JP2000095918A - Thermoplastic resin material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain at a low cost resin material which can be calendered without emitting much odor and having excellent processability by mixing a graft copolymer with a specified copolymer, an acrylic copolymer, and a phosphorus compound. SOLUTION: This material comprises 10-98.9 pts.wt. (A) graft copolymer prepared by grafting vinyl cyanide units, aromatic vinyl units, and other copolymerizable vinyl units onto a rubbery polymer through chemical bonding; 89.9-1 wt.% (B) copolymer comprising 10-45 wt.% vinyl cyanide units, 90-55 wt.% aromatic vinyl units, and 0-40 wt.% (the total amount is 100 wt.%) other copolymerizable vinyl units; 0.1-15 pts.wt. (the total amount of A to C is 100 pts.wt.) (C) acrylic copolymer comprising 10-95 wt.% methyl methacrylate units, 5-60 wt.% acrylic ester units, and 0-50 wt.% monomer units copolymerizable therewith; and 0.05-5 pts.wt. (D) phosphorus compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides direct calendering without the step of kneading and shaping into pellets and the like, has good calendering properties and thermal coloring properties, and has low odor generated during processing. Further, the present invention relates to a thermoplastic resin material capable of providing a rubber-modified styrene resin sheet having less fish eyes.

[0002]

2. Description of the Related Art An acrylonitrile-styrene copolymer reinforced with a conjugated diene rubber, a so-called ABS resin and a rubber-modified thermoplastic resin similar thereto, have excellent moldability, mechanical strength and chemical resistance. Is used in a wide range of applications. In order to form a thin sheet, the calendering method is the most productive,
There is a demand that the ABS resin be formed into a sheet by this processing method without impairing its performance. For example,
JP-A 1-245045 discloses a method of blending a metal soap and a fatty acid ester with an ABS resin,
208798 and JP-A-9-216992,
Japanese Patent Application Laid-Open No. 10-640 proposes to improve the calender and roll processability by adding an acrylic polymer or a plasticizer to an ABS resin. However, with these methods, roll separation, bank rotation, rough surface of the material surface, etc. reach industrially practical levels, but after long-term operation and repeated recycling of scrap material, thermal coloring becomes remarkable, Many phenomena that change the color occur,
It has been difficult to continuously form a calender sheet of a rubber-modified styrenic material. Also, usually, the resin and various modifiers are kneaded once with a pelletizer or Banbury mixer, etc.
A step of dispersing the rubber and the modifier into a pellet form is essential. This is because if this step is omitted, many fish eyes due to the dispersion of the rubber are generated, and a phenomenon unfavorable in quality occurs. However, in the calendering of a rubber-modified styrenic material, this kneading step is a factor that increases the processing cost of the rubber-modified styrenic resin sheet, and the kneading step can be omitted, and a sheet with excellent appearance can be easily obtained. The materials obtained are eager.

[0003]

The rubber-modified styrenic resin has various excellent performances, can be continuously produced, and can be calendered at a low cost with little thermal coloring. It can be used in many fields. Therefore, as described above, it is desired to develop a material which does not impair the original performance of the rubber-modified styrenic resin, has excellent calendering properties, has less thermal coloring, eliminates the kneading step, and causes less fisheye. Further, the calendering process has a large exposed area of the heated material, and therefore the odor peculiar to the material often impairs the working environment. Therefore, a material which does not easily generate such an odor is desired. In addition, since rubber-modified styrenic resins and various stabilizers and processing aids to be mixed with them are often obtained in powder form, taking their uniform dispersibility into account, the powder can be directly used in a calendering machine. The process of introduction is desired.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is possible to obtain a product having a good appearance by continuous calendering, to have a low odor at the time of processing and to have excellent workability. It is to provide a low-cost thermoplastic resin material.

[0005]

SUMMARY OF THE INVENTION The present invention provides a resin composition having a specified structure and form which solves the above-mentioned problems. That is, the gist of the present invention is that a monomer unit containing a vinyl cyanide-based unit, an aromatic vinyl-based unit, and other copolymerizable vinyl-based units in a rubber-like polymer has a chemical bond. 10 to 98.9 parts by weight of the grafted graft copolymer (A), 10 to 45% by weight of vinyl cyanide units, 90 to 55% by weight of aromatic vinyl units, and 0 other copolymerizable vinyl units 89.9 to 1 part by weight of a copolymer (B) consisting of a monomer unit consisting of ４０40% by weight (total 100% by weight);
0.1 to 95% by weight of methyl methacrylate units, 5 to 60% by weight of acrylate units, and 0 to 50% by weight of monomer units copolymerizable therewith, in an acrylic copolymer (C) 0.1 to 0.1%. 15 parts by weight (however, (A) + (B) +
(In the case where the total of the resin mixture composed of (C) is 100 parts by weight), and 0.05 to 5 parts by weight of the phosphorus compound (D). Satisfy each of the requirements. The residual sulfur content in the thermoplastic resin material is 400 ppm or less. A tension is applied to a strand discharged after the thermoplastic resin material is melted at a resin temperature of 190 ° C., and the tension when the strand breaks is 0.15 to 0.45 N.

Examples of the rubbery polymer include a diene rubber having a diene unit as a main component, an acrylic rubber having a acrylate unit having 1 to 18 carbon atoms as a main component, and ethylene-propylene non-conjugated. A diene terpolymer rubber, one rubber-like polymer selected from the group consisting of polyorganosiloxane-based rubbers having a siloxane unit having an alkyl group having 1 to 6 carbon atoms in a side chain as a main component, or
It is preferable to use a combination of at least two or more rubbery polymers or a composite of at least two or more rubbery polymers. Further, the content of the entire rubber-like polymer in the thermoplastic resin material is preferably 5 to 60% by weight.

Further, the acrylic copolymer (C) comprises:
It is composed of 40 to 95% by weight of methyl methacrylate unit, 5 to 60% by weight of an acrylate ester and 0 to 30% by weight of a monomer unit copolymerizable therewith, and a chloroform solution (0.1 g / dl) is heated at 25 ° C. Reduced viscosity (ηs
p / C) is an acrylic copolymer (C-1) having 0.1 to 20 L / g, or (a) a polymer in which at least 5% by weight of its constituent units is methyl methacrylate Yes, the polymer chloroform solution (0.1 g / d
l) In the presence of 5 to 45 parts by weight of a polymer having an ηsp / C of less than 2 dl / g measured at 25 ° C.,
A mixture of 40 to 70 parts by weight of 0 to 70% by weight of a methacrylic acid alkyl ester having an alkyl group of 1 to 18 and 100 to 30% by weight of an acrylic acid ester having 1 to 18 carbon atoms is obtained by adding ηsp / In the presence of a two-stage polymer consisting of a polymer having component (a) and component (b) obtained by polymerization under the condition that C is 1 dl / g or less, (c) methacrylic acid is further added. Methyl 30-1
5 to 40 of a monomer (mixture) consisting of 00% by weight and 0 to 50% by weight of a monomer copolymerizable with the methyl methacrylate.
Parts by weight (provided that the total amount of the components (a), (b) and (c) is 100 parts by weight).
It is particularly preferable that 2) or a combination thereof is used.

As the phosphorus compound (D), a pentaerythritol-diphosphite compound represented by the following formula is desirable.

Embedded image Here, R ¹ and R ² each represent H, an alkyl group having 1 to 20 carbon atoms, a phenyl group, or an alkyl-substituted phenyl group having 1 to 20 carbon atoms. The thermoplastic resin material of the present invention is preferably in a powder form.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The graft copolymer (A) in the present invention is composed of 30 to 75% by weight of a rubbery polymer, 10 to 45 parts by weight of a vinyl cyanide monomer and an aromatic vinyl monomer. Monomer mixture 70-2 consisting of 55-90 parts by weight, 0-40 parts by weight of other copolymerizable vinyl monomers
5% by weight is the grafted copolymer. Here, the term "grafted" refers to a state in which a copolymer, which is a branch polymer, has a chemical bond with a rubbery polymer, which is a backbone polymer, and cannot be easily separated only by dispersing it in an organic solvent. It points.

As the rubbery polymer, a diene polymer (rubber) mainly composed of a conjugated diene unit such as 1,3-butadiene and an acrylate ester unit having 1 to 18 carbon atoms are mainly used. One selected from the group consisting of an acrylic rubber, an ethylene-propylene non-conjugated diene terpolymer rubber, and a polyorganosiloxane rubber containing a siloxane unit having an alkyl group having 1 to 6 carbon atoms in a side chain as a main component. The above-mentioned rubbery polymers may be used alone or in combination or in combination. The term "combined" as used herein indicates a state in which two or more rubbery polymers have no chemical or physical bond at all, and "complexed" means that two or more rubbery polymers are at a micro level. Indicates a state of being entangled or chemically bonded. In any case, the presence or absence of a chemical bond is not required, and selection can be made according to the intended use. For example, in applications in which only one property such as impact resistance, weather resistance, and coloring property during coloring is required, a single rubber-like polymer selected from the above-described group is preferable, and the performance of a plurality of resins is improved. In the required area, the combined use is preferable, and when a plurality of resin performances are required and the weather resistance is regarded as important, the combined use is preferable.

The diene-based polymer includes polybutadiene, styrene-butadiene copolymer rubber (SBR), acrylonitrile-butadiene copolymer rubber (NBR), isoprene rubber, chloroprene rubber and the like containing 1,3-butadiene unit as a main component. It can be used, particularly preferably polybutadiene or SBR.

The acrylic rubber can be prepared by using an acrylate unit having 1 to 12 carbon atoms, preferably 4 to 8 carbon atoms, as a main component, and using a crosslinking agent, preferably by emulsion polymerization. Can be used in combination, and the glass transition temperature thereof is lower than room temperature, and examples thereof include homo- or copolymers of butyl acrylate or 2-ethylhexyl acrylate. If the carbon number is outside the above range, sufficient rubber elasticity cannot be obtained.

The ethylene-propylene non-conjugated diene terpolymer is a terpolymer of ethylene, propylene and a non-conjugated diene monomer such as ethylidene norbornene or hexadiene.

As the polyorganosiloxane rubber,
Although not particularly limited, a polyorganosiloxane containing a vinyl polymerizable functional group is preferable.
More preferably, 0.3 to 3 mol% of a siloxane unit containing a vinyl polymerizable functional group and 97 dimethylsiloxane units
A polyorganosiloxane comprising at most 99.7 mol%, and further comprising 1 mol% or less of silicon atoms having three or more siloxane bonds based on all silicon atoms in the polydimethylsiloxane. As a method for producing the polyorganosiloxane, for example, a latex obtained by emulsifying a mixture of dimethylsiloxane and a siloxane-containing vinyl-containing functional group-containing siloxane or a mixture containing a siloxane-based cross-linking agent with an emulsifier and water at a high speed is used. After homogenization using a homomixer or a homogenizer that atomizes with a jet force from a high-pressure generator, polymerization is performed at a high temperature using an acid catalyst, and then the acid is neutralized with an alkaline substance. And the like. Examples of the method of adding the acid catalyst used for the polymerization include a method of mixing with a siloxane mixture, an emulsifier and water, and a method of dropping an emulsified product of the siloxane mixture into fine particles at a constant rate in a high-temperature acid aqueous solution. Considering the ease of controlling the particle size of the siloxane, a method of dropping an emulsion in which the siloxane mixture is finely divided into a high-temperature aqueous acid solution at a constant rate is preferred.

The dimethylsiloxane used for the production of the polyorganosiloxane includes a dimethylsiloxane-based cyclic having three or more members, and preferably a three- to seven-membered ring. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like. These may be used alone or as a mixture of two or more. Further, as the vinyl polymerizable functional group-containing siloxane, those containing a vinyl polymerizable functional group and capable of bonding via a dimethylsiloxane bond,
Considering the reactivity with dimethylsiloxane, various alkoxysilane compounds containing a vinyl polymerizable functional group are preferred. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydimethylsilane, methacryloyloxysiloxanes such as γ-methacryloyloxypropyldiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane, vinylsiloxanes such as tetramethyltetravinylcyclotetrasiloxane, p-vinylphenyldimethoxymethylsilane, and further γ-mercaptopropyl Dimethoxymethylsilane,
and mercaptosiloxanes such as γ-mercaptopropyltrimethoxysilane. These vinyl polymerizable functional group-containing siloxanes can be used alone or as a mixture of two or more. As the siloxane-based crosslinking agent, a trifunctional or tetrafunctional silane-based crosslinking agent, for example, trimethoxymethylsilane, triethoxydiphenylsilane, tetramethoxysilane, tetraethoxysilane,
Tetrabutoxysilane or the like is used.

The lower limit of the weight-average particle size of the rubber-like polymer as the dispersed particle size in the resin is 100 nm or more, more preferably 150 nm or more, and the upper limit is less than 500 nm, more preferably less than 400 nm. The method for adjusting the dispersion particle diameter of the rubbery polymer to the above range is not particularly limited, and examples thereof include a method of growing during polymerization to increase the particle diameter, and a method of producing particles smaller than 100 nm in advance and then preparing an acid, salt, or acid. A method of increasing the particle size to a desired particle size by adding a polymer latex containing a group can be used. The content of the rubbery polymer in the graft copolymer (A) is suitably from 30 to 75% by weight. If it is less than 30% by weight, the calendering processability is inferior, and if it exceeds 75% by weight, fish eyes of the calendar sheet increase.

Examples of the vinyl cyanide monomer used in the graft copolymer (A) include acrylonitrile, methacrylonitrile, ethacrylonitrile, maleonitrile, fumaronitrile and the like. Is preferably acrylonitrile. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pt-butylstyrene, and halogenated styrene. But,
As raw materials for the rubber-modified styrenic resin, styrene and / or
Alternatively, α-methylstyrene is preferred. Other copolymerizable vinyl monomers include acrylic ester monomers having 1 to 18 carbon atoms, methacrylic ester monomers having 1 to 18 carbon atoms, and unsaturated carboxylic anhydride monomers. And a maleimide-based monomer. Specifically, (meth) acrylic acid, maleic anhydride, methyl (meth) acrylate, ethyl (meth) acrylate,
N-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate,
N-hexyl (meth) acrylate, chloromethyl (meth) acrylate, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and the like can be used.

The usable ratio of the vinyl cyanide monomer, the aromatic vinyl monomer and other copolymerizable monomers used depends on the quality of the rubber-modified styrene resin sheet and the thermal coloring property. For the reason, when the total of them is 100 parts by weight, 10 to 45 parts by weight of a vinyl cyanide monomer, 55 to 90 parts by weight of an aromatic vinyl monomer, and other copolymerizable monomers A range of 0 to 40 parts by weight is preferred. The method for producing the graft copolymer (A) is not particularly limited, but the production of the vinyl cyanide monomer and the aromatic vinyl monomer and other vinyl monomers in the presence of the rubbery polymer is not limited. Examples of the method include graft copolymerization of the mixture by emulsification, suspension, lump, or a combination of two or more of them. From the viewpoint of controllability of the structure, emulsification or a combination of emulsion polymerization and other polymerization methods is preferable.

The copolymer (B) comprises 10 to 45% by weight of a vinyl cyanide unit, 55 to 90% by weight of an aromatic vinyl unit, and 0 to 40% by weight of another copolymerizable monomer unit.
(Total 100% by weight). The vinyl cyanide monomer, the aromatic vinyl monomer and other copolymerizable monomers in the copolymer (B) are all the same as those used in the graft copolymer (A). Are preferred. The method for producing the copolymer (B) is not particularly limited, but it can be produced by emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization or a combination of two or more of these.

The acrylic copolymer (C) used in the present invention comprises 10 to 95% by weight of methyl methacrylate units, 5 to 60% by weight of acrylate units, and monomer units copolymerizable therewith. It is a copolymer consisting of 0 to 50% by weight. The acrylic copolymer (C) needs to have a methyl methacrylate unit and an acrylate ester unit as essential components in its constituent units.
A polymer not containing these has almost no effect of improving the releasability around a bank or from a roll with respect to a rubber-modified styrenic resin. When the amount of the methyl methacrylate unit is more than 95% by weight, the releasability from the roll is poor. On the other hand, when the amount of the acrylate unit is more than 60% by weight, the periphery of the bank is deteriorated. Here, the methyl methacrylate unit and the acrylate unit are each derived from a methacrylate ester and an acrylate ester, and the acrylate is an ester of acrylic acid and an alkyl group having 1 to 18 carbon atoms. Yes,
Methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, acrylic acid Benzyl, phenyl acrylate and the like. Of these, it is preferable to use n-butyl acrylate and ethyl acrylate.

As the monomer units constituting the acrylic copolymer (C), if necessary, alkyl methacrylate units other than methyl methacrylate, or copolymerizable with methyl methacrylate and acrylic acid ester can be used. It is possible to introduce monomer units. Examples of the alkyl methacrylate ester excluding methyl methacrylate to introduce the above structural unit are esters of methacrylic acid and an alkyl group having 1 to 18 carbon atoms, and ethyl methacrylate,
N-butyl methacrylate, isobutyl methacrylate,
T-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, and the like.Examples of monomers copolymerizable with methyl methacrylate and acrylate include acrylonitrile, Monofunctional monomers such as styrene, α-methylstyrene, and vinyl acetate, and polyfunctional monomers such as allyl methacrylate and triallyl cyanurate are exemplified. When using a polyfunctional monomer,
The content is preferably 2% by weight or less in the acrylic copolymer (C).

The method for producing the acrylic copolymer is not particularly limited, but those produced by emulsion polymerization are preferred. Preferred forms of the acrylic copolymer (C) include 40 to 95% by weight of methyl methacrylate, 5 to 60% by weight of an acrylate ester, and 0 to 3 of other copolymerizable monomers.
0% by weight and its chloroform solution (1 g /
L) has a reduced viscosity (ηsp / C) of 1 measured at 25 ° C.
It is a copolymer (C-1) of 0 to 200 dL / g. As a more preferred form, methyl methacrylate 70-95
% By weight, ethyl acrylate or butyl acrylate 5
-30% by weight, and ηsp / C is 3-150 dL /
g of the copolymer. Regarding the ratio of methyl methacrylate and acrylate, the balance between the dispersibility of the acrylic copolymer (C) during the processing of the rubber-modified styrene resin and the bank circumference on the roll of the resin composition was excellent. From the viewpoint of achieving the above, it is preferable to be within this range. If ηsp / C is less than 1 dL / g, the performance of the rubber-modified styrenic resin is impaired, and if ηsp / C exceeds 200 dL / g, the acrylic copolymer (C) cannot be added to the rubber-modified styrenic resin. Dispersibility deteriorates and fish eyes occur.

Another preferred form of the acrylic copolymer (C) is a three-stage polymer (C-2) described below.
That is, (a) a polymer in which at least 5% by weight of its constituent units is methyl methacrylate, and ηs
(b) In the presence of 5 to 45 parts by weight of p / C less than 2 dl / g, (b) 0 to 70% by weight of alkyl methacrylate having an alkyl group having 1 to 18 carbon atoms
And the acrylic acid ester in an amount of from 40 to 70% by weight are mixed with 40 to 70 parts by weight of the component (b) alone having an ηsp / C of 1
In the presence of a two-stage polymer consisting of a polymer having the component (a) and the component (b) obtained by polymerization under the condition of dl / g or less, (c) methyl methacrylate 30 5 to 40 parts by weight of a monomer (mixture) composed of 0 to 100% by weight and 0 to 50% by weight of a monomer copolymerizable with methyl methacrylate [(a), (b)
And the total amount of component (c) is 100 parts by weight]. Here, examples of the alkyl methacrylate having an alkyl group having 1 to 18 carbon atoms include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, and methacrylic acid. -2-ethylhexyl, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate and the like. Also,
Examples of the acrylate having an alkyl group having 1 to 18 carbon atoms include those described above as examples of the acrylate. Further, as for the monomer copolymerizable with methyl methacrylate, those described above are also exemplified.
By giving the form of the three-stage polymer as described above, the dispersibility (uniform compatibility) of the acrylic copolymer (C) in the rubber-modified styrene resin and the roll processing of the rubber-modified styrene resin It becomes possible to make the property excellent.

As the acrylic copolymer (C), the acrylic copolymer (C-1) and the acrylic copolymer (C-2) can be used alone or in combination. The copolymer (C-1) has a large effect of improving the periphery of the bank, and the copolymer (C-2) has an effect of improving the releasability from the roll.
Less than. Further, the copolymer (C-2) has a large effect of improving the releasability from the roll, and the effect of improving the bank circumference is smaller than that of the copolymer (C-1). Therefore, by using the copolymers (C-1) and (C-2) together, a greater effect can be expected with a small amount of addition.

The composition ratio of the graft copolymer (A) is 10 to 98.9 parts by weight based on 100 parts by weight of the resin mixture. If the amount is less than 10 parts by weight, the proportion of the rubbery polymer necessarily decreases, and if it exceeds 98.9 parts by weight, the roll processability deteriorates. The composition ratio of the copolymer (B) is 89.9 to 1 part by weight based on 100 parts by weight of the resin mixture. When the amount is more than 89.9 parts by weight, the proportion of the rubbery polymer is inevitably reduced. When the amount is less than 1 part by weight, the roll processability deteriorates. The amount of the acrylic copolymer (C) to be added is within the range of 0.1 to 15 parts by weight per 100 parts by weight of the resin mixture, and the desired thermoplastic resin material is obtained. When the amount of the acrylic copolymer (C) is less than 0.1 part, the releasability of the rubber-modified styrene resin around the bank or from the heating roll is inferior. The performance is impaired, and more fish eyes are generated. When two or more acrylic copolymers (C) are used in combination, the total amount thereof must be within the above range. The content of the total rubbery polymer in the thermoplastic resin material is 5 to 60% by weight.
It is desirable that When the amount is less than 5% by weight, the original performance as a rubber-modified resin cannot be exhibited, and when the amount is more than 60% by weight, the roll processability deteriorates.

As the phosphorus compound (D) used in the present invention, a known alkyl or aryl phosphate compound can be used, but one object of the present invention is to obtain a resin composition having less thermal coloring. A pentaerythritol-di-phosphite compound represented by the following formula is preferred.

Embedded image Here, R ¹ and R ² represent H, an alkyl group having 1 to 20 carbon atoms, a phenyl group, and a phenyl group substituted with an alkyl group having 1 to 20 carbon atoms, respectively. Examples include bis (nonylphenyl) pentaerythritol-di-phosphite,
Di-stearylpentaerythritol di-phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol di-phosphite, bis (2,6-di-
(t-butyl-4-methylphenyl) pentaerythritol-di-phosphite and the like can be used. The minimum amount of the phosphorus-based stabilizer used is 100 parts by weight of the composition, and the minimum amount is 0.1.
05 parts by weight, preferably 0.1 parts by weight, the maximum amount being 5 parts by weight, preferably 3 parts by weight. If the amount is less than 0.05 part by weight, the thermal coloring of the resin becomes remarkable, and if it exceeds 5 parts by weight, calender (roll) processability is poor.

In order to impart excellent calender (roll) workability, which is the object of the present invention, to the rubber-modified styrenic resin, it is important to control the tension required for melting and breaking the resin mixture. . Resin temperature 1
The strand extruded from a 1.0 mm diameter die at 90 ° C. is taken out, and the lower limit of the tension at the time of breaking is 0.15.
N, more preferably 0.20N. If it is less than this, many fish eyes are generated in the sheet, and the releasability from the roll is greatly deteriorated.
On the other hand, the upper limit is 0.45 N, and more preferably 0.40 N. If the upper limit is exceeded, the winding property on rolls and the bank revolving property deteriorate. Any method may be used to change the breaking strength of the resin when it is melted. For example, the composition or molecular weight of the graft copolymer (A) or the copolymer (B), or a cross-linked structure thereof may be used. For example, a method of causing the user to take the information can be used.

In order to obtain a rubber-modified styrenic resin which is excellent in thermal coloring property and has little odor generated during processing, it is apparent that it is necessary to suppress the sulfur content remaining in the resin mixture. It has become This remaining sulfur content can be easily measured by a known method.
400 ppm in terms of the amount of sulfur element in the resin mixture
Or less, more preferably 300 ppm or less. If it exceeds this, not only the thermal coloring deteriorates as described above to impair the quality as a product, but also a large amount of odor during processing is generated, thus deteriorating the working environment. Any method may be used to reduce the remaining sulfur content, but it is necessary to minimize or not use sulfur-containing substances in various chemicals used in the production and processing of raw materials. For example, do not use sulfuric acid, aluminum sulfate, or magnesium sulfate in the coagulation process from a polymer latex.For example, a method of changing a coagulant to calcium chloride, calcium acetate, etc. A method of hardly remaining by changing the pH of the
In addition, a method of reducing or not using mercaptan, which is widely used as a chain transfer agent at the time of polymerization, or changing to another chain transfer agent, and adding a sulfur (thioether) heat stabilizer at the time of compounding the powder. Reduction or no use.

One of the objects of the present invention is to omit the step of shaping into pellets or the like in order to reduce the processing cost and to make the shape easy to process. Therefore, the average particle size of the obtained resin mixture is as follows. 100 to 800 μm, preferably 1
It is controlled to 50 to 600 μm. If it is smaller than this, the powder becomes lighter and easily dissipates into the air during processing, which may worsen the working environment or, in worse circumstances, may cause a dust explosion. On the other hand, if it exceeds 800 μm, the resin is hardly melted, and the fisheye of the sheet deteriorates. The method of controlling the particle size distribution of the powder may be any method, but if the average particle size falls within this range, there is almost no practical problem, and the graft copolymer (A), copolymer (B), Acrylic copolymer (C),
It is not necessary that the phosphorus compound and each of the various stabilizers and modifiers all be in this particle size range. In particular, the object is achieved by controlling the particle size of the graft copolymer (A) and / or copolymer (B) having a large blending ratio. However, since the purpose of using a powder having a specific particle size is to reduce the cost during shaping, shaping the resin mixed powder with a pelletizer, a Banbury mixer, or the like is not limited at all, and quality and It does not deteriorate the working environment during processing. In addition, when the resin composition is melt-mixed into a pellet shape by shaping, it is not necessary to fall within the particle size distribution range of the powder.

The method of blending the graft copolymer (A), the copolymer (B), the acrylic copolymer (C), and the phosphorus compound (D) to obtain a desired powder is not particularly limited. However, for the purpose of the present invention to obtain a powder mixture having an average particle size of 100 to 800 μm, for example,
(A)-(D) a method of mixing each powder, an acrylic copolymer produced by emulsion polymerization on a graft copolymer (A) and / or (B) latex produced by emulsion polymerization (C) After mixing the latex, a polymer may be recovered from the mixed latex to obtain a powder mixture, and then a method of mixing a powdery phosphorus-based stabilizer may be used.

When compounding these (A) to (D),
It is necessary to add various stabilizers as needed.
Examples of stabilizers include hindered phenols, (D)
Other than phosphite-based, thioether-based antioxidants,
Examples include benzotriazole-based and benzophenone-based ultraviolet absorbers and hindered amine-based light stabilizers. Also,
In addition to the stabilizer, various coloring agents, metal soaps, plasticizers, lubricants and the like can be added. The addition of a metal soap among these is preferred for the rubber-modified styrenic resin of the present invention. In particular, when the proportion of the rubbery polymer in the composition is small, the effect of improving the releasability from the roll by the acrylic copolymer (C) may be small. The effect of improving the releasability from flakes can be exhibited more greatly. Examples of metal soaps include salts of stearic acid such as magnesium, calcium, barium and zinc.

Further, a flame retardant, an antistatic agent, an antibacterial / antifungal agent and the like can be added according to the purpose. Examples of flame retardants and flame retardant aids include tetrabromobisphenol A, bis (dibromopropyl) tetrabromobisphenol A, octabromodiphenyl ether, decabromodiphenyl ether, hexabromocyclododecane, brominated polycarbonate, polyvinyl chloride, end-modified -Unmodified brominated epoxy flame retardants (for example, a polymer of glycidyl ether of tetrabromobisphenol A), phosphates (tributyl phosphate, tricresyl phosphate, etc.), and halogenated phosphates (Tris (2, 3-dibromopropyl) phosphate, tris (bromochloropropyl) phosphate, etc.), antimony trioxide, chlorinated polyethylene, Teflon and the like. Examples of the antistatic agent include amine-based, ammonium salt-based, sulfonate-based, polyoxyethylene-based, and polyether-polyamide block-based. Examples of antibacterial and antifungal agents include organic agents such as imidazole, thiazole, nitrile, haloalkyl, and pyridine, and inorganic agents such as silver, zinc, copper, and titanium. Is exemplified. Of these, it is preferable to use a silver-based material that is thermally stable and has high performance. Silver-based antibacterial agents include zeolite, silica gel,
Good examples include silver, silver ions, silver complexes, and silver compounds supported on a porous structure such as zirconium phosphate, calcium phosphate, hydrotalcite, hydroxyapatite, and calcium silicate. ,
Examples thereof include silver salts of alkyl phosphates.

Further, in order to give the sheet of the thermoplastic resin material of the present invention an appearance such as a stone tone, a pearl tone, a metallic tone, etc., a colored fluorine resin, urethane resin, epoxy resin, phenol resin, urea resin, Polyester resin / fiber, aramid resin / fiber, glass fiber, carbon fiber,
It is also possible to add ceramic fibers, metal particles and fibers such as aluminum, stainless steel, and copper, iriodine, talc, mica, and the like.

[0034]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. Further, “parts and%” in the examples represent “parts by weight and% by weight” unless otherwise specified.

[Evaluation Method] [Measurement of Weight Average Particle Diameter] The rubbery polymer latex was directly observed with a transmission electron microscope, the particle diameter of 200 to 300 particles was measured, and the average particle diameter was determined. Was. [Measurement of Graft Ratio] Graft copolymer obtained (including one not chemically bonded to rubbery polymer) 0.5
g was dispersed in 80 ml of acetone, extracted at 65 ° C. for 3 hours, and the mixture was centrifuged at 14,000 rpm. The insolubles were dried under vacuum, and the graft ratio was calculated from the weight ratio and the ratio of the rubbery polymer charged during the polymerization. [Measurement of Reduced Viscosity (ηsp / C)] A predetermined amount of a sample was dissolved in a solvent and measured at a temperature of 25 ° C. using an Ubbelohde tube. [Measurement of powder particle size] The mixed powder was measured according to JIS408. [Measurement of residual sulfur content] The residual sulfur content was determined by the atomic absorption method. [Measurement of Melting Strength] Using a Capillograph (manufactured by Toyo Seiki Seisaku-sho, Ltd.), a resin was die-dies (inner diameter 1.0 mm) at a cylinder temperature of 190 ° C. and a piston descending speed of 10 mm / min.
And discharge the discharged strand from the other. The take-up speed at that time was gradually increased, and the tension at which the resin was broken was measured.

[Rollability on Roll] Using a 6-inch roll, 100 g of the resin powder mixture was mixed at a roll kneading temperature of 180.
° C, roll rotation speed 14 × 16 rpm, roll interval 0.3
The roll was rotated and kneaded in mm, and the state of adhesion to the roll was observed. The evaluation was performed using a five-step method, where 5 indicates a state of very close contact, 1 indicates a state of very poor contact, and the closer the number is to 5, the better the roll winding property. Show. [Around Bank] The condition of the bank on the resin roll was observed under the above conditions. The evaluation was performed using a five-step method, where 5 indicates that the bank was rod-shaped and smoothly rotated, and the bank rotation was good.
Indicates that the bank entrains the wavy air and the bank rotation is poor, and the closer the number is to 5, the better the bank rotation and the better the appearance of the sheet. [Removability from Roll] After the resin was kneaded with the roll under the above conditions for 3 minutes, the releasability from the roll surface was evaluated. The evaluation is performed using a five-step method, where 5 is the highest peelability, 1 is the lowest peelability, and the closer the value is to 5, the better the peelability from the roll. [Evaluation of Odor During Roll Processing] When the resin was kneaded with the roll under the above conditions for 3 minutes, the odor generated by the resin at a distance of 1 m from the roll was evaluated by olfaction. The evaluation was performed using a five-step method. 5 indicates that the odor was the least, 1 indicates the most unpleasant state, and the numerical value closer to 5 indicates that the odor during processing is better (3 times) And three averages).

[Evaluation of thermal coloring property] Under the above conditions, the resin was kneaded with a roll, and after 3 minutes and 10 minutes from the start, the resin was sampled and the color difference of a sheet pressed to a thickness of about 1 mm was measured by Murakami Color Research Laboratory. High-speed spectrophotometer (CMS-1500)
And the change in color between the sample after 10 minutes and the sample after 3 minutes was indicated as ΔYI and ΔE. [Evaluation of fish eye on sheet surface] 25mmφ uniaxial small non-venting extruder
At a barrel temperature of 180 ° C., a T-die temperature of 190 ° C., a screw rotation speed of 30 rpm and a width of about 10
To prepare a sheet of 0 mm × thickness 150 [mu] m, were counted upward projected area 0.05 mm ² or more of the number of fish eyes of the sheet area 0.05 m ² per visually.

[Preparation of Various Components] [Graft Copolymer A-1, Copolymer B-1] In a 10 L stainless steel autoclave equipped with a thermometer and a stirrer,
The following components were charged. Deionized water (hereinafter simply referred to as water) ... 150 parts Sodium oleate ... 0.5 parts Disproportionated potassium rosinate ... 1.3 parts Anhydrous sodium sulfate ... 0.2 parts Water Sodium oxide: 0.02 parts t-dodecyl mercaptan: 0.2 parts Potassium persulfate: 0.3 parts Styrene: 5 parts

After the replacement with nitrogen, 95 parts of 1,3-butadiene was charged with stirring and the internal temperature was raised to 50 ° C. This temperature was maintained for 5 hours, after which the temperature was increased stepwise to a final temperature of 80 ° C. After performing polymerization for a total of 36 hours, the remaining butadiene was removed by devolatilization. Finally, a rubbery polymer having a solid content of 39.8%, a weight average particle diameter of 270 nm, and a gel content of 92% was obtained. Subsequently, the following components were charged into a 5 L glass reactor equipped with a thermometer and a stirrer, and the internal temperature was raised to 60 ° C. The above rubber-like polymer (as solid content) ... 45 parts Water (including water in the rubber-like polymer) ... 135 parts Disproportionated potassium rosinate ... 0.3 parts Sodium hydroxide ...・ 0.02 parts Dextrose ・ ・ ・ 0.35 parts Acrylonitrile ・ ・ ・ 5.8 parts Styrene ・ ・ ・ 14.2 parts Cumene hydroperoxide ・ ・ ・ 0.15 parts

An aqueous solution comprising the following components was added thereto to initiate polymerization. Ferrous sulfate heptahydrate 0.005 parts Anhydrous sodium pyrophosphate 0.1 part Water 5 parts Then, when the heat of polymerization disappeared, a mixture of the following three components was added for 2 hours. The mixture was fed into a kettle for polymerization, and the latex was cooled. Acrylonitrile: 10.2 parts Styrene: 24.8 parts Cumene hydroperoxide: 0.2 parts To this was added 0.2 parts of an antioxidant, and twice the amount of the obtained latex The solution was poured into a 0.4% sulfuric acid aqueous solution adjusted to 75 ° C., and then the pH of the slurry was adjusted to 5, and the temperature was increased to 92 ° C. and maintained for 5 minutes. Dehydration and washing were repeated and finally dried to obtain a milky white powdery copolymer having an average particle size of 350 nm. 97% yield. The graft ratio of the obtained graft polymer was 80%, and the intended graft copolymer (A-1) insoluble in acetone was obtained by grafting 36% of the branch polymer to 45% of the rubbery polymer. Will be. The remaining 19% corresponds to the copolymer (B) having no chemical bond, and ηsp of a DMF solution (0.2 g / dl) of the copolymer (B-1) which is an acetone-soluble component.
/ C was 0.81 dl / g.

[Graft copolymer A-2, copolymer B-
2] The following components were charged into a 5 L glass reactor equipped with a thermometer and a stirrer, and the internal temperature was raised to 40 ° C under stirring. Water: 175 parts n-butyl acrylate: 99.1 parts Allyl methacrylate: 0.6 parts 1,3-butylene methacrylate: 0.3 parts Dipotassium alkenyl succinate: 1.0 Part t-butyl hydroperoxide 0.1 part Rongalit 0.3 part sodium sulfate 0.2 part

Further, a mixture comprising the following three components was added to initiate polymerization. Ferrous sulfate heptahydrate 0.0005 parts Disodium ethylenediaminetetraacetate 0.0005 parts Water 5 parts Polymerization is continued until there is no heat generated by polymerization, weight average particle diameter 320 nm, solid content An acrylic rubber latex of 34.6% was obtained. Subsequently, the following components were charged and heated to 80 ° C. with stirring. This rubber-like polymer latex (solid content) ... 45 parts Water (including water in the rubber-like polymer) ... 200 parts Rongalit ... 0.2 parts Dipotassium alkenyl succinate ... 0.8 Department

A mixture of the following components was added to 18
It was fed into the system over 0 minutes to carry out polymerization. Acrylonitrile 13.8 parts Styrene 41.2 parts n-octyl mercaptan 0.05 parts t-butyl hydroperoxide 0.1 parts Then, the above graft copolymer (A- The same treatment as in the preparation of 1) was performed to obtain a graft copolymer (A-2).
Yield 98%. The graft ratio of the obtained graft polymer was 7
The target graft copolymer (A-2), which is 5%, and is insoluble in acetone, is obtained by grafting 33.8% of a branch polymer to 45% of a rubbery polymer. The remaining 21.2% corresponds to the copolymer (B) having no chemical bond.
Ηsp / C of the MF solution (0.2 g / dl) is 0.85 dl /
g.

[Graft copolymer A-3, copolymer B-
3] The following components were charged into a 5 L glass reactor equipped with a thermometer and a stirrer, and the internal temperature was raised to 50 ° C. with stirring. Rubber latex (solid content) produced from graft copolymer A-1 5 parts Water (including water in rubber latex) 175 parts n-butyl acrylate 39.4 parts Allyl methacrylate ··· 0.4 parts 1,3-butylene methacrylate ··· 0.2 parts Dipotassium alkenyl succinate ··· 0.4 parts t-butyl hydroperoxide ··· 0.1 parts Rongalit ··· 0.1 3 parts Sodium sulfate 0.1 part

Further, a mixture of the following three components was added to initiate polymerization. Ferrous sulfate heptahydrate: 0.0005 parts Disodium ethylenediaminetetraacetate: 0.0015 parts Water: 5 parts The polymerization was continued until the heat of polymerization disappeared, the weight average particle diameter was 290 nm, and the solid content was A 19.5% composite rubber latex was obtained. Thereafter, polymerization and recovery operations were carried out in the same manner as for the graft copolymer (A-2), and the graft copolymer (A
-3) was obtained. 97% yield. The graft ratio of the obtained graft polymer was 84%, and the intended acetone-insoluble graft copolymer (A-3) was a rubber-like polymer 4
57.8% is grafted with 37.8% of the branch polymer. The remaining 17.2% corresponds to the copolymer (B) having no chemical bond. Ηsp of the DMF solution (0.2 g / dl) of the copolymer (B-3) which is an acetone-soluble component is used. / C
Was 0.82 dl / g.

[Graft copolymer A-4, copolymer B-
4] A mixture consisting of the following components was put into a 5 L glass reactor equipped with a thermometer and a stirrer by a homomixer at 10,000.
Preliminarily stirred at rpm. Water: 200 parts Sodium dodecylbenzenesulfonate: 1.0 parts Dodecylbenzenesulfonic acid: 1.0 parts Okdamethylcyclotetrasiloxane: 97.5 parts Tetraethoxysilane: 2.0 Part γ-methacryloyloxypropyldimethoxymethylsilane ... 0.5 part Then, an emulsified liquid emulsified and dispersed at a pressure of 30 MPa by a homogenizer is added, heated at 80 ° C for 5 hours, and then left at 20 ° C for 48 hours. Thereafter, the pH of the latex was neutralized to 7 with an aqueous sodium hydroxide solution to complete the polymerization, and a polyorganosiloxane rubber latex having a weight average particle diameter of 150 nm and a solid content of 31.5% was obtained.

Further, the following components were charged, and the internal temperature was raised to 50 ° C. with stirring. The polyorganosiloxane rubber latex (as solid content): 5 parts Water (including water in the rubber latex): 175 parts n-butyl acrylate: 39.4 parts Allyl methacrylate: 0.0 4 parts 1,3-butylene methacrylate ... 0.2 parts Dipotassium alkenyl succinate ... 0.4 parts t-butyl hydroperoxide ... 0.1 parts Rongalit ... 0.3 parts Sodium sulfate 0.1 part Further, a mixture comprising the following three components was added to initiate polymerization. Ferrous sulfate heptahydrate 0.0005 parts Disodium ethylenediaminetetraacetate 0.0005 parts Water 5 parts

The polymerization was continued until the heat of polymerization disappeared, to obtain a composite rubber latex having a weight average particle diameter of 200 nm and a solid content of 19.8%. Thereafter, the graft copolymer (A-
Polymerization and recovery operations were performed in the same manner as in 2) to obtain a graft copolymer (A-4). Yield 98%. The graft ratio of the obtained graft polymer was 80%, and the intended graft copolymer (A-4) insoluble in acetone was obtained by grafting 36.0% of a branch polymer to 45% of a rubbery polymer. You are doing. The remaining 19.0% corresponds to a copolymer (B) having no chemical bond, and the acetone-soluble copolymer (B-4) in a DMF solution (0.2 g / d)
ηsp / C of 1) was 0.87 dl / g.

[Graft copolymer A-5, copolymer B-
5] In the preparation example of the graft copolymer (A-1), the sulfuric acid aqueous solution concentration at the time of coagulation was set to 0.8%, and the pH of the slurry was adjusted.
The processing was carried out in the same manner except that was changed to 1.5. yield,
The graft ratio and the reduced viscosity of the acetone-soluble component were equivalent to (A-1). [Graft Copolymer A-6, Copolymer B-6] In the preparation example of graft copolymer (A-1), t-dodecyl mercaptan 0.3 was added to the mixture supplied in the second stage during the graft polymerization. The same processing was performed except that the part was used.
A milky white powdery copolymer having a thickness of 70 nm was obtained. Yield 9
7%. The graft ratio of the obtained graft polymer was 63%, and the desired graft copolymer (A-6) insoluble in acetone was a rubbery polymer of 45% and a branch polymer of 2%.
This means that the graft is 8.4%. Also, 26.
6% corresponds to the copolymer (B) having no chemical bond, and ηsp / C of the DMF solution (0.2 g / dl) of the acetone-soluble copolymer (B-6) is 0.2%. It was 52 dl / g.

[Copolymer B-7] Acrylonitrile unit 28%, styrene unit 72
%, A copolymer (B-7) having a ηsp / C of 0.73 dl / g as measured at 25 ° C. in a DMF solution (0.2 g / dl)
I got [Copolymer B-8] ηsp / C of 39% of acrylonitrile unit, 61% of styrene unit and DMF solution (0.2 g / dl) measured at 25 ° C. is 0.4 by a known emulsion polymerization method.
A copolymer (B-8) having a flow rate of 2 dl / g was obtained. [Copolymer B-9] Acrylonitrile unit 23%, α by a well-known emulsion polymerization method in the same manner as copolymer B-8.
-77% methylstyrene unit, DMF solution (0.2 g /
dl) measured at 25 ° C. is 0.46 dl / g.
(B-9) was obtained.

[Copolymer B-10] In the same manner as for Copolymer B-7, ηsp / C was measured at 25 ° C. for a 21% acrylonitrile unit, 79% styrene unit, and DMF solution (0.2 g / dl). Is 0.41 dl / g (B-
10) was obtained. [Copolymer B-11] Similarly to copolymer B-7, acrylonitrile unit 34%, styrene unit 66%, DM
Ηsp / C of F solution (0.2 g / dl) measured at 25 ° C.
Was 2.2 dl / g, to obtain a copolymer (B-11).

[Acrylic Copolymer C-1] The following components were charged into a 5 L glass reactor equipped with a thermometer and a stirrer, and the temperature was raised to 65 ° C. while stirring under a nitrogen flow to initiate polymerization. Water: 200 parts Methyl methacrylate: 80 parts Butyl acrylate: 20 parts Sodium dioctyl sulfosuccinate: 1.5 parts Ammonium persulfate: 0.2 parts Polymerization was continued for 4 hours. The obtained polymer latex was coagulated with a 5% aqueous aluminum chloride solution, washed and dried to obtain a white powdery acrylic copolymer (C-
1) was obtained. A chloroform solution of this (C-1) (0.1%) was used.
1g / dl) was measured at 25 ° C., and ηsp / C was 11.8.
dl / g.

[Acrylic Copolymer C-2] The following components were charged into a 5 L glass reactor equipped with a thermometer and a stirrer, and the temperature was raised to 65 ° C. while stirring under a nitrogen flow, followed by polymerization for 4 hours. (Ηsp / C of this polymer is 1.5
dl / g). Water: 280 parts Methyl methacrylate: 30 parts n-octyl mercaptan: 0.003 parts Sodium dioctyl sulfosuccinate: 1.5 parts Ammonium persulfate: 0.2 parts Subsequently, the following 3 The mixture composed of the components was supplied over 1 hour to carry out polymerization. The ηsp / C of a polymer obtained by polymerizing only this component under the same conditions was 0.6 dl / g. Butyl methacrylate 30 parts Butyl acrylate 20 parts n-octyl mercaptan 0.5 part Further, a mixture comprising 20 parts of methyl methacrylate and 0.002 part of n-octyl mercaptan. Was supplied over 30 minutes to carry out polymerization. The polymer latex finally obtained is coagulated with a 5% aqueous solution of aluminum sulfate, washed and dried to obtain a powdery acrylic copolymer (C-
2) was obtained.

[Phosphorus Compound D-1] Di-stearylpentaerythritol di-phosphite (Adeka Stab PEP-8 manufactured by Asahi Denka Kogyo KK) [Phosphorus compound D-2] bis (2,6-di- t-butyl-4-methylphenyl) pentaerythritol-di-phosphite (ADEKA STAB PEP- manufactured by Asahi Denka Kogyo KK)
36) [Phosphorus Compound D-3] Bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite (ADK STAB PEP-24G manufactured by Asahi Denka Kogyo KK)

[Examples 1 to 15 and Comparative Examples 1 to 8] The obtained graft copolymer (A, partially containing the copolymer (B)), the copolymer (B) separately produced, and an acrylic copolymer The copolymer (C) and the phosphorus compound (D) were mixed in a blending ratio of parts by weight shown in Tables 1 and 2, and 0.4 part of magnesium stearate and 0.8 part of ethylenebisstearylamide were further added. Were mixed with a Henschel mixer to obtain the desired powder mixtures. Various physical properties of these powder mixtures were evaluated under the above conditions.

[0056]

[Table 1]

[0057]

[Table 2]

As is apparent from the above, by using the thermoplastic resin material of this embodiment, the roll workability is excellent, and the generation of odor, heat coloring property and fish eye can be reduced. On the other hand, Comparative Examples 1 and 2 having a large residual sulfur content
In Comparative Example 3 where the melt tension is low, peelability from the roll is poor, fish eyes are often generated, and in Comparative Example 4 where the melt tension is high, bank rotation is poor. In Comparative Example 5 not including the acrylic copolymer (C), Comparative Example 6 in which the periphery of the bank was poor, the peelability from the roll was poor, and the amount of the acrylic copolymer (C) was large.
However, the peelability from the roll is poor. In Comparative Example 7 containing no phosphorus compound, thermal coloring was caused, and in Comparative Example 8 containing a large amount of phosphorus compound, the releasability from a roll was poor.

[0059]

Industrial Applicability The thermoplastic resin material of the present invention can be calendered without undergoing a shaping step, has good moldability when subjected to calendering, and has a low odor during processing. Further, the appearance of the obtained resin sheet, especially the fish eye is small. Therefore, it has become possible to use the rubber-modified styrenic resin in a wide range of industrial fields.

Claims (9)

[Claims] 1. A graft copolymer in which a monomer unit containing a vinyl cyanide-based unit, an aromatic vinyl-based unit, and another copolymerizable vinyl-based unit is grafted to a rubber-like polymer through a chemical bond. (A) 10 to 98.9 parts by weight, 10 to 45% by weight of vinyl cyanide units, 90 to 55% by weight of aromatic vinyl units, and 0 to 40% by weight of other copolymerizable vinyl units. Monomer units (total 10
(B) (89.9 to 1 part by weight), 10 to 95% by weight of methyl methacrylate unit, 5 to 60% by weight of acrylate unit, and a monomer copolymerizable therewith. 0.1 to 15 parts by weight of an acrylic copolymer (C) consisting of 0 to 50% by weight of a body unit (however, (A) + (B) +
(In the case where the total of the resin mixture composed of (C) is 100 parts by weight) and 0.05 to 5 parts by weight of the phosphorus compound (D), and satisfies the following requirements. Thermoplastic resin material. The residual sulfur content in the thermoplastic resin material is 400 ppm or less. A tension is applied to a strand discharged after the thermoplastic resin material is melted at a resin temperature of 190 ° C., and the tension when the strand breaks is 0.15 to 0.45 N. 2. The rubbery polymer is a diene rubber containing a diene unit as a main component, an acrylic rubber containing an acrylate unit having 1 to 18 carbon atoms as a main component, an ethylene-propylene non-conjugated diene. A terpolymer rubber, which is one rubbery polymer selected from the group consisting of polyorganosiloxane-based rubbers having a siloxane unit having an alkyl group having 1 to 6 carbon atoms in a side chain as a main component; The thermoplastic resin material according to claim 1, wherein 3. The rubber-like polymer is a diene rubber having a diene-based unit as a main component, an acrylic rubber having a acrylate unit having 1 to 18 carbon atoms as a main component, an ethylene-propylene non-conjugated diene. Ternary copolymer rubber, which is used in combination with at least two or more rubbery polymers selected from the group consisting of polyorganosiloxane rubbers having a siloxane unit having an alkyl group having 1 to 6 carbon atoms in the side chain as a main component. 2. The thermoplastic resin material according to claim 1, wherein 4. The rubbery polymer is a diene-based rubber having a diene-based unit as a main component, an acrylic rubber having a acrylate unit having 1 to 18 carbon atoms as a main component, an ethylene-propylene non-conjugated diene. Ternary copolymer rubber, selected from the group consisting of polyorganosiloxane rubbers containing siloxane units having alkyl groups having 1 to 6 carbon atoms in the side chain as a main component, and compounding at least two or more rubbery polymers The thermoplastic resin material according to claim 1, wherein 5. The thermoplastic resin material according to claim 1, wherein the content of the total rubbery polymer in the thermoplastic resin material is 5 to 60% by weight. 6. The acrylic copolymer (C) comprises 40 to 95% by weight of methyl methacrylate unit, 5 to 60% by weight of acrylate ester and 0 to 30% by weight of a monomer unit copolymerizable therewith. And a reduced viscosity (ηs) of a chloroform solution (0.1 g / dl) measured at 25 ° C.
The thermoplastic resin material according to claim 1, wherein the thermoplastic resin material is an acrylic copolymer (C-1) having a p / C of 1.0 to 200 dL / g. 7. The acrylic copolymer (C),
(A) A polymer in which at least 5% by weight of its constituent units is methyl methacrylate, and the ηsp / C of the polymer chloroform solution (0.1 g / dl) measured at 25 ° C. is less than 2 dl / g. In the presence of 5 to 45 parts by weight of a polymer, (b) 0 to 70% by weight of an alkyl methacrylate having an alkyl group having 1 to 18 carbon atoms and 1 to 1 carbon atoms
(A) component obtained by polymerizing 40 to 70 parts by weight of a mixture of 100 to 30% by weight of acrylic ester of No. 8 under the condition that ηsp / C of component (b) alone is 1 dl / g or less. And (c) 30 to 100% by weight of methyl methacrylate and a monomer 0 copolymerizable with the methyl methacrylate in the presence of a two-stage polymer comprising a polymer having the component (b) as a constituent unit. A three-stage polymer obtained by polymerizing 5 to 40 parts by weight of a monomer (mixture) consisting of 50% by weight [however, the total amount of components (a), (b) and (c) is 100 parts by weight] The thermoplastic resin material according to claim 1, wherein the thermoplastic resin material is (C-2). 8. The thermoplastic resin material according to claim 1, wherein the phosphorus compound (D) is a pentaerythritol-diphosphite compound represented by the following formula. Embedded image Here, R ¹ and R ² each represent H, an alkyl group having 1 to 20 carbon atoms, a phenyl group, or an alkyl-substituted phenyl group having 1 to 20 carbon atoms. 9. The method according to claim 1, wherein the powder is in the form of a powder.
9. The thermoplastic resin material according to any one of items 1 to 8.