JP2005320466A - Molding material and molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molding material composed of a rubber-reinforced styrenic resin affording a molded product having excellent weather and chemical resistances and appearance, especially high glossiness, high sharpness, high hardness, scarcely scratched, resultantly usable without coating and having the excellent chemical and weather resistances. <P>SOLUTION: The molding material is composed of the rubber-reinforced styrenic resin (A). Furthermore, the rubber-reinforced styrenic resin (A) contains a (co)polymer (B) composed of a methacrylic ester and, as necessary, other vinylic monomers. The content of a rubber-like polymer (a) is 2-35 mass% based on the whole rubber-reinforced styrenic resin (A) and the content of the methacrylic ester is 30-90 mass% based on the whole rubber-reinforced styrenic resin (A). The content of an oligomer is ≤2,500 ppm. The molded product is composed of the molding material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a molding material that gives a molded article having excellent weather resistance, appearance, and chemical resistance. Specifically, in order to have high glossiness, it has high clarity and high hardness when a colorant is added. Therefore, the present invention relates to a molding material that is difficult to be scratched and can therefore be used without painting, and that gives a molded product whose appearance does not deteriorate even when the surface is cleaned with ethanol.

  Rubber-reinforced styrene resins represented by acrylonitrile-butadiene-styrene (ABS) resin and impact-resistant polystyrene (HIPS) are excellent in mechanical properties, physical properties, electrical properties, etc. , Widely used in OA / home appliance field, vehicle field, sanitary field, etc.

However, when the rubber-reinforced styrene-based resin is extruded, a stain may occur on the surface of the molded product. When a high appearance is required, the rubber-reinforced styrene-based resin has to be used after coating the surface.
In recent years, there has been a demand for molded products that can be used without coating from the viewpoint of cost reduction. For molded products molded with rubber-reinforced styrene-based resins, appearance properties such as glossiness and sharpness, surface It is desired to further improve the hardness, chemical resistance, weather resistance and the like.

JP 57-117557 A

  Accordingly, an object of the present invention is a resin composition containing a rubber-reinforced styrene resin, which is excellent in weather resistance, appearance and chemical resistance, and particularly has high glossiness, high sharpness and high hardness. It is an object of the present invention to provide a molding material that is difficult to be scratched and can be used without painting, and that gives a molded product having excellent chemical resistance and weather resistance, and a molded product made of the molding material.

As a result of intensive studies to achieve the above object, the present inventor used a specific amount of methacrylic acid ester as a monomer component in a rubber-reinforced styrene resin containing a specific amount of a rubbery polymer, By making the content of the oligomer in the specific amount or less, it was found that a molded product having excellent weather resistance, appearance and chemical resistance and usable without coating was obtained, and the present invention was completed.
That is, according to one aspect of the present invention, the rubber-reinforced styrene resin (A) is a molding material made of a rubber-reinforced styrene resin (A). A (co) polymer (B) composed of a monomer, the rubber-like polymer content is 2 to 35% by mass of the rubber-reinforced styrene resin (A), and the methacrylic acid ester content is A molding material is provided that is 30 to 90% by mass of the entire rubber-reinforced styrene resin (A) and has an oligomer content of 2500 ppm or less.
Moreover, according to the other situation of this invention, the molded article which consists of the said molding material is provided. This molded article is excellent in weather resistance, appearance and chemical resistance, and is suitable for use without coating. In addition, when the molding material is extruded, a good appearance can be obtained because there is little generation of gas during molding and no stain is produced in the molded product. When the molding material is injection-molded, the surface of the molded product has high gloss and high definition, so that a good appearance can be obtained. Since the molded article of the present invention is excellent in weather resistance and chemical resistance, it is suitable for outdoor use and also as a housing.

  According to the present invention, in a rubber-reinforced styrene resin containing a methacrylic acid ester as a monomer component, the content of the rubbery polymer is 2 to 35% by mass of the composition, and the methacrylic acid ester content is 30% to 90% by mass of the entire rubber-reinforced styrene resin, and the remaining oligomer content is 2500 ppm or less, so that the mechanical strength and moldability are maintained well, there is no stain, and the gloss is high and the sharpness is good. A molded product that has a good appearance and can be used without painting is obtained. This molded product is excellent in surface hardness, excellent in resistance to chemicals such as ethanol and weather resistance, and is suitable as a molded product for outdoor use.

The present invention will be described in detail below.
In the present specification, “(co) polymerization” and “(co) polymer” are “homopolymerization” and / or “copolymerization”, and “homopolymer” and / or “copolymerization”, respectively. “(Meth) acryl” and “(meth) acrylate” mean “acryl” and / or “methacryl”, and “acrylate” and / or “methacrylate”, respectively.

The molding material of the present invention contains a rubber-reinforced styrene resin (A) as an essential component.
The rubber-reinforced styrene-based resin may be composed of the following component (A-1) or a so-called “component (A-1)” blended with a (co) polymer of the following component (A-2). It may be a graft-blend type rubber reinforced styrene resin.

Component (A-1): a rubber-reinforced styrene resin obtained by polymerizing a vinyl monomer (b-1) containing an aromatic vinyl compound in the presence of the rubbery polymer (a),
Component (A-2): A (co) polymer obtained by (co) polymerizing the vinyl monomer (b-2) in the absence of the rubbery polymer (a).

In the component (A-1), a (co) polymer composed of a vinyl monomer (b-1) such as an aromatic vinyl compound is usually physically or chemically bonded to the rubber polymer (a). A (co) polymer between the grafted body (that is, grafted) and the vinyl monomer (b-1) not grafted to the rubbery polymer (a) (hereinafter sometimes referred to as “non-grafted body”) Is included. When the methacrylic acid ester is contained in the vinyl monomer (b-1), the (co) polymer (non-graft) between the latter vinyl monomers (b-1) is the (co-polymer) of the present invention. ) Corresponds to the polymer (B).
Moreover, when a methacrylic acid ester is contained in the vinyl-type monomer (b-2) of a component (A-2), the said component (A-2) corresponds to the (co) polymer (B) of this invention. To do.
In the present invention, the “methacrylic ester content” is not only the amount of the methacrylic ester portion in the (co) polymer (B) but also the total amount of the methacrylic ester portion in the graft. Means things.

The rubber-reinforced styrene resin (A) of the present invention containing the (co) polymer (B) can be obtained by the following four methods.
(1) A method for preparing the component (A-1) by polymerizing a vinyl monomer (b-1) containing an aromatic vinyl compound and a methacrylic acid ester in the presence of the rubbery polymer (a). .
(2) In the presence of the rubbery polymer (a), the vinyl monomer (b-1) containing an aromatic vinyl compound but not containing a methacrylic acid ester is polymerized to obtain the component (A-1). A (co) polymer (A-2) obtained by (co) polymerizing a vinyl monomer (b-2) containing a methacrylic acid ester in the absence of the rubbery polymer (a). And blending the component (A-1) and the component (A-2). If necessary, (co) polymer obtained by (co) polymerizing vinyl monomer (b-2) not containing methacrylate ester in the absence of rubbery polymer (a). (A-2) may be used.
(3) (Co) polymer (A-2) obtained by (co) polymerizing vinyl monomer (b-2) containing methacrylic acid ester in the absence of rubbery polymer (a) And blending the component (A-2) and the component (A-1) obtained by the method (1) above. If necessary, (co) polymer obtained by (co) polymerizing vinyl monomer (b-2) not containing methacrylate ester in the absence of rubbery polymer (a). (A-2) may be used.
(4) A (co) polymer (A-2) obtained by (co) polymerizing a vinyl monomer (b-2) containing no methacrylic acid ester in the absence of the rubbery polymer (a). ) And blending the component (A-2) and the component (A-1) obtained by the method (1) above. If necessary, a (co) polymer (co) polymer obtained by (co) polymerizing a vinyl monomer (b-2) containing a methacrylic ester in the absence of the rubbery polymer (a) ( A-2) may be used.

  Usually, it is preferable to prepare the rubber-reinforced styrene resin (A) of the present invention by the method (2). In this case, the (co) polymer (A-2) may be a homopolymer of a methacrylic acid ester or a copolymer of a methacrylic acid ester and another vinyl monomer. The content of the methacrylic acid ester in the (co) polymer (A-2) is preferably 50% by mass or more. The higher the content of the methacrylic acid ester, the easier the reduction of the content of the oligomer in the rubber-reinforced styrene resin (A). As the methacrylic acid ester, any of those described below for the component (A-2) can be used, but methyl methacrylate is preferred. The component (A-2) is preferably a solution polymerized product. In this case, the preferable compounding ratio of the component (A-1) and the component (A-2) is (A-1) / (A-2) = 5-60 / 95-40 (mass%).

Even when prepared by any of the above methods, the content of methacrylic acid ester in the rubber-reinforced styrene resin (A) of the present invention is 30 to 90% by mass, preferably 35%, of the entire rubber-reinforced styrene resin (A). It is -85 mass%, More preferably, it is 35-80 mass%. When it is less than 30% by mass, the weather resistance, hardness, and color vividness are poor. When it exceeds 90% by mass, impact resistance and molding processability are inferior.
This methacrylic ester content is the amount of the methacrylic ester used in the vinyl monomer (b-1) or (b-2), and a (co) polymer containing a methacrylic ester as a monomer component (A -2) can be achieved by appropriately changing the blending amount.
Hereinafter, each component (A-1) and (A-2) is demonstrated.

(A-1) Component:
The rubbery polymer (a) used in component (A-1) includes polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-acrylic copolymer, styrene-butadiene-styrene block copolymer. Diene (co) polymers such as polymers, styrene-isoprene-styrene block copolymers, isobutylene-isoprene copolymers, hydrogenated products of these diene (co) polymers, ethylene-α-olefin copolymers [For example, ethylene-propylene-copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-butene-1-copolymer, ethylene-butene-1-nonconjugated diene copolymer], polyurethane rubber, acrylic And rubbers such as silicone rubbers and silicone rubbers. These can be used individually by 1 type or in combination of 2 or more types. Of these rubber polymers, diene (co) polymers, hydrogenated diene (co) polymers, ethylene-α-olefin copolymers, acrylic rubbers, and silicone rubbers are preferred. System (co) polymers and acrylic rubbers are particularly preferred.

  In the present invention, the rubbery polymer (a) is preferably obtained by emulsion polymerization. In that case, the gel content of the rubbery polymer (a) is usually 98% by mass or less, preferably 40 to 98% by mass, more preferably 50 to 95% by mass, particularly preferably, It is 60-90 mass%. When the gel content is 40 to 98% by mass, it is possible to obtain a resin composition that gives a molded product exhibiting particularly excellent impact resistance and the molded product surface appearance.

The gel content was determined by adding 1 g of rubber polymer (a) to 100 ml of toluene and allowing it to stand at room temperature for 48 hours, followed by filtration with a 100 mesh wire mesh (mass W ₁ ) to separate toluene insoluble matter and wire mesh. It is a value calculated by the following equation after vacuum drying at 80 ° C. for 6 hours and weighing (mass W ₂ ).
Gel content (%) = [{W ₂ (g) −W ₁ (g)} / 1 (g)] × 100
The gel content can be adjusted by appropriately setting the type and amount of the molecular weight adjusting agent, the polymerization time, the polymerization temperature, the polymerization conversion rate and the like during the production of the rubbery polymer.

When using a latex-like rubbery polymer obtained by an emulsion polymerization method or a re-emulsification method as the rubbery polymer (a), the average rubber particle diameter is preferably in the range of 500 to 30000 mm, and more Preferably, it is 1000-20000cm, Most preferably, it is 1500-8000cm. The average rubber particle diameter almost corresponds to the particle diameter of the rubbery polymer (a) dispersed in the rubber-reinforced styrene resin (A).
The molding material satisfying the particle size characteristics can be produced by appropriately setting the polymerization conditions so that the latex produced during the emulsion polymerization of the rubbery polymer (a) satisfies the particle size characteristics. In the re-emulsification method, a rubber polymer satisfying the above particle size characteristics can be obtained by appropriately adjusting the stirring conditions in the emulsification step, the type and amount of the emulsifier, the dissolution concentration of the rubber polymer, and the like.

  The content of the rubber polymer is 2 to 35% by mass, preferably 5 to 30% by mass, and more preferably 5 to 28% by mass, based on the entire rubber-reinforced styrene resin (A). If it is less than 2% by mass, the impact resistance is poor. If it exceeds 35% by mass, molding processability and appearance are poor.

The vinyl monomer (b-1) contains an aromatic vinyl compound as an essential monomer component, and may contain other vinyl monomers copolymerizable therewith as necessary. .
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, pt-butylstyrene, ethylstyrene, vinylnaphthalene, o- Examples thereof include methylstyrene and dimethylstyrene, and these can be used alone or in combination of two or more. Among these, the aromatic vinyl compound preferably used is styrene and / or α-methylstyrene, and even when two or more aromatic vinyl compounds are used in combination, the styrene content in the aromatic vinyl compound is 20% by mass. The above is preferable.

  Other vinyl monomers copolymerizable with aromatic vinyl compounds include vinyl cyanide compounds, (meth) acrylic acid esters, maleimide group-containing unsaturated compounds, and other various functional group-containing unsaturated compounds. Is mentioned. The vinyl monomer (b-1) usually contains an aromatic vinyl compound as an essential monomer component, and if necessary, a vinyl cyanide compound, a (meth) acrylic acid ester and a maleimide group-containing component. One or more selected from the group consisting of saturated compounds are used in combination as monomer components, and if necessary, at least one of various other functional group-containing unsaturated compounds is used in combination as monomer components. The

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and acrylonitrile is preferred. These can be used individually by 1 type or in combination of 2 or more types. When a vinyl cyanide compound is used, chemical resistance is imparted. When using a vinyl cyanide compound, the usage-amount is in the (b-1) component, Preferably it is 1-60 mass%, More preferably, it is 5-50 mass%.
As (meth) acrylic acid esters, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate and other acrylic acid alkyl esters, methyl methacrylate, ethyl methacrylate, Examples include methacrylic acid alkyl esters such as 2-ethylhexyl methacrylate and cyclohexyl methacrylate. These can be used individually by 1 type or in combination of 2 or more types. Of these, methyl methacrylate is preferred. The use of (meth) acrylic acid ester is preferable because it imparts transparency or a sense of transparency. When (meth) acrylic acid ester is used, the amount used thereof is preferably 1 to 80% by mass, more preferably 5 to 80% by mass in the component (b-1).

  Examples of the maleimide group-containing unsaturated compound include maleimide compounds such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. These can be used individually by 1 type or in combination of 2 or more types. Further, this maleimide compound may be introduced by a method in which maleic anhydride is copolymerized and then imidized. When a maleimide group-containing unsaturated compound is used, heat resistance is imparted. When using a maleimide group containing unsaturated compound, the usage-amount is in the (b-1) component, Preferably it is 1-60 mass%, More preferably, it is 5-50 mass%.

  Other various functional group-containing unsaturated compounds include carboxyl group-containing unsaturated compounds, acid anhydride group-containing unsaturated compounds, epoxy group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, substituents or unsubstituted amino groups Examples include unsaturated compounds and oxazoline group-containing unsaturated compounds. These functional group-containing unsaturated compounds can be used alone or in combination of two or more.

Examples of the carboxyl group-containing unsaturated compound include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid. These can be used individually by 1 type or in combination of 2 or more types.
Examples of the acid anhydride group-containing unsaturated compound include unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, and citraconic anhydride. These can be used individually by 1 type or in combination of 2 or more types.
Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether. These can be used individually by 1 type or in combination of 2 or more types.
Examples of the hydroxyl group-containing unsaturated compound include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, and 3-hydroxy-2- Examples thereof include methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N- (4-hydroxyphenyl) maleimide and the like. These can be used individually by 1 type or in combination of 2 or more types.

Examples of substituted or unsubstituted amino group-containing unsaturated compounds include aminoethyl acrylate, aminoethyl methacrylate, aminopropyl methacrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, and N-vinyl. Examples include diethylamine, N-acetylvinylamine, acrylic amine, methacrylamine, N-methylacrylamine, acrylamide, N-methylacrylamide, and p-aminostyrene. These can be used individually by 1 type or in combination of 2 or more types.
Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline. These can be used individually by 1 type or in combination of 2 or more types.

When such a functional group-containing unsaturated compound is used, when the rubber-reinforced styrene resin is blended with another polymer, the compatibility between the two can be improved. Preferred monomers for achieving such effects are epoxy group-containing unsaturated compounds, carboxyl group-containing unsaturated compounds, and hydroxyl group-containing unsaturated compounds, more preferably hydroxyl group-containing unsaturated compounds, particularly preferably. 2-hydroxylethyl (meth) acrylate.
The amount of the functional group-containing unsaturated compound used is the total amount of the functional group-containing unsaturated compounds used in the rubber-reinforced styrene resin, and is preferably 0.01 to 20% by mass with respect to the entire rubber-reinforced styrene resin. The amount of the molding material of the present invention is preferably 0.01 to 10% by mass, and more preferably 0.05 to 5% by mass.
Preferred vinyl monomer (b-1) combinations include (a) aromatic vinyl compound / vinyl cyanide compound, (b) aromatic vinyl compound / (meth) acrylic acid alkyl ester, (c) aromatic Vinyl compound / vinyl cyanide compound / (meth) acrylic acid alkyl ester, (d) aromatic vinyl compound / maleimide compound / vinyl cyanide compound, and (e) aromatic vinyl compound / 2-hydroxylethyl (meth) acrylate / Vinyl cyanide compounds are mentioned.

Component (A-1) used in the present invention is a method such as emulsion polymerization, solution polymerization, suspension polymerization of the vinyl monomer (b-1) in the presence of the rubber polymer (a). It can be produced by polymerization. The component (A-1) is preferably obtained by polymerizing 95 to 30% by mass of the vinyl monomer (b-1) in the presence of 5 to 70% by mass of the rubbery polymer (a) (here The total of the rubber polymer (a) and the vinyl monomer (b-1) is 100% by mass).
In this case, as a polymerization initiator, a molecular weight regulator, an emulsifier, a dispersant, a solvent, and the like used for the polymerization, those usually used in these polymerization methods can be used as they are. As a preferable method for producing the component (A-1), the vinyl monomer (b-1), an additional emulsifier, and polymerization start in the presence of the rubbery polymer (a) obtained by emulsion polymerization. A method of graft copolymerization using an agent is generally used under conditions of a polymerization temperature of 30 to 90 ° C., a polymerization time of 1 to 15 hours, and a polymerization pressure of −1.0 to 5.0 kg / cm ² .

The graft ratio of the component (A-1) is preferably 10 to 200% by mass, more preferably 20 to 150% by mass, and particularly preferably 30 to 120% by mass. In addition, a graft ratio (mass%) is calculated | required by following Formula.
Graft ratio (mass%) = {(TS) / S} × 100
In the above formula, 1 g of component (A-1) is added to 20 ml of acetone (but acetonitrile is used when the rubbery polymer (a) is an acrylic rubber), and 2 hours by a shaker. After shaking, it is the mass (g) of insoluble matter obtained by centrifuging for 60 minutes with a centrifuge (rotation speed: 23,000 rpm) to separate the insoluble matter and the soluble matter, and S is the component ( A-1) The mass (g) of the rubber-like polymer (a) contained in 1 g.
The intrinsic viscosity (measured in methyl ethyl ketone at 30 ° C.) of the component (A-1) acetone (but acetonitrile when the rubbery polymer (a) is an acrylic rubber) is usually used. 0.3 to 1.5 dl / g, preferably 0.3 to 1.3 dl / g, more preferably 0.4 to 1.0 dl / g, particularly preferably 0.4 to 0.8 dl / g. is there. When the intrinsic viscosity is less than 0.3 dl / g, the impact resistance is inferior, while when it exceeds 1.5 dl / g, the fluidity is inferior. This intrinsic viscosity can be controlled by chain transfer agent, polymerization time, polymerization temperature, and the like.
It is preferable that the oligomer content of a component (A-1) is 200-800 ppm.
A component (A-1) can be used individually by 1 type or in combination of 2 or more types.

(A-2) Component:
Examples of the vinyl monomer (b-2) constituting the (co) polymer of the component (A-2) include the aromatic vinyl compounds and vinyl cyanide listed as the vinyl monomer (b-1). A compound, a (meth) acrylic acid ester, a maleimide group-containing unsaturated compound, and various other functional group-containing unsaturated compounds can be used. These compounds can be used alone or in combination of two or more. Component (A-2) may be a single composition (co) polymer, or may be a blend of two or more (co) polymers having different compositions.
In particular, the vinyl monomer (b-2) has a methacrylic acid ester, particularly methyl methacrylate as an essential monomer component, and if necessary, an aromatic vinyl compound and, if necessary, a vinyl cyanide compound in a single amount. It is preferable to contain as a body component. Furthermore, one or two or more selected from the group consisting of an acrylate ester and a maleimide group-containing unsaturated compound can be used in combination as a monomer component, and if necessary, at least of other various functional group-containing unsaturated compounds One type can be used in combination as a monomer component.
The use ratio of the methacrylic acid ester, the aromatic vinyl compound and the vinyl cyanide compound is 40 to 100: 0 to 30:30 to 30 in terms of methacrylic acid ester: aromatic vinyl compound: vinyl cyanide compound (mass ratio). , Preferably 50 to 90: 5 to 30: 5 to 20 (note that the total of methacrylic acid ester, aromatic vinyl compound and vinyl cyanide compound is 100).
The component (A-2) includes methacrylic acid ester homopolymers, but the methacrylic acid ester homopolymers may be used in combination with the component (A-2) having other compositions. preferable.

When blending rubber-reinforced styrene resin and other polymers, in order to improve the compatibility of both, epoxy group-containing unsaturated compound, carboxyl group-containing unsaturated compound or hydroxyl group-containing as functional group-containing unsaturated compound An unsaturated compound is preferably used, more preferably a hydroxyl group-containing unsaturated compound, and particularly preferably 2-hydroxylethyl (meth) acrylate.
The preferable usage-amount in the (b-2) component of an acrylate ester, a maleimide group containing unsaturated compound, and another functional group containing unsaturated compound is the same as the usage-amount in the said (b-1) component.

The component (A-2) can be produced by the same method as the component (A-1) except that the polymerization of the vinyl monomer (b-2) is performed in the absence of a rubbery polymer. Those obtained by solution polymerization are preferred.
The intrinsic viscosity (measured in methyl ethyl ketone at 30 ° C.) of the component (A-2) is usually 0.3 to 1.5 dl / g, preferably 0.3 to 1.3 dl / g, more preferably 0.8. 4 to 1.0 dl / g, particularly preferably 0.4 to 0.8 dl / g. This intrinsic viscosity can be controlled by chain transfer agent, polymerization time, polymerization temperature, and the like.
The oligomer content of the component (A-2) is preferably 300 to 2000 ppm.
The component (A-2) can be mixed with the component (A-1) by an appropriate method.

  The rubber-reinforced styrene resin (A) can be used by blending with other polymers by a method such as melt-kneading. Examples of such other polymers include olefin resins such as polyethylene and polypropylene; polyamide resins such as PA6, PA66, PA46, and PA12; thermoplastic polyester resins such as polybutylene terephthalate, polyethylene terephthalate, and polyarylate; polycarbonate resins and polyphenylene ethers Or polyphenylene ether resins such as polyphenylene ether / styrene resins; polyacetal, vinyl chloride resin, polysulfone, PPS, polyether sulfone, ethylene-vinyl acetate copolymer, EVOH, etc. Can be used in combination with more than one species.

  In the molding material of the present invention, depending on the purpose and application, further, inorganic filler, metal powder, reinforcing agent, plasticizer, heat stabilizer, light stabilizer, antioxidant, ultraviolet absorber, dye, pigment, Additives such as antistatic agents and lubricants can be added as appropriate.

The molding material of the present invention can be prepared by melting and kneading each resin component with various extruders, Henschel mixers, Banbury mixers, kneaders, rolls, feeder ruders, etc., and kneading with other components as appropriate. A preferable production method is a method using an extruder, a Henschel mixer or a Banbury mixer.
Furthermore, when each component is kneaded, these components may be kneaded in a lump, or may be kneaded in multiple stages, divided and blended with an extruder, a Henschel mixer, or a Banbury mixer.
In addition, after knead | mixing with a Henschel mixer, a Banbury mixer, a kneader etc., it can also pelletize with an extruder.
The molding material of the present invention can be formed into a molded product by a known molding method such as injection molding, press molding, sheet or film extrusion molding, vacuum molding, profile extrusion molding, foam molding or the like.

  In the present invention, the oligomer content in the molded article is 2500 ppm or less, preferably 2000 ppm or less, more preferably 1500 ppm or less. When it exceeds 2500 ppm, the amount of gas generated during the molding process increases, resulting in poor appearance and poor ethanol resistance. Since the oligomer content in the molded article is generally less than or equal to the oligomer content of the molding material, the oligomer content in the molding material is 2500 ppm or less, preferably 2000 ppm or less, more preferably 1500 ppm or less. A desired molded product can be obtained.

In order to achieve the oligomer content, for example, at least one of the following methods (I) to (III) can be employed.
(I) A method of reducing oligomer formation by optimizing the polymerization conditions in the polymerization step of the component (A-1) and / or (A-2).
(II) A method of performing extrusion by optimizing extrusion conditions using an extruder having a function of easily removing oligomers in the pellet extrusion step of the component (A-1) and / or (A-2).
(III) A method of extruding in the same manner as in the above (II) in a pellet extrusion step of a mixture obtained by blending the above component (A-1) and component (A-2).

  Molded articles molded from the molding material of the present invention include molded articles used outdoors such as rain gutters, air conditioner duct covers, resin sashes, bamboo fences, TV front panels, portable audio devices, cellular phones, game machines, etc. It can be used for various purposes such as housings.

  Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, parts and% are based on mass unless otherwise specified. In addition, various evaluation methods and components used in the examples were as follows.

〔Evaluation methods〕
1. Measurement of oligomer content in molding material or molded product Using pellets of molding material or a cut product obtained by carefully cutting the molded product used for the measurement of the following Charpy impact strength as a sample, dissolve it in methyl ethyl ketone solvent, and add the standard substance (p Add -ethylnitrobenzene) and mix.
Thereafter, the polymer content is reprecipitated with n-pentane, and the supernatant is concentrated and injected into a gas chromatograph equipped with a flame ionization detector. In the molding material or molding from the chromatograph obtained under the following test conditions. Quantify oligomers in the product.
Test conditions / gas chromatograph; GC-14APF manufactured by Shimadzu Corporation
-Data processor: Shimadzu C-R6A
・ Column: TC-5 0.53mm × 30m
-Temperature; COL 130- (7.5) -290
Inj. Det 290
・ Carr; He 20ml / min

2. Generated Gas A flat plate having a width of 30 mm and a thickness of 4 mm was formed using a T-die having a width of 90 mm by a 50 mm sheet extrusion apparatus at a cylinder and a die temperature of 180 ° C. The gas generated from the mold die at that time was visually observed and judged. The criteria for this are as follows:
○: Less generated gas
Δ: A little generated gas,
X: A lot of generated gas.
If the amount of generated gas is large, it is bad for the environment, mold contamination occurs, and the surface appearance (gloss, aesthetics, vividness, etc.) of the molded product is inferior.

3. Ethanol resistance 0.5 parts of standard carbon black is added to 100 parts of molding material and colored material is injection-molded on a flat plate of 80 x 55 mm thickness 2.4 mm. The surface of the resulting molded product is ethanol After making 20 round trips with gauze containing, the surface was visually observed and judged. The criteria for this are as follows:
○: no whitening
Δ: Some whitening is observed,
X: There are many whitening parts.

4). Gloss A material that is colored by adding 0.5 parts of standard carbon black to 100 parts of molding material is injection molded onto a flat plate of 80 × 55 mm thickness 2.4 mm, and the gloss of the surface of the resulting molded product ( Measurement was performed at 60 ° light source with GLOSS METER GM-26D manufactured by Murakami Color Research Laboratory.

5). Pencil hardness A material colored by adding 0.5 parts of standard carbon black to 100 parts of molding material is injection-molded into a flat plate of 80 x 55 mm thickness 2.4 mm, and the resulting molded product is Yasuda Corporation. Seiki Seisakusho NO. It measured based on JISK5400 in 553-M FILM HARDESS TESTER.

6). Weather resistance 0.5 parts of standard carbon black was added to 100 parts of molding material, and colored material was injection-molded into a flat plate of 80 x 55 mm thickness 2.4 mm. Irradiation was conducted for 1000 hours under conditions of black panel temperature of 63 ° C. and rainfall for 18 minutes in 120 minutes using SUNSHINE WEATHER METER S80 manufactured by Co., Ltd., and color change before and after exposure was visually observed and judged. The criteria for this are as follows:
○: No discoloration
Δ: Some discoloration is observed,
X: Discoloration is observed.

7). Charpy impact strength Injection molding was performed in accordance with ISO 179, and Charpy impact strength was measured. The unit is KJ / ^{m 2.}
8). Melt mass flow rate The fluidity was measured according to ISO 1133. The unit is g / 10 minutes.

[Use ingredients]
Component (A-1-1): ABS resin comprising a constituent component having a polybutadiene rubber content of 42%, an acrylonitrile content of 16%, and a styrene content of 42%. Graft rate 52%, intrinsic viscosity of acetone soluble matter (methyl ketone, 30 ° C.) 0.45 dl / g, oligomer content 480 ppm.
Component (A-1-2): ASA resin having an acrylic rubber content of 50%, an acrylonitrile content of 14%, and a styrene content of 36%. Graft ratio 65%, intrinsic viscosity of acetonitrile soluble matter (methyl ketone 30 ° C.) 0.51 dl / g, oligomer content 400 ppm.

Component (B-1): Two jacketed polymerization reaction vessels equipped with ribbon wings with an internal volume of 30 L were connected and purged with nitrogen, and then 23 parts of styrene, 18 parts of acrylonitrile, methyl methacrylate were added to the first reaction vessel. 59 parts and 20 parts of toluene were continuously added. A solution of 0.12 part of tert-dodecyl mercaptan and 5 parts of toluene as a molecular weight regulator, and a solution of 0.1 part of 1,1′-azobis (cyclohexane-1-carbonitrile) and 5 parts of toluene as a polymerization initiator Was fed continuously. The polymerization temperature of the first group was controlled at 110 ° C., the average residence time was 2.0 hours, and the polymerization conversion was 57%. The obtained polymer solution was continuously taken out from the first reaction vessel by the same amount as the styrene, acrylonitrile, toluene, molecular weight regulator, and polymerization initiator supplied by the pump provided in the second reactor. To the reaction vessel. The polymerization temperature of the second reaction vessel was 130 ° C., and the polymerization conversion was 70%. The copolymer solution obtained in the second reaction vessel was directly removed from the unreacted monomer and solvent under the conditions of 200 to 250 ° C. and a vacuum degree of −600 mmHg using an extruder with a biaxial three-stage vent. Volatile, a pellet-shaped resin (B-1) having a bound methyl methacrylate content of 72% by weight, a bound styrene content of 21% by weight, a bound acrylonitrile content of 7% by weight, an intrinsic viscosity [η] of 0.5 dl / g, and an oligomer content of 3500 ppm. Obtained.

Component (B-2): Using a twin-screw, three-stage vented extruder, the pellet resin (B-1) was passed twice under the conditions of 200 to 250 ° C. and a vacuum degree of −730 mmHg to reduce oligomer components. Was done. A resin (B-2) having a bound methyl methacrylate content of 72%, a bound styrene content of 21%, a bound acrylonitrile content of 7%, an intrinsic viscosity (methyl ketone 30 ° C.) of 0.5 dl / g, and an oligomer content of 1000 ppm was obtained.

Component (B-3): A methacrylate resin having an oligomer content of 500 ppm, a methyl methacrylate content of 100%, and an intrinsic viscosity (methyl ketone 30 ° C.) of 0.6 dl / g.
AS resin: AS resin having an oligomer content of 3000 ppm, a bound acrylonitrile content of 24%, and a bound styrene content of 76%.

Examples 1-4, Comparative Examples 1-4
The compounding ingredients shown in Table 1 were thoroughly mixed using a Henschel mixer, and then the mixture of Examples 1 to 3 and Comparative Examples 1 to 4 was used at 200 ° C. using a twin-screw 1-stage vented extruder. Extrusion was performed under the conditions of a degree of vacuum of −700 mmHg to obtain pellets.
The mixture of Example 4 was extruded twice by using a twin-screw three-stage vented extruder under the conditions of 230 ° C. and a degree of vacuum of −700 mmHg to obtain pellets.
Using the above pellets, test pieces were prepared and evaluated according to the above evaluation method. The results are shown in Table 1.

The molded articles of Examples 1 to 4 are within the scope of the present invention, and the intended effect of the present invention is obtained.
On the other hand, Comparative Example 1 is an example in which the rubbery polymer content is less than the range of the present invention, and the impact resistance is inferior.
Comparative Example 2 is an example in which the oligomer content exceeds the range of the present invention, the amount of generated gas is large, and the ethanol resistance is inferior.
Comparative Example 3 is an example in which the amount of methacrylic acid ester is less than the range of the present invention, and is inferior in ethanol resistance, gloss, hardness, and weather resistance.
Comparative Example 4 is an example in which the content of the rubbery polymer exceeds the range of the present invention, and is inferior in gloss, hardness, and moldability.

The molding material of the present invention provides a molded product that generates less gas during molding, does not cause stains on the molded product, and has high gloss and high image clarity. Furthermore, a molded article having high surface hardness and excellent chemical resistance and weather resistance is provided. Therefore, the molded product of the present invention can be used without painting, and is suitable for use as a molded product or a casing for outdoor use.

Claims (5)

  A molding material comprising a rubber-reinforced styrene resin (A), wherein the rubber-reinforced styrene resin (A) is a (co) polymer comprising a methacrylic acid ester and optionally another vinyl monomer. (B), the rubber-like polymer content is 2 to 35 mass% of the whole rubber-reinforced styrene resin (A), and the methacrylic acid ester content is the whole rubber-reinforced styrene resin (A). The molding material which is 30-90 mass% and whose oligomer content is 2500 ppm or less.   A molded article comprising the molding material of claim 1.   The molded product according to claim 2, which is formed by extrusion.   The molded article according to claim 2 or 3, wherein the molded article is used outdoors. The molded article according to any one of claims 2 to 4, which is a molded article used as a casing.