer (B-3) Reduced viscosity (measurement temperature: 25) consisting of 29 parts of acrylonitrile and 71 parts of styrene and having an N, N-dimethylformamide solution (the concentration is the same as in Production Example 7). An acrylonitrile-styrene copolymer (B-3) having a (° C.) of 0.60 dl / g was produced by a known suspension polymerization.

(Production Example 10) Production of thermoplastic resin (F-1) A mixture of 15 parts of acrylonitrile and 35 parts of styrene is subjected to emulsion graft polymerization by a known method with respect to 50 parts of polybutadiene, and acrylonitrile-butadiene-styrene (ABS) system. A graft copolymer (F-1) was produced.

(Examples 1-10, Comparative Examples 1-4) Manufacture of a thermoplastic resin composition The graft copolymers (A-1) and (A-2) manufactured as described above, and a vinyl copolymer (B -1) to (B-3), polyalkylene glycol (C), and if necessary, other thermoplastic resin (F-1) were blended in the composition shown in Table 1 and mixed by a Henschel mixer. At that time, 0.3 part of barium stearate and 0.4 part of ethylenebisstearylamide were also blended. Subsequently, the obtained mixture was supplied to a deaeration type extruder (PCM-30 manufactured by Ikekai Tekko Co., Ltd.) heated to 260 ° C. and kneaded to obtain pellets of a thermoplastic resin composition.
As the polyalkylene glycol (C), four types of polyethylene glycols having different mass average molecular weights in terms of polystyrene were used. The polystyrene-reduced mass average molecular weight of each polyalkylene glycol (C) is shown below.
(C-1): polystyrene equivalent weight average molecular weight 50,000
(C-2): polystyrene-reduced mass average molecular weight 400
(C-3): polystyrene-reduced mass average molecular weight 1,000
(C-4): polystyrene-reduced mass average molecular weight 4,000,000

(Evaluation test)
The following evaluation was performed about the obtained thermoplastic resin composition.
(1) Charpy impact strength Measured according to ISO 179 using a specimen molded with a 2 ounce injection molding machine with a cylinder temperature set at 250 ° C.
(2) Weather resistance test 3 parts of titanium oxide added to the composition shown in Table 1 and colored in white was molded into a plate of 100 mm x 100 mm x 3 mm, and a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) ), The black panel temperature was 63 ° C., the cycle condition was 60 minutes (rainfall: 12 minutes), and the treatment was performed for 1,000 hours. Before and after the treatment, each was measured using a color difference meter (spectral colorimeter CM-508d manufactured by Minolta Camera Co., Ltd.), and the degree of color change (ΔE) was calculated.
(3) Moldability (mold slipperiness)
Visual evaluation was performed from the resin discharge state during the above-described profile extrusion molding and the generation of scratches and chattering marks due to the mold on the surface of the molded product. Judgment criteria are “Good” when the slipperiness of the mold is good and there is no appearance defect such as scratches or chattering marks due to the mold, “No” when there is an appearance defect and it is not practical. The middle was evaluated as “Δ”.

(result)
The evaluation results are shown in Table 1.
A graft copolymer in which a vinyl polymer is grafted to a composite rubber-like polymer (R) containing polyorganosiloxane and a poly (meth) acrylate ester containing a (meth) acrylate monomer unit ( In Examples 1 to 10 in which A), a vinyl copolymer (B), and a polyalkylene glycol (C) were blended, all of the obtained thermoplastic resin compositions exhibited high Charpy impact strength. The sunshine weather meter showed little discoloration and good weather resistance, and was excellent in moldability.

  On the other hand, in Comparative Example 1 and Comparative Example 3 in which the vinyl copolymer (B) or polyalkylene glycol (C) was not blended, the obtained thermoplastic resin compositions had remarkably poor moldability. there were. In Comparative Example 2 in which the graft copolymer (A) was not blended, the resulting thermoplastic resin composition had extremely poor impact resistance. In Comparative Example 4 in which the graft copolymer (A) was not blended and another thermoplastic resin (F) was blended, the weather resistance was remarkably poor.

In addition, comparison between Example 1 and Example 2 revealed that the larger the particle diameter of the polyorganosiloxane constituting the graft copolymer (A), the impact resistance can be improved.
From comparison between Example 1, Example 3, and Example 4, it is clear that the weather resistance can be improved when the amount of the (meth) acrylic acid ester monomer unit contained in the vinyl copolymer (B) is large. It became. However, the impact resistance tended to decrease as the amount of the (meth) acrylic acid ester monomer unit of the vinyl copolymer (B) increased.
From a comparison between Example 1 and Examples 5 to 7, it was revealed that the impact resistance is improved as the molecular weight of the polyalkylene glycol (C) used is increased. However, from Example 7, it was found that when the molecular weight of the polyalkylene glycol (C) exceeds 3,000,000, the moldability is slightly lowered.
From the comparison of Example 1, Example 8 and Example 9, as the amount of polyalkylene glycol (C-1) added increases, the moldability improves, but the impact resistance tends to decrease. It became clear.

  The thermoplastic resin composition and molded product thereof according to the present invention are excellent in impact resistance, weather resistance and molding processability, and are used for vehicle parts (particularly various exterior parts used without painting and interior parts around the dashboard). ), Wall materials, window frames, rain gutters, building material parts such as various hose covers, miscellaneous goods such as tableware and toys, household appliance parts such as vacuum cleaner housings, television housings, air conditioner housings, OA equipment housings, interior members, ship members And can be suitably used for communication equipment housings and the like.

Claims (7)

A vinyl polymer is grafted to a composite rubber-like polymer (R) containing a polyorganosiloxane (S) and a poly (meth) acrylate ester (M) containing a (meth) acrylate ester monomer unit. 1 to 99 parts by mass of the graft copolymer (A),
99 to 1 part by mass of the vinyl copolymer (B) (provided that the total of the graft copolymer (A) and the vinyl copolymer (B) is 100 parts by mass);
While containing other thermoplastic resin (F) 0-80 parts by mass,
0.1-100 mass parts of polyalkylene glycol (C) is further contained with respect to a total of 100 mass parts of a graft copolymer (A), a vinyl-type copolymer (B), and another thermoplastic resin (F). A thermoplastic resin composition characterized by comprising:   The vinyl copolymer (B) is at least one unit selected from the group consisting of vinyl cyanide monomer units, aromatic vinyl monomer units, and (meth) acrylic acid ester monomer units. The thermoplastic resin composition according to claim 1, comprising a monomer unit.   The thermoplastic resin composition according to claim 2, wherein the vinyl copolymer (B) contains 40% by mass or more of a (meth) acrylic acid ester monomer unit.   The thermoplastic resin composition according to any one of claims 1 to 3, wherein the polyalkylene glycol (C) has a polystyrene-reduced mass average molecular weight of 500 to 3,000,000.   Other thermoplastic resins (F) are acrylonitrile-styrene-N-substituted maleimide terpolymer, styrene-maleic anhydride-N-substituted maleimide terpolymer, polycarbonate resin, polybutylene terephthalate, polyethylene terephthalate, 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 polyvinyl chloride, modified polyphenylene ether, and polyamide.   A molded article obtained by molding the thermoplastic resin composition according to any one of claims 1 to 5.   A molded article obtained by extruding or forming the thermoplastic resin composition according to any one of claims 1 to 5 into a sheet shape.