JP2002060573A - Thermoplastic resin composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition capable of providing a molding having sufficient transparency while retaining heat resistance and impact resistance. SOLUTION: The thermoplastic resin composition comprises (A) 20-91 pts.wt. of a styrene-based copolymer resin which is obtained by copolymerizing 1-50 wt.% of methacrylic acid with 99-50 wt.% of styrene or 98-25 wt.% of styrene and 1-25 wt.% of α-methylstyrene and has <=10% haze value, (B) 9-80 pts.wt. of a methyl methacrylate-based resin having <=10% haze value and (C) 3-30 pts.wt. of a graft copolymer resin which is obtained by copolymerizing (a) 20-80 wt.% of a rubber-like polymer with 80-20 wt.% of a mixture of (b) 10-90 wt.% of methyl methacrylate and (c) 90-10 wt.% of styrene and has 1.510-1.550 refractive index and <=20% haze value. The method for producing the thermoplastic resin composition is also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a specific styrenic polymer resin, a methyl methacrylate resin and a specific graft copolymer resin, and is excellent in molding processability and heat resistance.
The present invention also relates to a thermoplastic resin composition having excellent performance in impact strength, transparency, and appearance of a molded product, a method for producing the same, and a molded product made of the resin composition.

[0002]

2. Description of the Related Art Polystyrene resins, styrene / acrylonitrile copolymer resins and methyl methacrylate resins have been known as resins having excellent transparency.
These resins have excellent transparency, dimensional stability, electrical properties, and coloring properties, and are used in various fields. However, since they are not always satisfactory in terms of heat distortion temperature and impact strength, their use in the fields of medical equipment, parts for light electrical appliances, parts for automobiles, food containers, etc. where these performances are required is limited. Have been.

In order to improve the heat distortion temperature, which is a drawback of polystyrene resin, a styrene monomer (hereinafter abbreviated as styrene) and a methacrylic acid monomer (hereinafter abbreviated as methacrylic acid) are copolymerized. Although some measures have been taken, a kind of styrene copolymer resin such as styrene / methacrylic acid copolymer resin obtained in this way has an improved heat distortion temperature, but has a poor impact strength.

Therefore, in order to improve these drawbacks,
For example, Japanese Patent Publication No. 6-092514 discloses that a styrene-based copolymer resin, a methyl methacrylate-based resin, and a rubbery polymer are blended at a specific ratio. However, although the resin composition described in this publication has good heat resistance and impact resistance, the obtained molded product is not always sufficiently transparent.

[0005]

Accordingly, an object of the present invention is to provide a thermoplastic resin composition capable of obtaining a molded article having sufficient transparency while maintaining heat resistance and impact resistance, and It is an object of the present invention to provide a manufacturing method thereof.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a composition of a specific styrene copolymer, a methyl methacrylate resin and a specific graft copolymer resin has been obtained. As a matrix phase of the composition, a styrene-based copolymer and a methyl methacrylate-based resin are formed with a specific composition, and a dispersed phase of the composition is formed with a graft copolymer resin, thereby providing excellent transparency. The inventors have found that both heat resistance and impact resistance can be provided, and have completed the present invention.

That is, the present invention relates to (1) (A) 1 to 50% by weight of a methacrylic acid monomer and 99 to 50% of a styrene monomer.
0.4 mm in thickness according to JIS K-7105, obtained by copolymerizing the styrene monomer by 98 to 25% by weight and the α-methylstyrene monomer by 1 to 25% by weight.
20 to 91 parts by weight of a styrene copolymer resin having a haze value of 10% or less in a sheet, and 9 to 80 parts by weight of a methyl methacrylate resin having a haze value of 10% or less in a (B) sheet having a thickness of 0.4 mm. And (C) (a) the rubbery polymer 2
0 to 80% by weight, and (b) methyl methacrylate monomer 1
A mixture of 0 to 90% by weight and 80 to 20% by weight of a mixture composed of 90 to 10% by weight of the styrene monomer (C) has a refractive index (n23D) of 1.510%. ~ 1.
Haze value of 550 and 0.4 mm thickness sheet is 2
0% or less of a graft copolymer resin of 3 to 30 parts by weight,

The refractive index of a mixture of (A) a styrene copolymer resin and (B) a methyl methacrylate resin (n （23)
D) is the refractive index (n ▲ 23 ▼) of (C) the graft copolymer resin.
D) in the range of -0.01 to +0.01, and the viscosity (η1) of the mixture of (A) resin and (B) resin;
(C) The ratio of the viscosity (η2) of the resin is 2 ≦ η2 / η1 ≦ 15.
A thermoplastic resin composition having a haze value of 10% or less in a sheet having a thickness of 0.4 mm,

(2) (C) the graft copolymer resin is (a) 20 to 80% by weight of a rubbery polymer, (b) 5 to 49% by weight of a methyl methacrylate monomer, and (c) 90 to 90% by weight of a styrene monomer. 1
Sheet having a refractive index (n ▲ 23D) of 1.510 to 1.550 and a thickness of 0.4 mm, which is obtained by copolymerizing an acrylonitrile monomer with 5 to 50% by weight of (d) an acrylonitrile monomer. The thermoplastic resin composition according to (1), wherein the haze value at 20% or less,

(3) The thermoplastic resin composition according to (1) or (2), wherein (a) the rubbery polymer of the graft copolymer resin (C) is a homopolymer of butadiene,

(4) The thermoplastic resin composition according to (1) or (2), wherein (a) the rubbery polymer of (C) the graft copolymer resin is a copolymer of butadiene and styrene,

(5) The thermoplastic resin composition according to (1) or (2), wherein the (a) rubbery polymer of the graft copolymer resin (C) is a copolymer of butadiene, styrene and acrylonitrile. When,

(6) In addition to (A) 20 to 91 parts by weight of resin, (B) 1 to 79 parts by weight of resin, and (C) 3 to 30 parts by weight of resin, further (D) JIS K-7105 Styrene-methacrylic acid ester-based copolymer resin 1 to 10% or less in haze value based on a 0.4 mm thick sheet
(A) resin, (B) resin and (D)
The refractive index (n ▲ 23D) of the mixture with the resin is in the range of -0.01 to +0.01 of the refractive index (n ▲ 23D) of the resin (C), and the resin (A) And the viscosity (η3) of the mixture of the resin (B) and the resin (D), and the viscosity (η) of the resin (C)
The ratio of 2) is 2 ≦ η2 / η3 ≦ 15, and the haze value of a 0.4 mm thick sheet is 10% or less, according to any one of (1) to (5). A thermoplastic resin composition,

(7) The (C) graft copolymer resin containing a rubbery polymer is finely dispersed with an average particle diameter of 0.05 to 2 μm (1) to (6). The thermoplastic resin composition according to any one of,

(8) (A) Methacrylic acid monomer 1 to 50
JIS K obtained by copolymerizing a styrene monomer by 99 to 50% by weight or a styrene monomer by 98 to 25% by weight and an α-methylstyrene monomer by 1 to 25% by weight.
Styrenic copolymer resins 20 to 91 having a haze value of 10% or less on a 0.4 mm thick sheet according to -7105
Parts by weight, and (B) methyl methacrylate resin 9 to 80 having a haze value of 10% or less in a 0.4 mm thick sheet
Parts by weight, (C) (a) 20 to 80% by weight of a rubbery polymer
And (b) 10 to 90% by weight of methyl methacrylate monomer
And (c) a copolymer obtained by copolymerizing 80 to 20% by weight of a mixture of 90 to 10% by weight of a styrene monomer, having a refractive index (nｎ23D) of 1.510 to 1.550, In mixing a graft copolymer resin having a haze value of 20% or less with a sheet having a thickness of 0.4 mm and 3 to 30 parts by weight,

The refractive index of a mixture of (A) a styrene copolymer resin and (B) a methyl methacrylate resin (n 樹脂 23)
D) is the refractive index (n ▲ 23 ▼) of (C) the graft copolymer resin.
D) is within the range of -0.01 to +0.01, and the ratio of the viscosity (η1) of the mixture of the resin (A) and the resin (B) to the viscosity (η2) of the resin (C) is 2 ≦ η2 / η1 ≦ 15
The mixing ratio of the resin (A) and the resin (B) is adjusted so that the (C) graft copolymer resin containing the rubbery polymer has an average particle diameter of 0.05 to 2 μm. Characterized by being melt-kneaded so as to be finely dispersed, thickness 0.4 m
a method for producing a thermoplastic resin composition having a haze value of 10% or less in an m sheet;

(9) The graft copolymer resin (C) comprises (a) 20 to 80% by weight of a rubbery polymer, (b) 5 to 49% by weight of a methyl methacrylate monomer, and (c) 90 to 80% by weight of a styrene monomer. 1
% By weight and (d) 5 to 50% by weight of an acrylonitrile monomer to obtain a refractive index (n ▲ 23D) of 1.510 to 1.550, and a sheet having a thickness of 0.4 mm. The method for producing a thermoplastic resin composition according to (8), wherein the haze value of the thermoplastic resin composition is 20% or less;

(10) (A) of the graft copolymer resin (C)
The rubbery polymer is a homopolymer of butadiene (8)
Or a method for producing a thermoplastic resin composition according to (9),

(11) (C) Graft copolymer resin (a)
The method according to (8) or (9), wherein the rubbery polymer is a copolymer of butadiene and styrene,

(12) (A) of the graft copolymer resin (C)
The production method according to (8) or (9), wherein the rubbery polymer is a copolymer of butadiene, styrene, and acrylonitrile;

(13) (A) 20 to 91 parts by weight of resin, (B) 1 to 79 parts by weight of resin, (C) 3 to 30 parts by weight of resin, and (D) thickness according to JIS K-7105 When mixing 1 to 79 parts by weight of a styrene-methacrylate copolymer resin having a haze value of 10% or less in a 0.4 mm sheet, the resin (A), the resin (B) and the resin (D) are mixed.
The refractive index (n 混合 23D) of the mixture with the resin is in the range of -0.01 to +0.01 of the refractive index (n ▲ 23D) of the resin (C), and the resin (A) And the viscosity (η3) of the mixture of the resin (B) and the resin (D), and the viscosity (η) of the resin (C)
2) so that the ratio of 1.8 ≦ η2 / η3 ≦ 15,
The mixing ratio of the resin (A), the resin (B) and the resin (D) is adjusted, and the graft copolymer resin (C) containing the rubbery polymer has an average particle diameter of 0.05 to 2 μm. (8) to (1) characterized by being melt-kneaded so as to be finely dispersed.
2) The method for producing a thermoplastic resin composition according to any one of the above,

(14) The method for producing a thermoplastic resin composition according to any one of (8) to (13), wherein the melt-kneading is performed by a twin-screw extruder.

(15) A molded article comprising the thermoplastic resin composition according to any one of the above (1) to (7),

(16) The molded article according to (15), wherein the molded article is a sheet or a film; and

(17) The molded article includes the molded article according to (16), which is a container made of a sheet.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention comprises (A) a styrene copolymer resin, (B) a methyl methacrylate resin, and (C) a graft copolymer resin as essential components. The dispersed state of each component in the composition may be, for example, a mixed resin containing (A) a styrene-based resin and (B) a methyl methacrylate-based resin as main components, or (A) a styrene-based resin, (B) a methyl methacrylate-based resin, and styrene. It is preferable that a mixed resin mainly composed of a copolymer resin (D) composed of methacrylate and methacrylate forms a matrix resin phase, and the graft copolymer resin (C) is dispersed in the matrix.

Here, (A) the styrene copolymer resin means 1 to 50% by weight of a methacrylic acid monomer and 99 to 50% by weight of a styrene monomer or 98 to 25% by weight of a styrene monomer.
And 1 to 25% by weight of α-methylstyrene monomer are subjected to bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization in the presence of a radical generator and a chain transfer agent, JISK
A resin having a haze of 10% or less according to 7105.

(A) One example of a method for preparing a styrene copolymer resin is as follows: 1 to 50% by weight, preferably 2 to 40% by weight, of methacrylic acid and 99 to 50% by weight, preferably 98 to 98% by weight of styrene. 60% by weight, or 1-50% by weight, preferably 2-40% by weight, of methacrylic acid and 98-25%, preferably 97% by weight of styrene.
Using a mixture consisting of -30% by weight and 1-25% by weight of α-methylstyrene, preferably 2-20% by weight, and a known and commonly used radical generator and chain transfer agent,

Polyvinyl alcohol, sodium polyacrylate, polyvinylpyrrolidone, methylcellulose,
Suspension stabilizers such as hydroxyethylcellulose or carboxymethylcellulose, and sodium chloride;
In water in which a dispersing aid such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium carbonate or sodium alkylbenzene sulfonate is dissolved, at 50 to 150 ° C,
Preferably, there is a method of performing suspension polymerization at 80 to 140 ° C.

(A) The styrenic copolymer resin can be obtained after dehydration, washing, and drying after completion of the polymerization reaction. Further, if necessary, an antioxidant or a lubricant is also added to the (A) styrene copolymer resin,
Granulation can also be performed by an extruder or the like. Here, by setting the use amount of methacrylic acid to 1% by weight or more, the compatibility with the methyl methacrylate resin (B) is improved, and as a result, the transparency of the molded product is significantly improved. Further, when the amount is 50% by weight or less, deterioration in appearance of a molded article such as silver can be prevented.

Next, as the (B) methyl methacrylate resin, a homopolymer of methyl methacrylate or 80% by weight or more of methyl methacrylate and various acrylates such as methyl acrylate, ethyl acrylate or butyl acrylate; Various acrylates other than methyl methacrylate, such as ethyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate; various methacrylates other than methyl methacrylate, such as ethyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate; acrylic acid, methacrylic acid, Examples include copolymers of the above-mentioned methyl methacrylate such as styrene or acrylonitrile with various monomers copolymerizable therewith.

Among them, a resin having a haze of 10% or less according to JIS K7105 is preferred, and the use of a homopolymer of methyl methacrylate is more suitable from the viewpoint of compatibility with the styrene copolymer resin (A). . Here, when the haze is 10% or less, sufficient transparency of the methyl methacrylate-based resin (B) is obtained, and as a result, the transparency of the molded product is also significantly improved.

(B) An example of a method for preparing a methyl methacrylate-based resin is as follows. Methyl methacrylate alone or a mixture of this methyl methacrylate and one or more of the above-mentioned monomers is used to generate radicals. And bulk polymerization, solution polymerization or suspension polymerization in the presence of an agent and a chain transfer agent. It is needless to say that a general commercial product that can be used for this type of molding can be used as it is.

Further, (C) the graft copolymer resin is a mixture of 10 to 90% by weight of methyl methacrylate and 90 to 10% by weight of styrene in the presence of 20 to 80% by weight of the rubbery polymer. 80 to 20% by weight, or 20 to 80% by weight of the rubbery polymer.
In the presence of 5 to 49% by weight of methyl methacrylate, 90 to 1% by weight of styrene and 5 to 5% of acrylonitrile.
Of a mixture consisting of 0% by weight and 80 to 20% by weight, and has a refractive index (n ▲ 23 ▼ D) of 1.51.
0 to 1.550 and JIS K-71
Haze value of 0.4mm sheet conforming to ISO 05
A resin that is 0% or less is referred to.

Here, since the amount of the rubbery polymer used is at least 20% by weight, a molded article of the composition having excellent impact strength can be obtained. The heat distortion temperature of the molded article of the combined (C) composition is improved. In addition, from the viewpoint of excellent balance between the impact strength and the heat distortion temperature, the amount of the rubbery polymer used is preferably 50 to 50%.
Preferably it is 80% by weight.

When methyl methacrylate and styrene are grafted onto the rubbery polymer, the amount of methyl methacrylate to styrene is 10 to 90% by weight.
By doing so, the refractive index of the graft component can be made closer to that of the rubbery polymer, and the transparency of the graft copolymer resin (C) can be increased. Above all, the amount of methyl methacrylate relative to styrene is preferably from 50 to 80% by weight from the viewpoint of extremely excellent transparency.

On the other hand, when methyl methacrylate, styrene and acrylonitrile are grafted onto the rubbery polymer, the amount of each monomer used as the graft component is 5 to 49% by weight of methyl methacrylate, 90 to 1% by weight of styrene and When the acrylonitrile content is 5 to 50% by weight, the refractive index of the graft component approaches the rubber-like polymer, and the transparency of the graft copolymer resin (C) is remarkably improved.

Above all, the amount of each graft component used is preferably 35% because of its extremely excellent transparency.
It is preferable that the content of styrene is 60 to 31% by weight and that of acrylonitrile is 5 to 20% by weight. The graft ratio (branch portion weight / trunk weight) of the graft copolymer resin (C) thus obtained is 0.2 to 0.2%.
A range of 1.2 is appropriate.

The rubbery polymer may be a polybutadiene rubber such as low cis polybutadiene or high cis polybutadiene, or a homopolymer of butadiene or a butadiene copolymer such as acrylonitrile / butadiene copolymer rubber or styrene / butadiene copolymer rubber. For example, a copolymer of a vinyl monomer and a copolymerizable monomer is used.

In the graft copolymer resin (C),
One of the conditions is that the haze value of the sheet having a thickness of 0.4 mm is 20% or less. If the haze exceeds 20%, the resin composition obtained from the resin components (A) and (B) and the resin component (C) becomes inferior in transparency as a result. Absent. Next, one of the conditions is that the refractive index of the resin component (C) should be in a range of 1.510 to 1.550. Setting is the other essential component of the composition of the present invention (A)
It is necessary to keep the refractive index of the mixture of the resin component and the resin component (B) within a certain range, that is, within the range of ± 0.01 of the refractive index of the component (C). The refractive index was measured at 23 ° C. using an Abbe refractometer.

Further, the ratio of the viscosity (η1) of the mixed resin comprising the components (A) and (B) to the viscosity (η2) of the component (C) may be in the range of 2 ≦ η2 / η1 ≦ 15. It is necessary to maintain the transparency of the molded article. When the viscosity ratio is less than 2, the viscosity of the mixture of the component (A) and the component (B) forming the matrix phase becomes higher than the viscosity of the component (C) which is the dispersed phase, and the particles of the component (C) are fine. , And it is difficult to obtain a molded article exhibiting sufficient transparency.

On the other hand, when the viscosity ratio exceeds 15, the viscosity of the matrix phase becomes low, and similarly, the component (C) cannot be finely dispersed, and a molded article showing sufficient transparency can be obtained. Becomes difficult. The viscosity referred to in the present invention is a value measured by a viscoelasticity measuring device, using a RSD2E manufactured by Rheometrics Inc., at a measurement temperature of 240 ° C., a sample thickness of 1.6 to 2.2 mm, and a plate radius of 12. 5mm,
The frequency is measured at a rate of 10 r / s and a sweep strain of 1 to 8%.

In the preparation of the graft copolymer resin (C), a known and commonly used polymerization method such as emulsion polymerization, emulsion-suspension polymerization, solution polymerization or bulk polymerization can be applied as it is. General commercial products such as those used can also be used as they are.

Further, the styrene-methacrylic acid ester-based copolymer resin (D) is a styrene-based monomer having a haze value of 10% or less on a 0.4 mm-thick sheet according to JIS K-7105 and methacrylic acid. It refers to a copolymer with an acid ester monomer. Examples of the styrene monomer include styrene, α-methylstyrene, o-methylstyrene, m
-Methylstyrene, p-methylstyrene, ethylstyrene, isobutylstyrene, tertiarybutylstyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, etc. And styrene is preferred.

Examples of the methacrylate monomer include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, and methacrylic acid-2.
-Ethylhexyl and the like, and methyl methacrylate is particularly preferable in terms of performance such as cost, impact strength and rigidity. These methacrylates may be used alone or in combination of two or more.

The specific method for producing the styrene-methacrylic acid ester-based copolymer resin (D) is not particularly limited, and may be a conventional emulsion polymerization method, solution polymerization method, suspension polymerization method, bulk polymerization method, continuous bulk polymerization method. It can be produced by a polymerization method or the like.

The thermoplastic polymer composition of the present invention can contain optional additives, if necessary, according to the intended use. The type of the additive is not particularly limited as long as it is generally used for blending plastics. For example, silica, calcium carbonate, magnesium carbonate, calcium sulfate, inorganic fillers such as talc, organic fibers, titanium oxide Pigments such as carbon black and iron oxide, dyes, lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylenebisstearylamide, release agents, organic polysiloxanes,
And plasticizers such as mineral oil.

Further, benzotriazole-based or benzophenone-based ultraviolet absorbers represented by Tinuvin P and Tinuvin 327 (Nippon Ciba Geigy Co., Ltd.) as additives usually used for improving weather resistance, trade name Sumilizer GM or Sanol L, a hindered phenolic antioxidant represented by GS (Sumitomo Chemical Co., Ltd.) and Irganox 1076 (Nippon Ciba Geigy Co., Ltd.)
Hindered amine-based light stabilizers represented by S-770 (Sankyo Co., Ltd.), phosphorus-based antioxidants represented by trisnonylphenylphosphite, and organic sulfur-based antioxidants represented by dimyristylthiodipropionate And the like.

Also, a reinforcing agent such as a flame retardant, an ultraviolet absorber, an antistatic agent, glass fiber, carbon fiber, metal whisker,
A petroleum resin obtained by polymerizing a cracked oil fraction containing a large number of unsaturated hydrocarbons by-produced by the thermal decomposition of naphtha represented by a terpene resin, other additives, or a mixture thereof can also be added. .

The method for producing the resin composition of the present invention is not particularly limited, and a known method can be used. For example, the polymer material is heated to an appropriate temperature using a general admixer such as a roll, a Banbury mixer, a single screw extruder, a twin screw extruder, a co-kneader, and a multi-screw extruder. The resin composition can be obtained by an apparatus capable of kneading while applying a shear stress. However, in order to obtain high transparency of the molded article, a graft copolymer resin (C), which forms a dispersed phase by kneading, forms a matrix phase. Of a styrene copolymer resin (A) and a methyl methacrylate resin (B), or a mixture of a styrene resin (A), a methyl methacrylate resin (B), and a styrene-acrylate copolymer resin (D) It needs to be finely dispersed inside.

The particle size of the finely dispersed graft copolymer (C) is preferably from 0.05 to 2 μm, more preferably from 0.05 to 1 μm. When the particle size of the finely dispersed graft copolymer (C) is in this range, the molded article exhibits high transparency. In order to finely disperse the graft copolymer (C) in this way, it is particularly preferable to use a kneading device such as a twin-screw extruder exhibiting high shear stress.

The resin composition of the present invention obtained as described above can be prepared by various methods known in the art, for example, extrusion molding, injection molding, hollow molding, rotational molding, chemical foaming, physical foaming and the like. Easily molds into a wide variety of practically useful products such as sheets, foams, films, injection molded products of various shapes, hollow molded products, pressure molded products, vacuum molded products, vacuum pressure molded products, rotational molded products, etc. It can be used for automobile parts, electric parts, machine parts, food packaging containers and the like. Among them, it is particularly preferable to use it as the sheet or film of the present invention described in detail below.

The sheet and film of the present invention are obtained by molding the above-described thermoplastic resin composition into a sheet or film. In order to obtain the sheet of the present invention, for example, the above-mentioned (A) to (C) and other components are blended if necessary and melt-kneaded using a twin-screw extruder or the like. 180 to 300
After melting at a temperature of ° C., the sheet can be obtained by discharging from a mold at the tip of the extruder.

At this time, the mold that can be used is not particularly limited, and examples thereof include a strand die, a ring die, a T die, a circular die, a pipe die, a deforming die, and a net die. The thickness of the obtained sheet is preferably from 0.1 to 20 mm from the viewpoint of secondary workability. When obtaining the sheet, as a lubricant, calcium stearate,
Zinc stearate, magnesium stearate, aluminum stearate, ethylene bisstearyl amide and the like can be used.

The sheet obtained in this way can be used as a single layer, but can also be used as a laminated sheet using heat fusion or an adhesive. As a method of laminating, a method of coextruding a resin to form a multilayer is preferable. The resin raw material to be laminated by this co-extrusion is not particularly limited, but polystyrene resins such as polystyrene and high-impact polystyrene, polypropylene, high-density polyethylene, polyolefin-based resins such as low-density polyethylene, polyester, polymethyl pentene,
Polyamide, polycarbonate and the like can be laminated and used. These sheets or laminated sheets can be formed into a container by a known and commonly used method, and the molded product of the sheet thus obtained may be subjected to antistatic processing, coloring, or coating plating as necessary. .

[0056]

EXAMPLES The present invention will now be described in more detail with reference to Examples, but it should not be construed that the present invention is limited to these Examples. The values shown in the examples are determined by the following method.

(Heat deformation temperature) Measured according to JIS K 7191. (Izod impact strength) JIS K 6923 (1/4
(With inch notch). (Haze) Thickness 0.4 according to JIS K 7105
It measured using the sheet of mm.

(Viscosity) RDS2E manufactured by Rheometrics
Was performed using Frequency Sweep. Sample thickness: 1.6 to 2.2 mm Measurement temperature: 240 ° C. Radius: 12.5 mm Gap: 1.6 to 2.2 mm Strain: 1 to 8% Sweeptype logarithmic Frequency: 10 r / s

(Synthesis Example 1) (Synthesis Example of Styrene Copolymer Resin (A)) Into a 5 L stainless steel reactor equipped with a turbine type stirring blade, 2000 g of distilled water was charged, and a suspension stabilizer was added thereto. 10 g of carboxymethylcellulose and 0.05
g of sodium dodecylbenzenesulfonate and further dissolved therein, 770 g of styrene, 120 g of methacrylic acid, 3 g of tert-butylperoxy-3,3,3.
5-trimethylcyclohexane, 0.3 g tert-
Butyl peroxybenzoate and 3.5 g of α-methylstyrene dimer are added sequentially and then at 400 rpm
The temperature was raised to 90 ° C. while stirring at 110 ° C.
g of methacrylic acid was added over 6 hours, and after the addition was completed, the temperature was maintained at that temperature for 3 hours.
This temperature was maintained for another 3 hours to complete the polymerization.

The thus-obtained granular copolymer is washed, dehydrated, and dried, and has a refractive index (n ▼ 23 ▼ D) of 1.
5739 with a haze of 1.3% and a viscosity of 3.
An object of 4 × 10 ³ (Pa.S) was obtained. Hereinafter, this is abbreviated as resin (A-1).

Synthesis Example 2 (Same as above) Instead of tert-butylperoxy-3,3,5-trimethylcyclohexane, 2 g of benzoyl peroxide and 0.1 g of tert-butylperoxybenzoate were used.
Polymerization was conducted in the same manner as in Synthesis Example 1 except that the amount was changed to 5 g. The refractive index (n （23D) was 1.5739, the haze was 1.2%, and the viscosity was 2.5 × 10 ³ ( Pa.
S) was obtained. Hereinafter, this is referred to as resin (A-2).
Abbreviated.

(Synthesis Example 3) (Same as above) Styrene was set to 600 g, and the initial charge of methacrylic acid was set to 250 g, 2 g of di-tert-butyl peroxyhexahydroterephthalate, and 1 g of tert-butyl peroxybenzoate. Synthesis Example 1 except that 150 g of methacrylic acid was added from the time when the temperature was increased.
Polymerization was performed in the same manner as described above, and the refractive index (nｎ23 ▼ D) was 1.
563, a haze of 1.5% and a viscosity of 6.4
× 10 ³ (Pa.S) was obtained. Hereinafter, this is abbreviated as resin (A-3).

(Synthesis Example 4) (Same as above) Into the same reactor as in Synthesis Example 1, 2000 g of distilled water was charged, and 10 g of carboxymethylcellulose and 0.1 g of distilled water were added.
05 g of sodium dodecylbenzenesulfonate and further dissolved in 600 g of styrene, 100 g of α-methylstyrene, 150 g of methacrylic acid, 2 g of di-tert-butyl peroxyhexahydroterephthalate,
1 g of tert-butyl peroxybenzoate and 4
g of α-methylstyrene dimer were sequentially charged, and thereafter the refractive index (nｎ2323D) was 1.56 in the same manner as in Synthesis Example 1.
7, the haze is 1.5% and the viscosity is 3.1 × 1
A 0 ³ (Pa.s) to give the desired resin. Hereinafter, this is abbreviated as resin (A-4).

(Synthesis Example 5) [Graft copolymer resin (C)
Synthesis Example] 1900 g of distilled water was charged into a 5 L reactor equipped with a stirrer purged with nitrogen, and 50 g of a 20% aqueous sodium rosinate solution was further charged and dissolved as an emulsifier, butadiene having a solid content of 57.4% was dissolved therein. 104 rubber latex
5 g was charged. Next, 84 g of methyl methacrylate and 36 g of styrene were charged together with 0.5 g of tert-dodecyl mercaptan and 4 g of tris (nonylphenyl) phosphite, and the temperature was raised while blowing nitrogen gas to reach 65 ° C. At this time, 100 g of distilled water containing 2 g of potassium persulfate was added, and from the time when the temperature was raised to 70 ° C., 196 g of methyl methacrylate and 84 g of styrene were added over 2.5 hours, After the addition was completed, the temperature was maintained at the same temperature for 1.5 hours, then the temperature was raised to 80 ° C., and the temperature was maintained at the same temperature for 1 hour to perform emulsion polymerization.

Thereafter, the mixture was coagulated with magnesium sulfate,
Washing, dehydration and drying were performed to obtain a target resin. Hereinafter, this is abbreviated as resin (C-1). The refractive index of this product (n ▲ 23
▼ D) was 1.523, the haze was 15%, and the viscosity was 1.5 × 10 ³ (Pa.S).

(Synthesis Example 6) (Same as above) Instead of butadiene rubber latex, the solid content was 41%.
Was changed to use 1463 g of butadiene styrene copolymer rubber latex (styrene content = 25%), and the composition of the initial charge was 54 g of methyl methacrylate, 54 g of styrene, and 12 g of acrylonitrile. Was changed to 126 g of methyl methacrylate, 126 g of styrene, and 28 g of acrylonitrile, respectively, to obtain a powdery target substance in the same manner as in Synthesis Example 5. Hereinafter, this is abbreviated as resin (C-2). Its refractive index (n23D) is 1.53.
7, haze is 18%, viscosity is 1.1 × 10 ³ (Pa.
S).

(Synthesis Example 7) [Synthesis Example of Styrene-Methacrylate Copolymer Resin (D)] A mixed solution comprising 50 parts of styrene, 50 parts of methyl methacrylate and 10 parts of toluene was prepared, and organic peroxide was further prepared. 0.02 parts of 2, based on 100 parts of the monomer mixture
2-Bis (4,4-di-t-butylperoxycyclohexyl) propane was added, and bulk polymerization was continuously performed under the following conditions using an apparatus constituting a polymerization line shown in FIG.

The raw material solution is sent to a 20-liter stirred reactor (2) by a plunger pump (1), and is subjected to initial polymerization under dynamic mixing by a stirrer. This initial polymerization is then sent to the circulation polymerization line (I) by the gear pump (3). The circulation polymerization line (I) is a tubular reactor having an inner diameter of 2.5 inches (incorporation of 30 static mixing elements SMX type manufactured by Gebrüder Sulzer, Switzerland, static mixing elements) in order from the inlet (4), (5) and (6). ) And a gear pump for circulating the mixed solution (7)
It is composed of Between the tubular reactor (6) and the gear pump (7) there is an outlet following the acyclic polymerization line (II). Tubular reactors (8), (9), and (10) similar to the above, in order from the inlet to the non-circulation polymerization line (II)
And a gear pump (11) are connected in series.

Continuous supply amount of mixed solution: 10 liter / hour Reaction temperature in circulation polymerization line (I): 120 ° C. Reaction temperature in non-circulation polymerization line (II): 130 to 160
° C Reflux ratio: R = F1 / F2 = 5

The mixed solution obtained by the polymerization was heated to 225 ° C. with a heat exchanger to remove volatile components under a reduced pressure of 50 mmHg, and then pelletized to obtain a styrene-methacrylic ester resin of the present invention. . Its refractive index (n23D) is 1.543 and its haze is 0.6%.
And the viscosity was 2.1 × 10 ³ (Pa.S).

Example 1 The resin (A) obtained in Synthesis Example 1
-1) and “SUMIPEX MH” having a refractive index (n ▲ 23D) of 1.49, a haze of 0.4%, and a viscosity of 5.1 × 10 ⁴ (Pa.S) [Sumitomo Chemical Industries, Ltd. Methyl methacrylate resin manufactured by Co., Ltd .; hereinafter abbreviated as resin (B-1)], a refractive index (nｎ23 ▼ D) of 1.519, a haze of 7.5%, and a viscosity of 2 .8 × 10 ⁴ (P
a. S), "Kaneace M-511" [graft copolymer resin manufactured by Kaneka Chemical Industry Co., Ltd .;
3) is mixed at a ratio shown in Table 1, and the mixture is kneaded and extruded using a coaxial twin-screw extruder having a cylinder temperature of 240 ° C and a diameter of 30 mmφ to obtain pellets.

Next, the pellets were dried at 105 ° C. for 3 hours, and test pieces were prepared using an in-line screw molding machine, and physical properties were measured. In addition, pellets with a diameter of 30 mmφ
The sheet was extruded from a T-die by a single screw extruder to obtain a sheet molded product having a thickness of 0.4 mm, and the physical properties were measured.
The results are shown in the same table. In the table, η1 represents the viscosity of the mixture of the components (A) and (B), η2 represents the viscosity of the component (C), and η3 represents the viscosity of the mixture of the components (A), (B) and (D). .

Example 2 The resin (A) obtained in Synthesis Example 2
-2) and “SUMIPEX LG” having a refractive index (n ▲ 23DD) of 1.49, a haze of 0.4%, and a viscosity of 2.3 × 10 ⁴ (Pa.S) [Sumitomo Chemical Industries, Ltd. Methyl methacrylate resin manufactured by Co., Ltd .; hereinafter abbreviated as resin (B-2)], a refractive index (nｎ23 ▼ D) of 1.539, a haze of 9.5%, and a viscosity of 1. 3 × 10 ⁴ (Pa.
S), “Kaneace B-522” [graft copolymer resin manufactured by Kaneka Chemical Co., Ltd .; hereinafter, resin (C-4)
A test piece was prepared in the same manner as in Example 1 except that the resin (D-1) obtained in Synthesis Example 4 was blended at the ratio shown in Table 1 and physical properties were measured. The results are shown in the same table.

Example 3 The resin (A) obtained in Synthesis Example 3
-3), resin (B-2), and resin (C-4), except that they were blended at the ratios shown in Table 1 in the same manner as in Example 1 to prepare a test piece. It was measured. The results are shown in the same table.

Example 4 The resin (A) obtained in Synthesis Example 4
-4), a resin (B-1), and a resin (C-3), and a test piece was prepared in the same manner as in Example 1 except that the ratio was as shown in Table 1. It was measured. The results are shown in the same table.

Example 5 Resin (A-2) and resin (B
-1) and a resin (C-1) obtained in Synthesis Example 5, a test piece was prepared in the same manner as in Example 1 except that the resin was mixed at a ratio shown in Table 1, and physical properties were measured. did. The results are shown in the same table.

(Comparative Example 1) As shown in Table 1 except that the resin (B-1) was used in place of the resin (B-2), blending was carried out at the same ratio as in Example 3 to obtain a mixture. A test piece was prepared in the same manner as described above, and the physical properties were measured. Η2 / of the obtained resin
η1 was 2.0 or less, and the haze of the sheet was 18 which was poor in transparency.

Comparative Example 2 As shown in Table 1, Example 2 was repeated except that the resin (C-3) was used instead of the resin (C-4).
The test pieces were prepared in the same manner as in Example 1, and the physical properties were measured. Since the refractive index of the mixture of the component (A), the component (B) and the component (D) was different from the refractive index of the component (C) by 0.01 or more, the haze of the sheet was 23, which was poor in transparency.

[0079]

[Table 1]

[0080]

According to the present invention, it is possible to provide a thermoplastic resin composition capable of obtaining a molded article having sufficient transparency while maintaining heat resistance and impact resistance, and a method for producing the same.

[Brief description of the drawings]

FIG. 1 is a diagram showing an outline of a continuous bulk polymerization apparatus used in the synthesis of a styrene-methacrylic ester copolymer resin (D) of Synthesis Example 7.

[Explanation of symbols]

(1): Plunger pump (2): Stirred reactor (3): Gear pump (4): Tubular reactor with static mixing element (5): Tubular reactor with static mixing element (6): Tubular reactor having a static mixing element (7): Gear pump (8): Tubular reactor having a static mixing element (9): Tubular reactor having a static mixing element (10): Having a static mixing element Tubular reactor (I): Circulation polymerization line (II): Non-circulation polymerization line

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 33/12 C08L 33/12 51/04 51/04 (72) Inventor Takeshi Morita Takemi-ku, Chiba-shi, Chiba Miyanogidai 1-25-15 −204 F term (reference) 3E086 AB01 AD05 AD06 BA02 BA15 BB22 BB41 BB90 CA01 DA08 4F070 AA07 AA08 AA18 AA29 AA32 AB08 AB09 FA03 FA17 FB03 FC06 4F071 AA12 AA12X AA22A AF33 AF33 AF33 AF33 BA01 BB06 BC01 4J002 BC04W BC07W BC07Z BG05X BN04Z BN06Y GT00 4J026 AA68 AC11 AC12 AC15 BA05 BA27 BA31 BB02 BB03 BB04 DB03 DB04 DB08 DB32 FA03 GA01 GA02

Claims (17)

[Claims] (A) 1 to 50% by weight of a methacrylic acid monomer, 99 to 50% by weight of a styrene monomer or 98 to 25% by weight of a styrene monomer and 1 to 50% of an α-methylstyrene monomer.
JIS K-7 obtained by copolymerization with 25% by weight
20 to 91 parts by weight of a styrene copolymer resin having a haze value of 10% or less in a 0.4 mm-thick sheet conforming to No. 105;
% Of a methyl methacrylate-based resin of 9 to 80 parts by weight, (C) (a) a rubbery polymer of 20 to 80 parts by weight, and (b)
10 to 90% by weight of methyl methacrylate monomer and (C)
8 of a mixture consisting of 90 to 10% by weight of styrene monomer
And a refractive index (n) obtained by copolymerizing
(23) D) is 1.510 to 1.550 and the thickness is 0.
The refractive index (nｎ) of a mixture of (A) a styrene copolymer resin and (B) a methyl methacrylate resin, comprising 3 to 30 parts by weight of a graft copolymer resin having a haze value of 20% or less in a 4 mm sheet. 23 ▼ D) is -0.01 to +0.0 of (C) the refractive index (nD23D) of the graft copolymer resin.
1, and the ratio of the viscosity (η1) of the mixture of the resin (A) and the resin (B) to the viscosity (η2) of the resin (C) is 2 ≦ η2 / η1 ≦ 15. A thermoplastic resin composition characterized by a haze value of 10% or less in a sheet having a thickness of 0.4 mm. 2. The graft copolymer resin (C) comprises (a) 20 to 80% by weight of a rubbery polymer, (b) 5 to 49% by weight of a methyl methacrylate monomer, and (c) 90 to 1% of a styrene monomer. % By weight and (d) a copolymer of 5 to 50% by weight of an acrylonitrile monomer has a refractive index (n ▲ 23D) of 1.5.
The thermoplastic resin composition according to claim 1, which has a haze value of 10% to 1.550 and a haze value of 20% or less in a sheet having a thickness of 0.4 mm. 3. The thermoplastic resin composition according to claim 1, wherein (a) the rubbery polymer (A) of the graft copolymer resin is a homopolymer of butadiene. 4. The thermoplastic resin composition according to claim 1, wherein the (a) rubbery polymer (C) of the graft copolymer resin is a copolymer of butadiene and styrene. 5. The thermoplastic resin composition according to claim 1, wherein the (a) rubbery polymer (C) of the graft copolymer resin is a copolymer of butadiene, styrene and acrylonitrile. 6. In addition to (A) 20 to 91 parts by weight of resin, (B) 1 to 79 parts by weight of resin, and (C) 3 to 30 parts by weight of resin, further (D) in accordance with JIS K-7105 (A) resin, (B) resin and (D) resin containing 1 to 79 parts by weight of a styrene-methacrylic acid ester-based copolymer resin having a haze value of 10% or less on a 0.4 mm-thick sheet. Is within the range of -0.01 to +0.01 of the refractive index (n23D) of the resin (C), and the mixture of the resin (A) A sheet having a thickness of 0.4 mm, wherein the ratio of the viscosity (η3) of the mixture of the resin (B) and the resin (D) to the viscosity (η2) of the resin (C) is 2 ≦ η2 / η3 ≦ 15. The thermoplastic resin composition according to any one of claims 1 to 5, wherein a haze value of the thermoplastic resin is 10% or less. 7. The method according to claim 1, wherein the graft copolymer resin (C) containing the rubbery polymer is finely dispersed with an average particle diameter of 0.05 to 2 μm. The thermoplastic resin composition according to one of the above. 8. (A) 1 to 50% by weight of a methacrylic acid monomer, 99 to 50% by weight of a styrene monomer or 98 to 25% by weight of a styrene monomer and 1 to 50% of an α-methylstyrene monomer.
JIS K-7 obtained by copolymerization with 25% by weight
20 to 91 parts by weight of a styrene copolymer resin having a haze value of 10% or less in a 0.4 mm-thick sheet conforming to No. 105;
% Of a methyl methacrylate-based resin in an amount of 9 to 80 parts by weight, (C) (a) 20 to 80% by weight of a rubbery polymer, and (b)
10 to 90% by weight of methyl methacrylate monomer and (c)
80 of a mixture consisting of 90 to 10% by weight of styrene monomer.
-20% by weight, the refractive index (n ▲
23 ▼ D) is 1.510 to 1.550 and the thickness is 0.4
When mixing 3 to 30 parts by weight of a graft copolymer resin having a haze value of 20% or less in a mm sheet, the refractive index of a mixture of (A) a styrene copolymer resin and (B) a methyl methacrylate resin ( (23D) is -0.01 to + of the refractive index (n23D) of the graft copolymer resin (C).
0.01, and the viscosity (η1) of the mixture of the resin (A) and the resin (B) (η1) and the viscosity (η2) of the resin (C).
The mixture ratio of (A) resin and (B) resin is adjusted so that the ratio of 2 ≦ η2 / η1 ≦ 15, and (C) the graft copolymer resin containing a rubber-like polymer is the average particle size. Diameter 0.05
A haze value of 0.4 mm thick sheet is characterized by being melt-kneaded so as to be finely dispersed in a size of ~ 2 μm.
A method for producing a thermoplastic resin composition of 0% or less. 9. The graft copolymer resin (C) comprises (a) 20 to 80% by weight of a rubbery polymer, (b) 5 to 49% by weight of a methyl methacrylate monomer, and (c) 90 to 1% of a styrene monomer. % By weight and (d) 5 to 50% by weight of an acrylonitrile monomer, and has a refractive index (n ▲ 23D) of 1.
The method for producing a thermoplastic resin composition according to claim 8, wherein the haze value of the sheet having a thickness of 510 to 1.550 and a thickness of 0.4 mm is 20% or less. 10. The method for producing a thermoplastic resin composition according to claim 8, wherein (a) the rubbery polymer (A) of the graft copolymer resin is a homopolymer of butadiene. 11. The method according to claim 8, wherein (A) the rubbery polymer (A) of the graft copolymer resin is a copolymer of butadiene and styrene. 12. The method according to claim 8, wherein the (a) rubbery polymer of the graft copolymer resin (C) is a copolymer of butadiene, styrene and acrylonitrile. 13. (A) 20 to 91 parts by weight of a resin and (B)
1 to 79 parts by weight of the resin, 3 to 30 parts by weight of the resin (C), and (D) a thickness 0.4 according to JIS K-7105.
Styrene with a haze value of 10% or less in mm sheet
When mixing 1 to 79 parts by weight of the methacrylate copolymer resin, the refractive index (nｎ23 ▼ D) of the mixture of the resin (A), the resin (B), and the resin (D) is changed to the resin (C). And the viscosity (η3) of the mixture of the resin (A), the resin (B) and the resin (D) is within the range of -0.01 to +0.01 of the refractive index (n ▲ 23D) of (C) The mixing ratio of the resin (A), the resin (B) and the resin (D) is adjusted so that the ratio of the viscosity (η2) of the resin is 1.8 ≦ η2 / η3 ≦ 15. The graft copolymer resin (C) containing the polymer is melt-kneaded so as to be finely dispersed with a mean particle size of 0.05 to 2 μm. The method for producing a thermoplastic resin composition according to the above item. 14. The method for producing a thermoplastic resin composition according to claim 8, wherein the melt-kneading is performed by a twin-screw extruder. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 7. 16. The molded product according to claim 15, wherein the molded product is a sheet or a film. 17. The molded article according to claim 16, wherein the molded article is a container made of a sheet.