WO2003102076A1

WO2003102076A1 - Thermoplastic resin composition

Info

Publication number: WO2003102076A1
Application number: PCT/JP2003/007038
Authority: WO
Inventors: Tetsuo Noguchi; Yoshiaki Katoh
Original assignee: Denki Kagaku Kogyo Kabushiki Kaisha
Priority date: 2002-06-04
Filing date: 2003-06-03
Publication date: 2003-12-11
Also published as: CN1289593C; JP4534075B2; JPWO2003102076A1; AU2003241990A1; KR101050701B1; CN1659227A; KR20050024308A; HK1079807A1

Abstract

A thermoplastic resin composition excellent in transparency and capable of giving molded articles which are excellent in impact resistance and fabrication quality even when they have thin walls. The thermoplastic resin composition comprises a rubber-modified styrene resin composition comprising 60 to 80 % by mass of a continuous phase made of a styrene/(meth)acrylate copolymer and 40 to 20 % by mass of a dispersed phase made of a graft copolymer obtained by grafting a rubbery elastomer with a styrene/(meth)acrylate copolymer wherein the volume-mean particle diameter of the dispersed phase is 0.3 to 0.6 μm and the weight-average molecular weight (Mw) of the continuous phase and the constituent monomer units thereof satisfy a specific relationship and is characterized by containing 0.005 to 0.05 part by mass of an organopolysiloxane and, if necessary, 0.1 to 2.5 parts by mass of an ester lubricant per 100 parts by mass of the rubber-modified styrene resin composition.

Description

Description Thermoplastic resin composition Technical field

The present invention relates to a thermoplastic resin composition capable of obtaining a molded article having excellent transparency and exhibiting excellent impact resistance and molding workability even in an extremely thin wall. Background art

Conventionally, two or more monomers selected from styrene, methyl methacrylate and acrylonitrile are emulsified in a rubbery polymer latex obtained by emulsion polymerization of a mixture of butadiene and styrene, or acrylonitrile and butadiene monomer. It is known that a thermoplastic resin composition having excellent impact resistance and transparency can be obtained by mixing an MBS-based polymer obtained by polymerization with a rubber-modified styrene-based polymer. 4 6—3 2 7 4 8 Publication). However, although these thermoplastic resin compositions are certainly excellent in impact resistance, they have a drawback that good transparency cannot be obtained depending on molding conditions.

Furthermore, in recent years, molded products have become thinner, and at present the demands for thin-walled products having high rigidity and excellent thin-wall forming workability have become extremely high. As means for solving these problems, Japanese Patent Application Laid-Open No. 2001-226647 discloses a continuous phase of a specific styrene- (meth) acrylate copolymer and a specific graft copolymer. A rubber-modified styrene resin composition comprising a polymer dispersed phase has been proposed. However, for extremely thin molded products, impact resistance or moldability was not necessarily sufficient.

In view of the above situation, the present invention provides a thermoplastic resin composition which has excellent transparency and can obtain a molded article exhibiting excellent impact resistance and molding workability even in an extremely thin wall. Things. Disclosure of the invention

The present inventors have conducted intensive studies to solve such problems, and as a result, have found that a continuous phase of a specific styrene- (meth) acrylate copolymer and a dispersed phase of a specific graft copolymer are obtained. The present inventors have found that the above-mentioned problems can be solved by a thermoplastic resin composition containing a specific amount of an organic polysiloxane in a rubber-modified styrenic resin composition composed of the following, and completed the present invention. .

That is, the present invention has the following features.

1. (I) Styrene-based monomer, (meth) acrylate-based monomer, and, if necessary, a copolymer of these monomers and a copolymerizable vinyl monomer And (II) a styrene monomer and a (meth) acrylic ester monomer in the rubbery elastic body, with a continuous phase of 60 to 80% by mass of a styrene mono (meth) acrylate copolymer. Styrene- (meth) acrylate-based copolymers, which are copolymers of vinyl monomers that can be copolymerized with these monomers and are used as necessary A rubber-modified styrenic resin composition containing 40 to 20% by mass of a dispersed phase of a graft copolymer,

The volume average particle diameter of the dispersed phase is 0.3 to 0.6 zm, and the weight average molecular weight (Mw) of the continuous phase and X of the formula (1) obtained from the constituent monomer unit are expressed by the formula (2) And a thermoplastic resin composition comprising 0.005 to 0.05 parts by mass of an organic polysiloxane with respect to 100 parts by mass of the resin composition. —— ,,,,,,, — (meth) acrylate monomer unit (% by mass),, ^{X =} star summer average molecular weight ^{(Mw) X} V styrene monomer unit (% by mass) ⁽¹⁾

120000≤X≤160000 (2)

2. The rubber-modified styrenic resin composition comprises: (I) 60 to 70% by mass of a continuous phase of a styrene- (meth) acrylate copolymer; and (II) 40 to 70% by mass of a dispersed phase of a graft copolymer. 2. The thermoplastic resin composition according to the above 1, containing 30% by mass. 3. The thermoplastic resin composition according to the above 1 or 2, comprising 0.1 to 2.5 parts by mass of an ester lubricant relative to 100 parts by mass of the rubber-modified styrene resin composition.

4. The thermoplastic resin composition according to the above item 3, wherein the ester lubricant is a hardened castor oil.

5. The thermoplastic resin composition according to any one of the above items 1 to 4, wherein the organic polysiloxane is polydimethylsiloxane.

6. The continuous phase is composed of 20 to 70% by mass of a styrene-based monomer unit, 30 to 80% by mass of a (meth) acrylate-based monomer unit, and, if necessary, Any of the above-mentioned 1 to 5, which is a styrene-mono (meth) acrylate ester copolymer, which is a copolymer of 0 to 10% by mass of a vinyl monomer unit copolymerizable with a monomer. Item 2. The thermoplastic resin composition according to item 1.

7. The dispersed phase is composed of 30 to 80 parts by mass of a rubbery elastomer of polybutadiene and Z or styrene-butadiene copolymer, 20 to 70% by mass of styrene-based monomer units, and (acrylic) acrylic. A copolymer of 30 to 80% by mass of an acid ester monomer unit and 0 to 10% by mass of a vinyl monomer unit copolymerizable with these monomers and used as necessary. The thermoplastic resin composition according to any one of the above 1 to 5, which is a graft copolymer obtained by grafting 20 to 70 parts by mass of a styrene- (meth) acrylate ester-based copolymer. object.

8. The continuous phase is composed of 20 to 70% by mass of a styrene-based monomer unit, 30 to 80% by mass of a (meth) acrylate-based monomer unit, and used as necessary. A styrene- (meth) acrylate-based copolymer which is a copolymer of 0 to 10% by mass of a vinyl-based monomer unit copolymerizable with a monomer, and in which a polybutadiene and And / or 30 to 80 parts by mass of a styrene-butadiene copolymer rubber-like elastic material, 20 to 70% by mass of a styrene monomer unit, and 30 to 70% by mass of a (meth) acrylic acid ester monomer unit Styrene mono (meth) acryl, which is a copolymer of 80% by mass and 0 to 10% by mass of a vinyl monomer unit copolymerizable with these monomers and used as necessary. The above-mentioned 1 is a graft copolymer in which 20 to 70 parts by mass of an acid ester copolymer is grafted. According to any one of Itaru 5 Thermoplastic resin composition. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail. The styrene- (meth) acrylate-based copolymer constituting the continuous phase of the rubber-modified styrene-based resin composition of the present invention includes styrene-based monomers, (meth) acrylate-based monomers, and It is a copolymer of a vinyl monomer that can be used as necessary and that can be copolymerized with these monomers. The graft copolymer constituting the dispersed phase of the rubber-modified styrenic resin composition of the present invention includes: a rubbery elastic body, a styrene-based monomer, a (meth) acrylate-based monomer, and A graft copolymer obtained by grafting a styrene- (meth) acrylate copolymer, which is a copolymer of a vinyl monomer copolymerizable with these monomers and used as necessary. is there.

Styrene monomers used in the continuous phase and the dispersed phase of the present invention include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, ethylstyrene, -t-butylstyrene and the like. And styrene is preferred. These styrene monomers may be used alone or in combination of two or more.

Examples of the (meth) acrylate monomer used in the present invention include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and other methyl acrylates, methyl acrylate, and ethyl acrylate. And acrylate esters such as n-butyl acrylate, 2-methylhexyl acrylate, 21-ethylhexyl acrylate, and decyl acrylate, and are preferably methyl methacrylate or n-butyl acrylate. And particularly preferably methyl methacrylate. These (ester) acrylate monomers may be used alone or in combination of two or more.

Further, vinyl monomers that can be copolymerized with these monomers, which are used as needed, include acrylic acid, methacrylic acid, acrylonitrile, and methacrylic acid. Lonitrile, N-phenylmaleimide, N-cyclohexylmaleimide and the like.

Examples of the rubber-like elastic material used in the present invention include polybutadiene, styrene-butene diene block copolymer, and styrene-butadiene random copolymer.

The styrene monomer unit amount in the styrene-butadiene block copolymer or the styrene-butanediene random copolymer is preferably 60% by mass or less, particularly preferably 25% by mass or less (where 0 is Is not included) in order to obtain good impact resistance and transparency of the rubber-modified styrenic resin composition. The rubber-modified styrenic resin composition of the present invention has a continuous phase of 60 to 80% by mass of a styrene- (meth) acrylate copolymer and a dispersed phase of 40 to 20% by mass of a graft copolymer. %, Preferably 60 to 70% by mass of a continuous phase of a styrene- (meth) acrylate ester copolymer, and 40 to 30% by mass of a dispersed phase of a graft copolymer. I do. When the dispersed phase of the graft copolymer is less than 20% by mass, the impact resistance of a thin-walled molded product is insufficient, and when it exceeds 40% by mass, the molding processability becomes insufficient.

The mass ratio between the continuous phase and the dispersed phase was determined by stirring the rubber-modified styrene resin composition (mass A) in methyl ethyl ketone (MEK) at a temperature of 23 ° C for 24 hours. Then, the insoluble matter in MEK is separated by a centrifugal separator, and the dried matter is vacuum-dried, and the mass is measured (assuming the mass is B), which is obtained by the following equations (3) and (4).

(3) Continuous phase (% by mass) =-"-"-1 x 100

A

( Four )

B

Dispersed phase (% by mass) 2 'X 100

A Further, the dispersed phase of the graft copolymer has a volume average particle diameter of preferably 0.3 0.6 m, particularly preferably 0.3 0.45 m. If the volume average particle diameter is less than 0.3 m, the impact resistance of a thin-walled molded product is insufficient, and if it exceeds 0.6 m, the transparency is inferior.

Further, in the continuous phase of the styrene- (meth) acrylic acid ester copolymer, the weight average molecular weight (Mw) and X of the formula (1) obtained from its constituent units are within the range of the formula (2). is necessary. However, the weight average molecular weight of the continuous phase described here is the weight average molecular weight in terms of polystyrene obtained by measuring the MEK-soluble component of the rubber-modified styrene resin composition by gel permeation chromatography (GPC). . Meth) Acrylic ester monomer unit (% by mass) ^{x =} weight average molecular weight ( ^Mw styrene monomer unit (% by mass) ⁽¹⁾

1 20 0 00≤X≤ 1 6 0 0 0 0 (2)

When X is less than 1200, the impact resistance of the thin-walled molded product is insufficient, and when it exceeds 1,600, the moldability is insufficient, which is not preferable. Among them, 125 0 0 ≤X≤1550 0 is particularly preferred.

The amount of each monomer unit constituting the continuous phase styrene- (meth) acrylate copolymer is not particularly limited as long as the above conditions are satisfied. The unit is preferably 270% by mass, particularly preferably 240% by mass, and the (meth) acrylate monomer unit is preferably 380% by mass, particularly preferably 680% by mass. The amount of the vinyl monomer unit copolymerizable with these monomers, which is used as necessary, is preferably 0% by mass, particularly preferably 0.5% by mass.

Further, the amounts of the rubber-like elastic body and each monomer unit constituting the graft copolymer of the dispersed phase are not particularly limited as long as the above conditions are satisfied. preferable. That is, the rubbery elastic body is contained in an amount of 30 to 80 parts by mass, preferably 50 to 75 parts by mass, particularly preferably 50 to 70 parts by mass, and the styrene monomer unit is preferably 20 to 70 parts by mass. 70% by mass, particularly preferably 20 to 40% by mass, preferably 30 to 80% by mass, more preferably 60 to 80% by mass, of a (meth) acrylic acid ester-based monomer unit, And a vinyl monomer unit copolymerizable with these monomers, which is preferably used in an amount of 0 to 10% by mass, and particularly preferably 0 to 5% by mass. Acrylic ester copolymer is preferably a graft copolymer having a mass of 20 to 70 parts by mass, preferably 25 to 50 parts by mass, particularly preferably 30 to 50 parts by mass. Can be

The rubber-modified styrenic resin composition of the present invention can be produced by a known technique such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, a bulk-one suspension polymerization method, and an emulsion polymerization method. In addition, any of a palindrome polymerization method and a continuous polymerization method can be used.

The thermoplastic resin composition of the present invention contains an organic polysiloxane. Examples of the organic polysiloxane include polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, and the like, and polydimethylsiloxane is preferable. Further, if necessary, a modified type in which an epoxy group, an amino group, a propyloxyl group, a hydroxyl group, a methacryl group, or the like is introduced into the terminal or the molecule of the organic polysiloxane can be used. These organic polysiloxanes may be used alone or in combination of two or more.

In addition, the thermoplastic resin composition of the present invention preferably uses the organopolysiloxane and the ester-based lubricant in combination to improve the balance between transparency, impact resistance, and moldability. Examples of the ester-based lubricant include fatty acid polyhydric alcohol esters such as hydrogenated castor oil, fatty acid lower alcohol esters such as butyl stearate, and fatty acid polyglycol esters such as polyethylene glycol monostearate. Hardened castor oil.

The content of the organic polysiloxane is 0.05 to 0.05 part by mass, preferably 0.01 to 0.03 part by mass, based on 100 parts by mass of the rubber-modified styrene resin composition. Department. If the amount is less than 0.05 part by mass, the impact resistance of the thin-walled molded product is insufficient, and if the amount exceeds 0.05 part by mass, the transparency deteriorates, which is not preferable.

The preferred content of the ester-based lubricant is 0.1 to 2.5 parts by mass, and preferably 0.5 to 2 parts by mass, based on 100 parts by mass of the rubber-modified styrene resin composition. When the amount is less than 0.1 part by mass, the effect of using the organic polysiloxane and the ester-based lubricant in combination is small, and when the amount exceeds 2.5 parts by mass, the transparency is greatly reduced.

The thermoplastic resin composition of the present invention contains known additives such as an antioxidant, a weathering agent, a lubricant, a plasticizer, a coloring agent, an antistatic agent, and a mineral oil, and the performance of the thermoplastic resin composition of the present invention. You may mix | blend in the range which does not impair.

The thus obtained thermoplastic resin composition of the present invention can be processed into various molded articles by a method such as injection molding, compression molding and extrusion molding, and can be put to practical use. Mixing (mixing) in the case of producing various molded articles using the thermoplastic resin composition of the present invention, the melt extrusion method is not particularly limited, and a known method can be employed. For example, each raw material is uniformly mixed in advance with a tumbler, Henschel mixer, or the like, and supplied to a single-screw extruder or a twin-screw extruder to melt and mix to prepare pellets for molding. As a result, various molded products are manufactured.

Example

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

First, production of raw resin will be described.

(A) Manufacture of styrene- (meth) acrylate copolymer

Reference Example 1: Styrene- (meth) acrylate copolymer A-1

In a 250 liter autoclave, 100 kg of pure water, 0.5 g of sodium dodecyl benzene sulfonate, 250 g of tribasic calcium phosphate, 23 kg of styrene, 73 kg of methyl methacrylate, 4 kg of acrylonitrile Was added, and 100 g of t-butyl peroxyisobutyrate and 6.5 g of t-decyl mercaptan were added as polymerization initiators, and the mixture was stirred under a rotation speed of 150 rpm. Dispersed. The mixture was heated and polymerized at 90 ° C. for 8 hours and at 130 ° C. for 2.5 hours. After completion of the reaction, washing, dehydration and drying were carried out to obtain a beaded styrene- (meth) acrylic ester copolymer A-1.

Reference Example 2: Styrene- (meth) acrylate-based copolymer A-2

In Reference Example 1, except that the amount of t-dodecylmercaptan was changed to 800 g, a styrene- (meth) acrylate-based copolymer A-1 was produced in the same manner as the bead-like styrene- (meth) acrylate. Acrylic ester copolymer A-2 was obtained. Reference Example 3: Styrene- (meth) acrylate copolymer A-3

In Reference Example 1, except that t-dodecylmercaptan was changed to 500 g, it was produced in the same manner as the styrene- (meth) acrylate-based copolymer A-1. Acrylic ester copolymer A-3 was obtained. Reference Example 4: Styrene- (meth) acrylate-based copolymer A-4

In Reference Example 1, except that the amount of t-dodecylmercaptan was changed to 900 g, a styrene- (meth) acrylate-based copolymer A-1 was produced in the same manner as the beaded styrene- (meth) acrylate. Acrylic ester copolymer A-4 was obtained. Reference Example 5: Styrene- (meth) acrylate copolymer A-5

100 kg of pure water, 0.5 g of sodium dodecylpentenesulfonate, 0.5 g of calcium triphosphate, 250 g of styrene, 42 kg of styrene, and 58 kg of methyl methacrylate were put into a 250 liter autoclave, and polymerized. As an initiator, 100 g of t-butylperoxyisobutyrate and 300 g of t-dodecylmer force were added, and the mixture was dispersed under stirring at a rotation speed of 150 rpm. . The mixture was heated and polymerized at a temperature of 90 for 8 hours and at 130 ° C. for 2.5 hours. After completion of the reaction, washing, dehydration and drying were carried out to obtain a beaded styrene- (meth) acrylate ester copolymer A-5.

Reference Example 6: Styrene- (meth) acrylate copolymer A-6

A styrene- (meth) acrylate copolymer A-5 was produced in the same manner as in Reference Example 5 except that the t-dodecylmer force was changed to 600 g. (Meth) acrylic ester copolymer A-6 was obtained. (Mouth) Production of rubber-like elastic latex

Reference Example 7: Rubbery elastic latex G-1

56 kg of pure water, 400 g of potassium oleate, 1,200 g of potassium rosinate, 1.2 kg of potassium carbonate, and 400 g of potassium persulfate were added to a 200-liter autoclave and uniformly dissolved with stirring. . Next, 400 g of t-dodecylmercaptan and 80 kg of butadiene were added, and the mixture was polymerized at a temperature of 60 ° C for 30 hours with stirring, and then heated to 70 ° C and left for 30 hours to complete the polymerization. Body latex G-1 was obtained.

Reference Example 8: Rubber-like elastic latex G-2

56 kg of pure water, 400 g of potassium oleate, 1,200 g of potassium rosinate, 1.2 kg of potassium carbonate, and 400 g of potassium persulfate were added to a 200-liter autoclave and uniformly dissolved with stirring. . Next, 400 g of t-dodecyl mercaptan, 23.6 k of styrene, and 56.4 kg of butadiene were added, and the mixture was polymerized at 60 ° C for 24 hours with stirring, and further heated to 70 ° C for 24 hours. Was completed to obtain a rubber-like elastic latex G-2.

Reference Example 9: Rubber-like elastic latex G-3

In a 200-liter autoclave, 64 kg of pure water, 400 g of potassium oleate, 1,200 g of potassium rosinate, 1.2 kg of potassium carbonate, and 400 g of potassium persulfate were added and uniformly dissolved with stirring. Then, 400 g of t_dodecylmercaptan, 23.6 kg of styrene, and 56.4 kg of butadiene were added, and the mixture was polymerized at a temperature of 60 for 16 hours with stirring, and further heated to 70 ° C and left for 12 hours to perform polymerization. It was completed, and rubber-like elastic latex G-3 was obtained.

Reference Example 10: Rubber-like elastic latex G-4

In a 200 liter autoclave, 115 kg of pure water, 500 g of potassium oleate, 75 g of sodium pyrophosphate, 1.5 g of ferrous sulfate, 2.2 g of sodium ethylenediaminetetraacetate, and 22 g of Rongalite In addition, it was uniformly dissolved under stirring. Then, 14.5 kg of styrene, 35.5 kg of butadiene, 148 g of t-dodecyl mercaptan, 30 g of divinylbenzene, and 30 g of disopropyne 96 g of benzene hydroperoxide was added, and the mixture was reacted at a temperature of 50 ° C. for 16 hours with stirring to complete the polymerization, thereby obtaining a rubber-like elastic latex. After adding 45 g of sodium sulfosuccinate to the obtained rubber-like elastic latex and sufficiently stabilizing the mixture, a 0.2% by mass aqueous solution of hydrochloric acid and a 2% by mass aqueous solution of caustic soda were passed through separate nozzles to adjust the PH of the latex. The latex was added so as to maintain 8 to 9, and the latex was coagulated and enlarged to obtain a rubber-like elastic latex G-4 having a volume average particle diameter of 0.6.

(8) Production of graft copolymer-containing polymer

Reference Example 11: Graft copolymer-containing polymer B-1

The rubber-like elastic latex G-1 of Reference Example 7 was weighed at 30 kg in terms of solid content, transferred to a 200 L autoclave, added with 90 kg of pure water, and heated to a temperature of 5 Ot under a nitrogen stream while stirring. Warmed. 1.5 g of ferrous sulfate, 3 g of sodium ethylenediaminetetraacetate, and 100 g of Rongalite dissolved in 2 kg of pure water were added.7.5 kg of styrene, 22.5 kg of methyl methacrylate, 1-dodecyl t-dodecyl A mixture consisting of 60 g of mercaptan, a solution of 60 g of diisopropylbenzene hydropropoxide and 450 g of potassium oleate dispersed in 8 kg of pure water were separately added continuously over 6 hours. After the addition was completed, the temperature was raised to 70 ° C., 30 g of diisopropylbenzene hydroperoxide was further added, and the mixture was left for 2 hours to terminate the polymerization.

An antioxidant was added to the obtained emulsion, the solid content was diluted to 15% by mass with pure water, and then the temperature was raised to 7 OX :. Salting out was performed by adding dilute sulfuric acid with vigorous stirring. Thereafter, the temperature was raised to 95 ° C. to coagulate, and then dewatered, washed with water and dried to obtain a powdery copolymer B-1 containing the graft copolymer.

Reference Example 12: Graft copolymer-containing polymer B-2

30 kg of the rubber-like elastic latex G-2 of Reference Example 8 was weighed in terms of solid content and transferred to a 200 L autoclave, and 90 kg of pure water, 1.8 kg of styrene, and 4.2 kg of methyl methacrylate were added. In addition, the temperature was raised to 50 ° C under a nitrogen stream with stirring. Here, ferrous sulfate 1.5 g, sodium ethylenediaminetetraacetate A mixture consisting of 3 g of rubber, 100 g of Rongalit dissolved in 2 kg of pure water, and 10.5 kg of styrene, 13.5 kg of methyl methacrylate, and 90 g of t-dodecylmercaptan And a solution obtained by dispersing 60 g of diisopropylbenzene hydroperoxide and 450 g of potassium oleate in 8 kg of pure water were separately added continuously over 6 hours. After the addition was completed, the temperature was raised to 70 ° C., 30 g of diisopropylbenzene hydroperoxide was added, and the mixture was left for 2 hours to terminate the polymerization.

An antioxidant was added to the obtained emulsion, the solid content was diluted to 15% by mass with pure water, then the temperature was raised to 70 ° C, and salting out was performed by adding dilute sulfuric acid with vigorous stirring. Thereafter, the temperature was raised to 95 ° C. for coagulation, followed by dehydration, washing with water, and drying to obtain a powdery copolymer B-2 containing the graft copolymer.

Reference Example 13: Graft copolymer-containing polymer B-3

A powdery copolymer was prepared in the same manner as in the graft copolymer-containing polymer B-2 except that the rubber-like elastic latex was changed to the rubber-like elastic body G-3 in Reference Example 12. Containing polymer B-3 was obtained.

Reference Example 14: Graft copolymer-containing polymer B-4

In the same manner as in Reference Example 12 except that the rubber-like elastic latex was changed to rubber-like elastic body G-4, it was produced in the same manner as in the case of the graft copolymer-containing polymer B-2, and the powdery graft copolymer-containing Polymer B-4 was obtained.

Examples 1 to 11 and Comparative Examples 1 to 9

Styrene mono (meth) acrylate based copolymer produced in Reference Examples 1 to 6, graft copolymer-containing polymer produced in Reference Examples 11 to 14, polydimethylsiloxane (Shin-Etsu Chemical Co., Ltd.) Table 1 and Table 2 show KF-966), hydrogenated castor oil (Kao Wax 85-P manufactured by Kao Corporation), and ethylene bisstearic acid amide (Kao Wax EB-P manufactured by Kao Corporation). Were blended at the ratios indicated by. Next, the mixture was mixed with a Henschel mixer, and then melt-mixed with a twin-screw extruder (TEM-35B manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 220 ° C. to pelletize. Various physical properties were measured using the obtained sample pellets according to the following physical property measuring methods. I got it. The measured values are shown in Tables 1 and 2.

(1) Formability in thin-wall molding

Using an injection molding machine (NEOMAT 51 5/150) manufactured by Sumitomo Heavy Industries, Ltd., a 200 x 200 x 1.5 mm square plate was molded from the sample bellet under the following conditions 1 and 2. Then, the moldability in thin-wall molding was evaluated.

Condition 1: Cylinder temperature 190, mold temperature 40 ° C

Condition 2: Cylinder temperature 200 ° (, mold temperature 60 ° C

◎ · · A molded product with good appearance was obtained in both conditions 1 and 2.

〇 · · A molded product with good appearance was obtained under either Condition 1 or Condition 2.

X-· Molding failure such as poor filling, gas burning, rippled flow mark, etc. occurred, and a molded product with good appearance under both conditions 1 and 2 could not be obtained.

◎ and 〇 were judged to be acceptable.

(2) Impact resistance of thin molded products

Using an injection molding machine (SYCAP 165Z75) manufactured by Sumitomo Heavy Industries, Ltd., a sample bellet was molded under the conditions of a cylinder temperature of 220 ° C and a mold temperature of 60 ° C, and the dimensions were 90 x 90 x 1 mm. Was prepared. With respect to this test piece, a weight having a mass of 50 g and a mass of 100 g was dropped from a height of 50 cm using a DuPont type falling weight impact tester to evaluate the impact resistance of the thin-walled molded product.

A · · Non-destructive rate of 80% or more with a weight of 100 g

B · · Non-destructive rate of 80% or more with a weight of 50 g

C · · Non-destructive rate of less than 80% with a weight of 50 g

A and B were judged to be acceptable.

(3) Transparency (cloudiness)

Using an injection molding machine (IS-50EP) manufactured by Toshiba Machine Co., Ltd., the sample pellet was molded under the conditions of a cylinder temperature of 220 ° C and a mold temperature of 60 ° C, and a 55 x 90 x 3 mm square plate. Test pieces were prepared. The haze of this test piece was measured in accordance with ASTM D1003 (unit:%). Example 1 Example 2 Example 3: 'Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Styrene mono (meth) A-1 (parts by mass) 70 70 70 ; 70 65 65 65 65 Acrylic ester A-2 (parts by mass) 60 60

Copolymer A-5 (parts by mass) 65

Graft copolymer B-1 (parts by mass) 30 30 30: 30 35 35 40 40 35 35

Contained polymer B-2 (parts by mass)

Organic polysiloxane (parts by mass) 0.005 0.015 0.045: 0.015 0.015 0.015 0.015 0.015 U.U 丄 ΰ 0.015 0.015 hydrogenated castor oil (parts by mass); 0.5 1.52 3

Ethylenebisstearic acid amite '(parts by mass) 1.5 parts by weight Mass ratio of continuous phase; mass% 73 68 64 70 68 MMA of constituent monomer units 72. 6 72. 7 72. 8 57. 5 72 7 series

Variable value ratio St 23. 8 23. 8 23. 8 42. 5 23.8 Property (mass%) AN 3.6 3.3.5 3.40 3.5

Phase

Weight average molecular weight (Mw) 85000 86000 71000 113000 86000 H X value 148000 150000 124000 131000 150 Leakage Dispersed phase mass ratio; Material number * 27 32 36 30 32 G Rubber-like elastic material amount: Mass part 55 55 55 58 55

Minute

System Graft monomer amount 45 45 45 42 45

Scattered

相 74. 8 74. 8 74. 8 57. 8 74.8 Resin ratio (% by mass) of the monomer unit constituting the resin phase St. 25. 2 25. 2. 2. 25. 2 42. 2 25. 2 Volume Average particle size 0.40: 0.40: 0.40: 0.39 0.30 Molding processability in molded products 〇〇〇 ◎ 〇：: ◎! 〇: ◎, 〇 ◎: 〇 Impact resistance of thin molded products B: B: B B. A: A: A: A: A: A: A i A

□ Haze (%) 1.6; 2.0: 2.8 2.2: 2.2: 2.8! 2.5: 3.5: 2.9: 4.4: 4.9

MMA methyl methacrylate, St: styrene, AN: acryloni

Table 2

MMA Methyl methacrylate, St: Styrene, AN acrylonitrile

The rubber-modified styrenic resin composition was analyzed using a rubber-modified styrene-based (meth) acrylic ester-based copolymer and a graft copolymer-containing polymer that were previously mixed at the compounding ratios shown in Tables 1 and 2. Pellets of the styrene-based resin composition were prepared, and each analytical value was measured using the pellets according to the following measurement method. The analytical values are shown in Tables 1 and 2.

(1) Measurement of mass ratio between continuous phase and dispersed phase

The sample pellets (assuming mass A), whose mass has been measured in advance, are stirred in methyl ethyl ketone (MEK) at a temperature of 23 ° C. for 24 hours, and then the insoluble matter in MEK is separated by a centrifuge. After centrifugation operation, it was left still for 30 minutes. The operating conditions of the centrifuge are as follows.

Temperature: One 9 ° C

Speed: 20000 r pm

Time: 60 minutes

The supernatant and the precipitate separated from the centrifuged solution are separated, and the precipitate is dried using a vacuum drier. The mass is measured (assuming the mass is B), and the following formulas (3) and (4) are used. The mass ratio between the continuous phase and the dispersed phase was determined.

(3)

A-B

Continuous phase (% by mass) X 100

A

(Four)

B

Dispersed phase (% by mass) X 100

A

(2) Measurement of weight average molecular weight of continuous phase

The supernatant obtained by centrifuging the solution was fractionated, and methanol was added to precipitate a styrene- (meth) acrylate copolymer (continuous phase). The precipitate was collected and measured under the following GPC measurement conditions.

Equipment name: SYSTEM—21 Shod eX (Showa Denko KK)

Column: 3 PL gel MI XED-B in series Temperature: 40 ° C

Detection: Suggested refractive index

Solvent: tetrahydrofuran

Concentration: 2% by mass

Calibration curve: Prepared using standard polystyrene (PS) (manufactured by PL), and the weight average molecular weight was expressed in terms of PS.

(3) Measurement of monomer units constituting the continuous phase

The continuous phase (MEK-soluble) consisting of the styrene- (meth) acrylate-based copolymer obtained in the pretreatment of the previous measurement was dissolved in heavy-duty-mouthed form, and FT-N MR (manufactured by JEOL Ltd.) FX_90Q) was used to determine the constituent monomer units.

(4) Volume average particle size measurement of dispersed phase

Approximately lg of the sample pellet was stirred in 100 g of N, N-dimethylformamide (DMF) for 24 hours, diluted to an appropriate concentration with the addition of DMF, and measured by laser single-scattering scattering method. The measurement was carried out using a machine (Model No. 3230 of 111111).

(5) Percentage of monomer units constituting the dispersed phase

Reference Example 11 Each sample powder of the graft copolymer-containing polymer produced in 1 to 14 was stirred in methyl ethyl ketone (MEK) at a temperature of 23 ° C for 24 hours, and then insoluble in MEK by a centrifuge. After centrifugation, the mixture was allowed to stand for 30 minutes. The operating conditions of the centrifuge are as described above.

The supernatant of the solution after centrifugation was separated, and methanol was added to precipitate an ungrafted styrene- (meth) acrylate copolymer. This precipitate was collected, dissolved in a double-mouthed form, and the constituent monomer units were determined using FT-NMR (FX-90Q type manufactured by JEOL Ltd.).

In addition, in the graft copolymer-containing polymer produced in Reference Examples 11 to 14, the ratio of the constituent monomer units of the styrene- (meth) acrylate-based copolymer grafted to the rubbery polymer was used. Since the ratio of the constituent monomer units of the ungrafted styrene- (meth) acrylate ester copolymer can be considered to be the same, The measured value was defined as the ratio of the monomer units constituting the styrene- (meth) acrylate-based copolymer grafted to the rubber-like polymer.

(6) Measurement of the amount of rubber-like elastic material and the amount of graft monomer in the dispersed phase

The precipitate of the centrifuged solution was collected by filtration, dried with a vacuum drier, and used as a measurement sample of the dispersed phase. The obtained sample was swollen in a double-mouthed form, and the constituent monomer units were determined using FT-NMR (FX-90Q type manufactured by JEOL Ltd.). The mass ratio of the constituent monomer units of the styrene- (meth) acrylate ester copolymer obtained by the measurement in the above (5) (where the ratio of the styrene monomer unit is a and the (meth) acrylic acid ester unit is The ratio of the monomer units is b. However, the total amount of the constituent monomer units is 100.) The mass ratio of the constituent monomer units of the dispersed phase sample (here, the The ratio of units is c, the ratio of styrene monomer units is d, and the ratio of (meth) acrylic acid ester monomer units is e, where the total amount of constituent monomer units is 100.) From this, the amounts of the rubbery elastic body and the amount of the graft monomer were determined according to the following formulas (5) and (6).

(5) Amount of rubbery elastic body (parts by mass) = c + d_ex

b

(6) Graft monomer amount (parts by mass) = e (1 + —)

b

The constituent monomer units of the sample of the precipitate (dispersed phase) pretreated in the above (1) were determined by FT-NMR, and all of them were consistent with the constituent monomer units obtained above. I was

Examples relating to the thermoplastic resin composition of the present invention were all excellent in molding workability in thin-wall molding, impact resistance and transparency of a thin molded product, but a thermoplastic resin composition not meeting the conditions of the present invention. In the comparative example relating to the product, the molding property in thin-wall molding, the impact resistance and the transparency of the thin-wall molded product were inferior in any one of physical properties. Industrial applicability

According to the present invention, it is possible to provide a thermoplastic resin composition having excellent transparency and exhibiting excellent impact resistance and moldability even in an extremely thin molded product.

Claims

The scope of the claims

1. (I) Styrene-based monomer, (meth) acrylate-based monomer, and, if necessary, a copolymer of a vinyl-based monomer copolymerizable with these monomers The continuous phase of a styrene- (meth) acrylate-based copolymer is 6080% by mass, and (II) a styrene-based monomer and a (meth) acrylate-based monomer in a rubber-like elastic material. And a styrene- (meth) acrylate-based copolymer, which is a copolymer of a vinyl monomer copolymerizable with these monomers and used as necessary. A rubber-modified styrenic resin composition containing 40 to 20% by mass of a polymer dispersed phase,

The volume average particle diameter of the dispersed phase is 0.3 0.6 mm, and the X in Formula (1) obtained from the weight average molecular weight (Mw) of the continuous phase and its constituent monomer unit is A thermoplastic resin composition in the range and containing 0.005 0.05 parts by mass of the organic polysiloxane with respect to 100 parts by mass of the resin composition.

120000≤X≤ 160000 (2)

2. The rubber-modified styrenic resin composition is composed of (I) a continuous phase of styrene- (meth) acrylate copolymer of 60 70% by mass and (II) a dispersed phase of graft copolymer 40 30% by mass. %. The thermoplastic resin composition according to claim 1, wherein

3. The thermoplastic resin composition according to claim 1 or 2, wherein the rubber-modified styrenic resin composition is contained in an amount of 0.;

4. The thermoplastic resin composition according to claim 3, wherein the ester lubricant is hydrogenated castor oil.

5. The method according to claim 1, wherein the organic polysiloxane is polydimethylsiloxane. The selected thermoplastic resin composition according to item 1.

6. The continuous phase is composed of 20 to 70% by mass of a styrene-based monomer unit, 30 to 80% by mass of a (meth) acrylate-based monomer unit, and is used as necessary. 6. A styrene- (meth) acrylate-based copolymer, which is a copolymer of 0 to 10% by mass of a vinyl-based monomer unit copolymerizable with a monomer. Item 2. The thermoplastic resin composition according to item 1.

7. The dispersed phase is composed of 30 to 80 parts by mass of a rubber-like elastic body of polybutadiene and Z or styrene-butadiene copolymer, 20 to 70% by mass of a styrene-based monomer unit, and (acrylic) acrylic. A copolymer of 30 to 80% by mass of an acid ester monomer unit and 0 to 10% by mass of a vinyl monomer unit copolymerizable with these monomers and used as necessary. The thermoplastic resin composition according to any one of claims 1 to 5, which is a graft copolymer obtained by grafting 20 to 70 parts by mass of a styrene- (meth) acrylate ester-based copolymer.

8. The continuous phase is composed of 20 to 70% by mass of a styrene-based monomer unit, 30 to 80% by mass of a (meth) acrylate-based monomer unit, and is used as necessary. A styrene- (meth) acrylate-based copolymer which is a copolymer of 0 to 10% by mass of a vinyl-based monomer unit copolymerizable with a monomer, and in which a polybutadiene and And / or 30 to 80 parts by mass of a styrene-butadiene copolymer rubber-like elastic material, 20 to 70% by mass of a styrene monomer unit, and 30 to 70% by mass of a (meth) acrylic acid ester monomer unit Styrene mono (meth) acryl, which is a copolymer of 80% by mass and 0 to 10% by mass of a pinyl monomer unit copolymerizable with these monomers and used as necessary. The acid ester copolymer is a graft copolymer in which 20 to 70 parts by mass are grafted. 6. The thermoplastic resin composition according to any one of claims 1 to 5.