JPH09324103A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition having excellent properties to prevent the short-shot in blow molding and give uniform wall thickness in thermal forming (air pressure forming, vacuum forming, etc.) and contour extrusion molding. SOLUTION: This composition is composed of (I) a copolymer produced by the graft copolymerization of a rubbery polymer with a vinyl cyanide compound, an aromatic vinyl compound and optionally a monomer copolymerizable therewith, (II) an acrylic copolymer composed of a vinyl cyanide compound, an aromatic vinyl compound and optionally a monomer copolymerizable therewith and (III) an acrylic copolymer containing >=230wt.% of methyl methacrylate unit and satisfies the following conditions. (1) The die-swell ratio of the composition is 20-200, (2) the AN ratio of the composition is 0.25-0.50, (3) the reduced viscosity (ηsp/c) of a component obtained by extracting the composition with acetone is 0.5-1.5 and (4) the composition is a resin for blow molding, thermal forming or contour extrusion molding.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to blow molding, thermoforming (pressure molding, vacuum molding, etc.) and profile extrusion molding resins, which are used in blow molding, and are used in blow molding, heat molding and profile extrusion molding, respectively. The present invention relates to a thermoplastic resin composition having excellent meat prevention property.

[0002]

2. Description of the Related Art The blow molding method has been widely used mainly for polyolefin resin as a technique for molding a hollow container. However, since a large molded product can be obtained by using a relatively simple apparatus, engineering resin can be used. It is also drawing attention as a technique for molding the large-sized molded products used. For example, Japanese Patent Application Laid-Open No. 2-64149 describes blow molding using polyphenylene ether. Also, in recent years, ABS resins have been tried as a material for large blow-molded articles, for example, JP-A-3-243646,
JP-A-3-263451, JP-A-4-25431
Japanese Patent Laid-Open No. 4-120157 and the like.

In the blow molding method, since air is trapped between the parison and the mold at the time of molding, the molten resin does not reach the complicated shape portion and the mounting metal fitting portion to be inserted into the blow molded product. (Hereinafter referred to as meat filling). Conventionally, in order to solve such a problem, a method has been taken in which a die is provided with a hole for releasing air so as to eliminate air accumulation. Further, a forced air bleeding method such as evacuation is also taken. However, in many cases, the shape, size, position, and quantity of holes cannot be taken properly,
Even if properly taken, the traces of the holes are transferred to the blow-molded product and remain as convex protrusions, which does not always lead to a satisfactory situation.

On the other hand, a thermoforming method such as a vacuum forming method or a pressure forming method is also a technique for forming a large-sized molded article.
It is often used as a molding method for inner boxes of electric refrigerators and travel cases. Conventionally, vinyl chloride, polycarbonate, polyethylene terephthalate, etc. have been used as the material. ABS resins have also been tried, for example, JP-A-5
7-110414, JP-A-58-174410, JP-A-1-268761 and the like. In the vacuum molding method, after the resin which has been molded into a sheet shape is heated in advance, the sheet is transferred to the mold by stretching the sheet by evacuation, but at this time, the wall thickness of the corner portion of the molded product is the surrounding wall thickness. It causes a phenomenon that it becomes thinner than the thickness (hereinafter referred to as uneven thickness). In the air pressure molding method, a mechanical operation is added in addition to the evacuation at the time of die transfer, so that the uneven thickness tends to become larger.

The profile extrusion molding method is a technique for molding a molded product having a complicated cross-sectional shape, and various molded products such as a hollow molded product and a molded product sharing a rib with a hollow chamber are produced. As the material, vinyl chloride, ABS, polycarbonate, etc. are used. In this molding method, it is difficult to adjust the wall thickness of each part of the molded product, and it is the actual situation that the product is obtained by trial and error such as devising the shape of the die part in order to obtain a desired molded product. Therefore, prevention of uneven thickness from the material side is desired.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a thermoplastic resin which is excellent in wall-surrounding property during blow molding, and is excellent in preventing uneven thickness during thermoforming (vacuum molding, pressure molding, etc.) and profile extrusion molding. An object is to provide a resin composition.

[0007]

In view of the above situation, the present inventors have added a specific acrylic copolymer to an ABS resin composition, and further added a specific die swell ratio, AN
It has been found that a thermoplastic resin composition having an excellent wall thickness property at the time of blow molding by the ratio, reduced viscosity, and an uneven thickness preventing property at the time of thermoforming and profile extrusion molding can be provided, and has completed the present invention. .

That is, the present invention is as follows. A copolymer formed by graft-copolymerizing a vinyl cyanide compound and an aromatic vinyl compound on a rubbery polymer, a copolymer composed of a vinyl cyanide compound and an aromatic vinyl compound, and 30% by weight of a methyl methacrylate unit. A composition comprising the above acrylic copolymer, wherein (1) the die swell ratio of the composition is 20 or more and 200 or less, and (2) the AN ratio of the composition is 0.2.
5 or more and 0.50 or less, (3) the reduced viscosity (ηsp / c) of the component obtained by extracting from the composition with acetone is 0.5 or more and 1.5 or less, and (4) the composition is blown. Molding,
A thermoplastic resin composition, which is a resin for thermoforming and profile extrusion molding.

Or 2. Copolymers formed by graft-copolymerizing a rubbery polymer with a vinyl cyanide compound, an aromatic vinyl compound and a monomer copolymerizable therewith, and a copolymer comprising a vinyl cyanide compound and an aromatic vinyl compound And a composition comprising an acrylic copolymer containing 30% by weight or more of methyl methacrylate unit, wherein (1) the die swell ratio of the composition is 20 or more and 200 or less, and (2) the AN ratio of the composition is 0.25. 0.50 or less, (3) the reduced viscosity (ηsp / c) of the component obtained by extraction from the composition using acetone, 0.5 or more and 1.5 or less, (4) the composition is blow molded A thermoplastic resin composition, which is a resin for thermoforming or profile extrusion molding.

Or 3. A copolymer obtained by graft-copolymerizing a vinyl cyanide compound and an aromatic vinyl compound on a rubbery polymer, and a copolymer comprising a vinyl cyanide compound, an aromatic vinyl compound and a monomer copolymerizable therewith And a composition comprising an acrylic copolymer containing 30% by weight or more of methyl methacrylate unit, wherein (1) the die swell ratio of the composition is 20 or more and 200 or less, and (2) the AN ratio of the composition is 0.25. 0.50 or less, (3) the reduced viscosity (ηsp / c) of the component obtained by extraction from the composition using acetone, 0.5 or more and 1.5 or less, (4) the composition is blow molded A thermoplastic resin composition, which is a resin for thermoforming or profile extrusion molding.

Or 4. Vinyl cyanide compounds, aromatic vinyl compounds, and copolymers thereof with rubbery polymers obtained by graft-copolymerizing vinyl cyanide compounds, aromatic vinyl compounds, and monomers copolymerizable therewith A composition comprising a copolymer composed of possible monomers and an acrylic copolymer containing 30% by weight or more of methyl methacrylate units, wherein (1) the die swell ratio of the composition is 20 or more and 200 or less, (2) The AN ratio of the composition is 0.25 or more and 0.50 or less, and (3) the reduced viscosity (ηsp / c) of the component obtained by extracting acetone from the composition is 0.5 or more and 1.5 or less. (4) the composition is blow molded, thermoformed,
Provided is a thermoplastic resin composition, which is a resin for profile extrusion molding.

Hereinafter, the present invention will be described in more detail. Used as a copolymer (hereinafter referred to as graft copolymer (I)) obtained by graft-copolymerizing a rubbery polymer with a vinyl cyanide compound, an aromatic vinyl compound and optionally a monomer copolymerizable therewith. It is essential that the rubbery polymer to be used contains butadiene. In addition, other monomers such as aromatic vinyl, vinyl cyanide, (meth) acrylic acid ester and vinyl carboxylate compound which are copolymerized with butadiene can be used. It can also be copolymerized. Examples are polybutadiene,
Examples thereof include diene-based copolymers such as styrene-butadiene copolymers and acrylonitrile-butadiene copolymers and hydrogenated diene-based polymers. Among them, polybutadiene is desirable. The graft copolymer (I) is obtained by graft-polymerizing a vinyl polymer with a vinyl cyanide compound or an aromatic vinyl compound, and if necessary, a monomer copolymerizable therewith, for example, a maleimide compound, The (meth) acrylic acid ester compound, the vinyl carboxylate compound and the like can be used together in the graft polymerization.

A copolymer composed of a vinyl cyanide compound, an aromatic vinyl compound and a monomer copolymerizable therewith (hereinafter referred to as a copolymer (II)) is a vinyl cyanide compound and an aromatic vinyl compound. Or a vinyl cyanide compound or an aromatic vinyl compound and a monomer copolymerizable therewith. As the copolymerizable monomer, for example, a maleimide compound, a (meth) acrylic acid ester compound, a vinyl carboxylate compound, or the like can be used. The copolymer (II) can also be obtained in the graft polymerization process of the graft copolymer (I).

Examples of the vinyl cyanide compound used in the present invention include acrylonitrile and methacrylonitrile. One kind or a mixture of two or more kinds is used. In the graft copolymer (I) and the copolymer (II), different vinyl cyanide compounds may be used, or the same vinyl cyanide compound may be used. Examples of the aromatic vinyl compound used in the present invention include styrene and α-
Methylstyrene, α-chlorostyrene, bromostyrene, p-methylstyrene and the like can be mentioned, and one kind or a mixture of two or more kinds is used. Of these, styrene and α-methylstyrene are preferable. In the graft copolymer (I) and the copolymer (II), different aromatic vinyl compounds may be used, or the same aromatic vinyl compound may be used.

In the present invention, if necessary, a monomer such as a maleimide compound, a (meth) acrylic acid ester compound or a vinyl carboxylate compound which is copolymerizable with a vinyl cyanide compound or an aromatic vinyl compound can be used.
Examples of the maleimide compound include N-alkyl-substituted maleimides having an alkyl group having 1 to 4 carbon atoms, N-phenylmaleimide, nuclear-substituted N-phenylmaleimide, N-cyclohexylmaleimide, and the like. Examples of the (meth) acrylic acid ester compound include alkyl methacrylates having an alkyl group having 1 to 12 carbon atoms such as methyl methacrylate, and acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms such as methyl acrylate. . Examples of vinyl carboxylate compounds include acrylic acid, maleic anhydride, and methacrylic acid.

Acrylic copolymer containing 30% by weight or more of methyl methacrylate unit (hereinafter referred to as copolymer (III))
Examples thereof include a methyl methacrylate-alkyl acrylate copolymer. Alkyl acrylate is
For example, one or more monomers selected from alkyl acrylates having 1 to 10 carbon atoms such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate may be mentioned. The content of methyl methacrylate based on the total amount of the monomers constituting the copolymer (III) is desired to be at least 30% by weight or more, preferably 40 to 99% by weight. Further, the copolymer (III) has a reduced viscosity of at least 0.5, preferably 1 to 20 from the viewpoint of preventing resin drawdown during blow molding, thermoforming (vacuum molding, pressure molding, etc.) and profile extrusion molding. The range of is desired.

The rubbery polymer in the graft copolymer (I) can be prepared by any of emulsion polymerization method, solution polymerization method and bulk polymerization method. The graft copolymer (I) can be produced by any of solution polymerization method, bulk polymerization method and emulsion polymerization method. Of these, the emulsion polymerization method is preferable. A non-graft copolymer is co-produced in the process of this graft polymerization, and this is included in the copolymer (II). The method for producing the copolymer (II) and the copolymer (III) by copolymerization is not particularly limited, and any known solution polymerization method, bulk polymerization method, or emulsion polymerization method can be used.

The thermoplastic resin composition of the present invention must satisfy the following specified conditions. That is, (1) the die swell ratio of the composition is adjusted to 20 or more and 200 or less. The die swell ratio here is defined by the following equation. Die swell ratio = XY / Y × 100 X: Strand diameter Y: Orifice diameter (2 mm) In addition, the measurement method is a melt indexer and a temperature of 220.
The strand diameter is measured when the melt flow rate is measured under conditions of ° C and a load of 10 kgf. The die swell ratio is adjusted by adjusting the molecular weights of the graft component of the graft copolymer (I), the copolymer (II) and the copolymer (III). Particularly, it is effective that the reduced viscosity of the copolymer (III) is at least 0.5 or more, preferably 1 to 20. Further, there are a method of expanding the molecular weight distribution of the copolymer (II) to a high molecular weight side, a method of providing a branched structure, and the like.

(2) The AN ratio of the composition is adjusted to 0.25 or more and 0.50 or less. The AN ratio here is defined by the following equation. AN ratio = A / A + S A: Amount of vinyl cyanide compound in composition (wt.%) S: Amount of aromatic vinyl compound in composition (wt.%)

(3) Acetone is adjusted from the composition so that the reduced viscosity (ηsp / c) of the component obtained by extraction is 0.5 or more and 1.5 or less. The reduced viscosity here is ηsp / c measured at 30 ° C. with a 0.5% methyl ethyl ketone solution of the acetone extracted component. The reduced viscosity is adjusted by adjusting the ungrafted component of the graft copolymer (I), the molecular weight of the copolymer (II), the molecular weight of the copolymer (III), and the addition amount.

The thermoplastic resin composition of the present invention, when satisfying the above-mentioned specific conditions, has a survivability in blow molding, uneven thickness in thermoforming (vacuum molding, pressure molding, etc.) and profile extrusion molding. Preventability is significantly improved. If even one of the above-mentioned specific conditions is lacking, not only some or all of the improving effects of these characteristics are deteriorated, but also other practical characteristics are deteriorated. For example, when the die swell ratio is less than 20, not only the surrenderability during blow molding becomes insufficient, but also the drawdown of the parison becomes severe. If it exceeds 200, sizing during profile extrusion molding becomes difficult.

When the AN ratio is less than 0.25, the effect of adding the copolymer (III) is not sufficiently exerted and not only the survivability of blow molding becomes insufficient, but also the blow molded product. May be applied in a later process, causing problems such as inhaling paint during painting, which is not practical. 0.
If it exceeds 50, the resin is colored when the reworked product produced during blow molding or thermoforming is reused, which is not preferable. If the reduced viscosity of the acetone-extracted component is less than 0.5, drawdown during blow molding, sheet sagging during thermoforming, and strand sagging between the die and sizing during profile extrusion molding occur. If it exceeds 1.5, the load of the screw in the extruder at the time of blow molding or profile extrusion molding becomes large, which causes deterioration of the resin due to an increase in the resin temperature and lower productivity.

The thermoplastic resin composition of the present invention contains the graft copolymer (I) and the copolymer (I) so that the content of the rubbery polymer in the composition is preferably 10 to 30% by weight.
I) and the copolymer (III) are blended. If it is less than 10% by weight, the impact resistance is not sufficient, and if it exceeds 30% by weight, the resin is colored when the "burr" portion generated during blow molding and thermoforming is reused, blow molding and profile extrusion molding are performed. This causes a decrease in productivity due to an increase in screw load. In the present invention, an acrylic copolymer (III) containing 30% by weight or more of methyl methacrylate units is added to the ABS resin composition. Further, in order to effectively bring out the effect of the acrylic copolymer (III), it is effective that the reduced viscosity of the copolymer is at least 0.5 or more, preferably in the range of 1 to 20. The content of the copolymer (III) in the composition is preferably 0.5 to 10% by weight. If it is less than 0.5% by weight, the effect of addition is not sufficiently exhibited, and if it exceeds 10% by weight, the fluidity is extremely lowered and molding becomes difficult.

In order to finally obtain the thermoplastic resin composition of the present invention, the graft copolymer (I), the copolymer (II) and the copolymer (III) are mixed in the thermoplastic resin generally. Various mixing devices conventionally used can be used. For example,
Examples include a vented extruder, a plastomill, a kneader, a Banbury mixer, and a Brabender. Of these, a vented extruder is preferable. The thermoplastic resin composition of the present invention, if necessary, other thermoplastic resins, known heat stabilizers, ultraviolet absorbers, lubricants, release agents, flame retardants, antistatic agents, colorants, foaming agents, A fibrous or granular inorganic filler or the like can be optionally added. These are graft copolymer (I), copolymer (II) and copolymer (III)
May be added in the step of producing each, or may be added in the step of mixing these.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the scope of the following Examples. The parts and% used in the examples are based on weight unless otherwise specified. Various measurements were carried out by the following methods and procedures. Pellet Granulation Method A sample having a predetermined formulation was mixed in advance with a Henschel mixer, and melt-kneaded at 260 ° C. using a vented extruder to prepare pellets.

Blow molding method The cavity surface is modeled as a mirror surface with a roughness of 0.05a, and a portion without air vent holes is made in the range of 250 mm in length and width, and a hexagon nut of M6 is placed in the center with double-sided adhesive tape. After mounting, using a blow molding machine with accumulator, average wall thickness of about 2.5 mm, length 400 mm,
A square bottle having a width of 360 mm and a width of 200 mm was blow-molded, and the meat filling property was evaluated. The material was pre-dried in advance (about 90 ° C., 3 hours). Molding temperature (set value): 220-230 ° C (cylinder,
Accumulator, die) Resin temperature: Approx. 210-240 ° C Mold temperature (setting value): 65 ° C Blow pressure: 6kg / cm ²

Criteria for meat filleting property The condition of meat filleting on the threaded portion of the nut was visually judged. ◎: Very good (fully flesh on the screw part) ○: Good (most flesh on the screw part) △: Slightly poor (half flesh on the screw part) ×: Poor (state that almost no meat is turning around the screw part)

Sheet Forming Method Using a sheet extruder having a taper manifold type T-die, a sheet having a thickness of 2 mm and a width of 500 mm was extruded, and the extruded molded product was cut into a length of 500 mm. Molding temperature (set value): 220-230 ° C (cylinder,
Dice) Resin temperature: 210-240 ℃

Pneumatic molding method An upper mold having an opening in the lower part and a lower mold having the opening in the upper part framed in a square with an inner diameter of 400 mm and an outer diameter of 500 mm, and a cube of 400 mm on a side in the center when the upper and lower parts are stacked. Space is formed (lower depth: 300 mm, upper ceiling height: 100 mm), and further, 16 holes of 1 mm diameter are made at equal intervals on the bottom 4 sides of the inner surface in the lower part. It is connected to a decompression reservoir with a capacity of 96 liters adjusted to 100 hectopascals, a hole with a diameter of 10 mm is made in the center at the top, and it is connected to a pressure reservoir with a volume of 80 liters adjusted to 5000 hectopascals through a valve. Used the machine. 2m thickness obtained by sheet forming
m, 500 mm side sheet with infrared heater 190 ℃
After heating to, the upper and lower molds are fixed by sandwiching them between the upper mold and the lower mold. The valve leading from the lower mold to the pressure reservoir and the valve leading from the upper mold to the pressure reservoir were opened for molding, and the uneven thickness was determined.

Criteria for determining unevenness of wall thickness The thickness of the lower corners of the molded product corresponding to the four corners of the lower mold was measured (4 locations), and the ratio between the minimum value of the 4 points and the thickness of the center of the lower surface was measured. (Corner thickness (minimum value) / lower center thickness)
Was calculated and used as a measure of wall thickness uniformity. ⊚: Very good (0.8 ≦ ratio) ○: Good (0.6 ≦ ratio <0.8) Δ: Somewhat bad (0.4 ≦ ratio <0.6) ×: Bad (0.4> ratio) )

Profile extrusion molding method A single-screw 40Φ extruder provided with a die having a short cross section of 30 mm × 3 mm was used, and 8 m / mi was obtained through vacuum sizing.
The plate material was extruded at a speed of n to determine the uneven thickness. Molding temperature (set value): 220-230 ° C (cylinder,
Dice) Resin temperature: 210-240 ° C

Criteria for determining thickness unevenness The thickness of the central portion and the end portion of the plate material was measured, and the ratio (thickness at the end portion / thickness at the central portion) was calculated and used as a scale for the thickness uniformity. ⊚: Very good (0.95 ≦ ratio) ○: Good (0.9 ≦ ratio <0.95) Δ: Slightly poor (0.8 ≦ ratio <0.9) ×: Bad (0.8> ratio) )

Die Swell Ratio Measuring Method The diameter of the parison obtained under the melt flow rate measuring conditions of JIS K-7210 (temperature = 220 ° C., load = 10 kg) was measured, and the die swell ratio was calculated.

Acetone Extraction Method of Extraction Acetone 20 ml and 1 g of a pellet of the thermoplastic resin composition were placed in a centrifuge tube (5 tubes were prepared), shaken with a shaker for 2 hours, and then dissolved with a centrifuge insoluble matter. The minutes were separated. The supernatant was decanted, acetone was evaporated with an explosion-proof dryer, and an acetone extract was collected. Reduced viscosity measurement method Preliminarily dried 0.2500 g of acetone extract was precisely weighed, put into an ounce with 50 ml of methyl ethyl ketone, and put into a Cannon-Fenske type capillary tube No. 50 was used to measure the viscosity at a temperature of 30 ° C.

Reference Example 1: Preparation of Graft Copolymer (I) Polybutadiene rubber latex (rubber particle size 3000A)
40 parts (solid content), 100 parts of deionized water, 0.3 part of potassium rosinate and 0.2 part of t-dodecyl mercaptan were put into a polymerization tank equipped with a reflux condenser, and the gas phase part was replaced with nitrogen to 70 ° C. The temperature was raised. 20 parts of acrylonitrile, 40 parts of styrene, 0.15 parts of cumene hydroperoxide,
To a mixed solution of 0.4 part of t-dodecyl mercaptan and 50 parts of deionized water, 0.3 part of sodium formaldehyde sulfoxylate, 0.004 part of ferrous sulfate and 0.04 part of sodium ethylenediaminetetraacetate are added. The aqueous solution was added continuously for 7 hours for reaction. During this period, the temperature of the polymerization system was controlled at 70 ° C., and after the addition was completed, 0.02 part of cumene hydroperoxide was further added and the state was maintained for 1 hour to complete the reaction. A resin component was precipitated from the obtained latex using magnesium sulfate, washed, filtered and dried to obtain an ABS dry powder. This was designated as A-1. A similar reaction was carried out by changing the ratio of styrene and acrylonitrile, etc. to obtain A-2. Furthermore, in addition to styrene and acrylonitrile, butyl acrylate was added as a third component and the same reaction was carried out to obtain A-3. The analytical values of each copolymer are shown in Table 1.

[0036]

[Table 1]

Reference Example 2: Preparation of Copolymer (II) A monomer mixture consisting of 25 parts of acrylonitrile, 50 parts of styrene and 25 parts of ethylbenzene was placed in a continuous type, complete mixing type reactor preheated to 160 ° C. The liquid was continuously added, and the reaction was carried out while paying out a polymer solution corresponding to the added amount. After the solid content of the reaction system was stabilized at 50% by weight, the polymer solution dispensed was devolatilized and pelletized after granulation. This was designated as B-1. The same reaction was carried out by changing the ratio of styrene and acrylonitrile, etc., and B-2,
B-3 and B-4 were obtained. Furthermore, in addition to styrene and acrylonitrile, N-phenylmaleimide was added as a third component and the same reaction was carried out to obtain B-5. The analytical values of each copolymer are shown in Table 2.

[0038]

[Table 2]

Reference Example 3: Preparation of Copolymer (III) 250 parts of deionized water, 1 part of latemur, 0.8 part of seed latex and 0.002 part of sodium persulfate were placed in a polymerization tank equipped with a reflux condenser and charged with air. The temperature of the phase portion was raised to 75 ° C. while substituting with nitrogen. A mixed solution of 90 parts of methyl methacrylate and 10 parts of n-butyl acrylate, and sodium persulfate 0.
40 parts of deionized water containing 002 parts was continuously added for 7 hours for reaction. During this period, the temperature of the polymerization system was controlled at 75 ° C., and 4 parts of deionized water containing 0.005 part of sodium persulfate was added in 4 batches over 1 hour after the addition was completed. A resin component is precipitated from the obtained latex using aluminum sulfate, washed, filtered and dried,
A dry powder was obtained. This was designated as C-1. The amount of methyl methacrylate of this copolymer was 87 wt. %, And the reduced viscosity (ηsp / c) was 6.02.

[0040]

【Example】

Examples 1 to 6 and Comparative Examples 1 to 3 Pellets were prepared by a predetermined granulation method using each of the compounding ingredients shown in Table 3, blow molding, pressure molding and profile extrusion molding were performed, respectively, and filleting property and uneven thickness prevention were performed. The sex was measured. Further, the die swell ratio and the reduced viscosity (acetone extracted component) of each composition were measured. The results are also shown in Table 3. The comprehensive judgment is as follows. ⊚: Very good ○: Good Δ: Slightly bad ×: Poor From this table, the examples of the present invention are better than the comparative examples in wall thickness at the time of blow molding, and prevention of uneven thickness at the time of pressure air molding and profile extrusion molding. Excellent in performance.

[0041]

[Table 3]

[0042]

EFFECT OF THE INVENTION The thermoplastic resin composition of the present invention is excellent in filleting property during blow molding, and is also excellent in uneven thickness preventing property during thermoforming (vacuum molding, pressure molding, etc.) and profile extrusion molding. Therefore, it is useful as a molding material for these.

Claims (4)

[Claims] 1. A copolymer obtained by graft-copolymerizing a vinyl cyanide compound and an aromatic vinyl compound on a rubbery polymer, a copolymer comprising a vinyl cyanide compound and an aromatic vinyl compound, and methyl methacrylate. Unit is 30
A composition comprising an acrylic copolymer containing at least wt%,
(1) The die swell ratio of the composition is 20 or more and 200 or less, (2) the AN ratio of the composition is 0.25 or more and 0.50 or less, and (3) it is obtained by extracting acetone from the composition. A reduced viscosity (ηsp / c) of the component is 0.5 or more and 1.5 or less, and (4) the composition is a resin for blow molding, thermoforming, or profile extrusion molding, which is a thermoplastic resin composition. . 2. A rubbery polymer and a vinyl cyanide compound,
Aromatic vinyl compounds and copolymers obtained by graft copolymerizing monomers copolymerizable therewith, and copolymers comprising vinyl cyanide compounds and aromatic vinyl compounds,
A composition comprising an acrylic copolymer containing 30% by weight or more of methyl methacrylate unit, wherein (1) the die swell ratio of the composition is 20 or more and 200 or less, and (2) the AN ratio of the composition is 0.25 or more and 0. 50 or less, (3) the reduced viscosity (ηsp / of the component obtained by extracting the composition with acetone using the composition).
c) is 0.5 or more and 1.5 or less, and (4) the composition is a resin for blow molding, thermoforming, or profile extrusion molding, which is a thermoplastic resin composition. 3. A copolymer obtained by graft-copolymerizing a vinyl cyanide compound and an aromatic vinyl compound with a rubber-like polymer, a vinyl cyanide compound, an aromatic vinyl compound and a monomer copolymerizable therewith. A copolymer consisting of
A composition comprising an acrylic copolymer containing 30% by weight or more of methyl methacrylate unit, wherein (1) the die swell ratio of the composition is 20 or more and 200 or less, and (2) the AN ratio of the composition is 0.25 or more and 0. 50 or less, (3) the reduced viscosity (ηsp / of the component obtained by extracting the composition with acetone using the composition).
c) is 0.5 or more and 1.5 or less, and (4) the composition is a resin for blow molding, thermoforming, or profile extrusion molding, which is a thermoplastic resin composition. 4. A rubbery polymer, vinyl cyanide compound,
Aromatic vinyl compound and a copolymer obtained by graft-copolymerizing a monomer copolymerizable therewith, and a copolymer comprising a vinyl cyanide compound, an aromatic vinyl compound and a monomer copolymerizable therewith And a composition comprising an acrylic copolymer containing 30% by weight or more of methyl methacrylate units, wherein (1) the die swell ratio of the composition is 20 or more and 200 or more.
Hereinafter, (2) the AN ratio of the composition is 0.25 or more and 0.50.
Below, (3) the reduced viscosity (ηsp / c) of the component obtained by extracting from the composition with acetone is 0.5 or more and 1.5 or less.
Hereinafter, (4) a thermoplastic resin composition, wherein the composition is a resin for blow molding, thermoforming, or profile extrusion molding.