JPH07118508A - Thermoplastic resin composition and its production - Google Patents

Abstract

PURPOSE:To obtain the title compsn. having a high impact resistance by compounding an arom. polyester, a copolymer obtd. from an arom. vinyl compd., a vinyl cyanide compd., and an epoxy vinyl compd., and a specific modified olefin polymer. CONSTITUTION:Copolymer A obtd. by copolymerizing an arom. vinyl compd. (e.g. styrene), a vinyl cyanide compd. (e.g. acrylonitrile), and an epoxy vinyl compd. (e.g. glycidyl methacrylate) in a specified wt. ratio is mixed with copolymer B obtd. from an arom. vinyl compd. and a vinyl cyanide compd., giving compsn. C. 50-95 pts.wt. copolymer A or compsn. C is mixed with 5-50 pts.wt. modified olefin polymer contg. 0.1-10wt.% unsatd. dicarboxylic anhydride or carboxylic acid units and mixed further with 0-5 pts.wt. weathering agent to give a resin compsn., which is mixed with an arom. polyester in a wt. ratio of (10:90)-(70:30) to give the objective resin compsn.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a thermoplastic resin composition having excellent impact resistance and weather resistance, and further having balanced physical properties such as chemical resistance, heat resistance, rigidity and moldability, and its production. Regarding the method.

[0002]

2. Description of the Related Art Conventionally, in order to improve the impact resistance of an aromatic polyester resin, the aromatic polyester resin has a
A resin composition in which a BS resin (acrylonitrile-butadiene-styrene polymer) is mixed is known (Japanese Patent Laid-Open No. Sho 5).
0-3450, 56-14546, 57-13
No. 7350). However, although the impact resistance of these resin compositions is improved, the degree of improvement is not always sufficient. In addition, the weather resistance of the mixed ABS resin is not satisfactory because it has a double bond, and therefore the weather resistance of the mixed resin composition also deteriorates.

Therefore, in order to improve this weather resistance, A
A, which has better weather resistance than ABS resin instead of BS resin
It is possible to use an ES resin (acrylonitrile-EPDM-styrene polymer), but the impact resistance was not sufficiently improved (Japanese Patent Laid-Open No. 17677/1993).

[0004]

SUMMARY OF THE INVENTION The present invention has such drawbacks,
That is, the insufficient weather resistance of the resin composition of the aromatic polyester resin and the ABS resin and the aromatic polyester resin and the AE
The problem of insufficient impact resistance of the resin composition with S resin is solved. That is, the object of the present invention is to
A resin composition comprising an aromatic polyester resin, a copolymer obtained by improving a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer with a specified vinyl monomer, and a modified polyolefin-based polymer. It is intended to provide a thermoplastic resin composition which is excellent in impact resistance, weather resistance and chemical resistance, and has a good balance of other physical properties, when added.

[0005]

Means for Solving the Problems As a result of intensive research aimed at achieving the above object, an aromatic polyester resin is composed of an aromatic vinyl monomer, a vinyl cyanide monomer and a specified vinyl monomer. It has been found that the above object can be achieved by mixing a resin composition comprising a copolymer and a modified polyolefin-based polymer.

That is, the present invention provides a copolymer (A) comprising (I-1) an aromatic vinyl monomer, a vinyl cyanide monomer and an epoxy group-containing vinyl monomer, or the copolymer. 50 to 95 parts by weight of a composition of (A) and a copolymer (B) composed of an aromatic vinyl monomer and a vinyl cyanide monomer, and (I-2) a modified polyolefin-based polymer, Consisting of 5 to 50 parts by weight of a modified polyolefin polymer modified by an amount of 0.1 to 10% by weight of a saturated dicarboxylic acid anhydride monomer group or an unsaturated carboxylic acid monomer group, and a copolymer ( The amount of the vinyl monomer containing a copolymerized epoxy group in A) includes the copolymer (B) in 100 parts by weight of the copolymer (A) when the copolymer (B) is not included. When the total amount of the copolymer (A) and the copolymer (B) is 10
0.1 to 10 parts by weight in 0 part by weight, and 0 to 5 parts by weight of a weathering agent is added to 100 parts by weight of the composition of (I-1) and (I-2). The present invention provides a thermoplastic resin composition comprising 10 to 70% by weight of the following resin composition and 90 to 30% by weight of the (II) aromatic polyester resin, and a method for producing the same.

Specific examples of the aromatic vinyl monomer used in the copolymer (A) and the copolymer (B) of the present invention include styrene, α-methylstyrene, vinyltoluene,
And t-butylstyrene.

Specific examples of the vinyl cyanide monomer include:
Examples include acrylonitrile and methacrylonitrile.

Specific examples of the epoxy group-containing vinyl monomer used in the copolymer (A) include glycidyl methacrylate, glycidyl methyl methacrylate, vinyl glycidyl ether, allyl glycidyl ether, and methallyl glycidyl ether.

Further, the copolymer (A) and the copolymer (B)
May contain a monomer copolymerizable with the above-mentioned other monomers, if necessary. As a specific example, for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth)
Acrylate, cyclohexyl (meth) acrylate,
Decyl (meth) acrylate, octadecyl (meth) acrylate, hydroxyethyl (meth) acrylate,
There are methoxyethyl (meth) acrylate and the like, and these can be used alone or in combination. However, the expression methyl (meth) acrylate here indicates both methyl acrylate and methyl methacrylate.

The proportion of each component of the copolymer (A) is not particularly limited as long as it is within the range of copolymerization, but preferably the total amount of the aromatic vinyl monomer and the vinyl cyanide monomer is 99.9 to 70 parts by weight, more preferably 99.9 to
90 parts by weight, and the epoxy group-containing vinyl monomer is preferably 0.1 to 30 parts by weight, more preferably 0.1 to 10 parts by weight.

The ratio of the aromatic vinyl monomer and the vinyl cyanide monomer is preferably 50 to 90% by weight, more preferably 65 to 85% by weight as the aromatic vinyl monomer.
Is. If the proportion of the aromatic vinyl monomer is less than 50% by weight, the fluidity is lowered, and if it exceeds 90% by weight, the chemical resistance is lowered, which is not preferable.

Next, the ratio of the aromatic vinyl monomer and the vinyl cyanide monomer of the copolymer (B) of the present invention is not particularly limited, but preferably 50 to 50 as the aromatic vinyl monomer. 90% by weight, more preferably 65 to 85% by weight. If the proportion of the aromatic vinyl monomer is less than 50% by weight, the fluidity is lowered, and if it exceeds 90% by weight, the chemical resistance is lowered, which is not preferable.

The amount of the copolymerized epoxy group-containing vinyl monomer in the copolymer (A) of the present invention is 100 parts by weight of the copolymer (A) when the copolymer (B) is not contained. When the copolymer (B) is contained in the parts, the amount of each of the copolymer (A) and the copolymer (B) is 0.1 in 100 parts by weight.
The content of the copolymer (A) and the copolymer (B) is not limited within the range of 10 to 10 parts by weight.

When the amount of the epoxy group-containing vinyl monomer is less than 0.1 parts by weight, the impact resistance of the resin composition is poor, and when it exceeds 10 parts by weight, the impact resistance of the resin composition is low. It is inferior and the fluidity is extremely low.

The modified polyolefin-based polymer used in the present invention is a modified product of a polyolefin-based polymer and is a modified product of a homopolymer or a copolymer of an olefin monomer. Specific examples of the olefin monomer used include ethylene, propylene, 1-butene, isobutylene, 2-
Butene, cyclobutene, 3-methyl-1-butene, 4-
Examples include methyl-1-butene, 4-methyl-1-pentene, cyclopentene, 1-hexene, cyclohexene, 1-octene, 1-decene, 1-dodecene.

Illustrating a preferable composition range, ethylene is 20 to 90 mol%, and α-olefin monomer is 10 to 8.
It is particularly preferable that the content is 0 mol% and the other monomer is 0 to 10 mol%, and the ethylene content is 50 to 85 mol%. The glass transition temperature (Tg) of these modified polyolefin-based polymers is −10 ° C. or lower, particularly preferably −30 ° C. or lower.

Specific examples of the unsaturated dicarboxylic acid anhydride monomer group for modifying the polyolefin polymer include maleic anhydride, methylmaleic anhydride, 1,2-dimethylmaleic anhydride, ethylmaleic anhydride, and anhydrous. There are phenylmaleic acid and the like, and maleic anhydride is particularly preferable. In addition, specific examples of the unsaturated carboxylic acid monomer group include acrylic acid and methacrylic acid.

The modified polyolefin polymer is a resin modified with 0.1 to 10% by weight of an unsaturated dicarboxylic acid anhydride monomer group or an unsaturated carboxylic acid monomer group in the resin, and is modified. If the amount is less than 0.1 parts by weight, the impact resistance strength of the thermoplastic resin composition is poor, and if it exceeds 10% by weight, the impact resistance strength of the thermoplastic resin composition is poor and the fluidity is further lowered.

The term "modification" as used in the present invention means that the main chain or side chain of the polyolefin polymer has a monomer group used for modification, such as a maleic anhydride group or a methacrylic acid group. It is something to say. These modifications can be performed by using known techniques such as random copolymerization and graft polymerization. The modification method is not particularly limited, and for example, it is carried out according to the method disclosed in Japanese Patent Publication Nos. 39-6810, 52-43677, 53-5716, 56-9925 and 58-445. be able to.

[0021] Further, rather than modification by introduction into the main chain, a modified product such as ethylene.
The propylene copolymer grafted on the tertiary carbon is preferable from the viewpoint of low temperature impact value and the like. Further, it is preferable in terms of physical properties that the residual amount of unreacted monomer is 0.5% by weight or less.

The molecular weight of the modified polyolefin-based polymer is not particularly limited, but a weight average molecular weight of 50,000 to 500,000, particularly preferably 100,000 to 3 is preferred in view of the balance of impact resistance and moldability.
It is preferably 100,000.

Examples of these modified polyolefin polymers include commercially available Tuffmer MP-0620 (trade name, manufactured by Mitsui Petrochemical Co., Ltd.).

Further, as a weathering agent used in a thermoplastic resin composition comprising the copolymer (A), the copolymer (B), the modified polyolefin polymer and the aromatic polyester resin of the present invention, it is widely and generally used. You can use whatever you have. For example, there is a combination of an ultraviolet absorber, a light stabilizer and an antioxidant, but it is not always necessary to use three agents together.

For example, an ultraviolet absorber, a light stabilizer and an antioxidant are exemplified below. Specific examples of the ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] benzotriazole, 2 -(3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3 5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2-ethoxy-2 '
Examples include ethyl oxac acid bisanilide, 2-ethoxy-5-t-butyl-2′-ethyl oxac acid bisanilide, and 2-hydroxy-4-n-octoxybenzophenone.

Specific examples of the light stabilizer include bis (2,2
2,6,6, -Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4)
-Piperidyl) sebacate, dimethyl succinate 1-
(2-hydroxyethyl) -4-hydroxy-2,2
6,6-Tetramethylpiperidine polycondensate, poly [[6
-(1,1,3,3-tetramethylbutyl) amino-
1,3,5-triazine-2,4-diyl] [(2,
2,6,6-Tetramethyl-4-piperidyl) imino]
Hexamethylene [(2,2,6,6-tetramethyl-4
-Piperidyl) imino]], 1- [2- [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine.

Specific examples of the antioxidant include triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 2,
4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-
Triazine, pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], octadecyl-3- (3,5-di-
t-Butyl-4-hydroxyphenyl) propionate, 2,2-thiobis (4-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-) t-butyl-4-hydroxybenzyl) benzene and the like.

The aromatic polyester resin used in the present invention is not particularly limited, and is a polymer or copolymer obtained by a condensation reaction containing an aromatic dicarboxylic acid or its derivative and an aliphatic glycol or its derivative as main components. Etc. Specific examples thereof include polyesters containing an aromatic ring such as polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polypentamethylene terephthalate, polyhexamethylene terephthalate, and polydecamethylene terephthalate, which may be used alone or in combination. Can be used.

The thermoplastic resin composition of the present invention is (I-1)
And a resin composition of (I-2) and a resin of (II), and a weatherproofing agent is added if necessary. (I-1) is a copolymer (A) comprising an aromatic vinyl monomer, a vinyl cyanide monomer and a vinyl monomer containing an epoxy group, or the copolymer (A), and an aromatic vinyl A composition comprising a copolymer (B) consisting of a monomer and a vinyl cyanide monomer, (I-2) a modified polyolefin polymer, and (II) an aromatic polyester resin.

The resin composition forming the main part of (I) is 50 to 95 parts by weight, preferably 60 to 90 parts by weight, of the copolymer (A) or the composition of the copolymer (A) and the copolymer (B). 90 parts by weight and 5 to 50 parts by weight, preferably 10 to 40 parts by weight of a modified polyolefin polymer modified with an unsaturated dicarboxylic acid anhydride monomer group or an unsaturated carboxylic acid monomer group It is a thing. If the amount of the modified polyolefin-based polymer is less than 5 parts by weight, the impact resistance of the thermoplastic resin composition will be poor, and if it exceeds 50 parts by weight, heat resistance, rigidity and fluidity will be deteriorated.

Further, the thermoplastic resin composition forming the main part of the present invention comprises 10 to 70% by weight, preferably 30 to 70% by weight of the resin composition of (I) and the aromatic polyester resin of (II). 90 to 30% by weight, preferably 70 to 30% by weight. If the amount of the aromatic polyester resin exceeds 90% by weight, the impact strength will be low, and if it is less than 30% by weight, the chemical resistance will be poor.

The thermoplastic resin composition of the present invention can be made into a resin composition by adding other additives and / or modifiers depending on the use, and specifically, glass fiber, carbon Fibers, reinforcing fibers such as aramid fibers, inorganic fillers such as talc, silica, clay, mica and calcium carbonate, flame retardants, lubricants and colorants can be used.

Next, the mixing for obtaining the thermoplastic resin composition of the present invention can be carried out by using an ordinary melt-kneading apparatus. As a melt-kneading device that can be suitably used, a screw extruder, a Banbury mixer, a cokneader, a mixing roll, or the like is used.

The production method for obtaining the thermoplastic resin composition of the present invention is carried out by preliminarily preparing the copolymer (A) or the copolymer (A) and the copolymer (B) and the modified polyolefin polymer in advance. A two-stage melt-mixing method in which the weather resistance and the aromatic polyester resin or only the aromatic polyester resin is melt-mixed with the resin composition obtained by melt-mixing is preferable.

A specific melt mixing method is, for example, the copolymer (A), or the copolymer (A) and the copolymer (B) and the modified polyolefin polymer are melt-extruded to obtain a resin composition. A method in which a weathering agent and an aromatic polyester resin, or only an aromatic polyester resin is added to a pellet and melt-extruded and mixed.

During the melt mixing extrusion of the copolymer (A) or the copolymer (A) and the copolymer (B) and the modified polyolefin polymer, a weatherproofing agent and an aromatic polyester resin,
Alternatively, a method in which only the aromatic polyester resin is added and melt mixing and extrusion are performed.

During the melt-kneading of the copolymer (A) or the copolymer (A) and the copolymer (B) and the modified polyolefin polymer by using a mixing roll, a weathering agent and an aromatic polyester resin, Alternatively, various melt-mixing methods such as a method of adding and mixing only the aromatic polyester resin can be used, and the melt-mixing method is not particularly limited.

The thermoplastic resin composition of the present invention is used in OA equipment (printers, facsimiles, etc.) chassis, fans, casings, housings, FDD chassis, portable laptop computer housings, electronic connectors and switches. , Relays, coil bobbins, terminal blocks, chassis for low-electricity related items in the electric field (radio cassette, etc.), electric parts such as VTR mechanical side plates, dryer heads, electric tools in the general and precision machinery field, mechanical parts for cameras, optical devices, agricultural machinery parts It is useful for applications such as instrument panels, meter cases, pillars, door mirrors, housings and motorcycle cowlings in the automobile field.

[0039]

EXAMPLES The present invention will be described in more detail with reference to the following examples. Further, these are merely examples, and do not limit the content of the present invention. The methods for measuring various physical properties are as follows.

(1) Impact strength: Notched IZO was used in accordance with ASTM D-256 using a 1/4 "thick test piece.
D was measured. (2) Weather resistance: A fade meter was used to expose a notched IZOD test piece having a thickness of 1/4 "under the conditions of a temperature of 83 degrees Celsius and an irradiation time of 1000 hours to obtain ASTM D-25.
6, the impact strength was measured, and the retention rate was calculated by comparing with the impact strength before irradiation.

(3) Chemical resistance: ASTM D-638 1
The dumbbell-shaped test piece was bent, kerosene was applied to the dumbbell-shaped test piece, and the dumbbell-shaped test piece was allowed to stand at room temperature for 24 hours and then observed. Dumbbell-shaped test pieces without cracks and crazes were marked with ◯, and those with these were marked with x.

(4) Heat resistance: According to ASTM D-648, a test piece having a thickness of 1/4 "was used, and a load was 18.6 kg / c.
The heat distortion temperature (HDT) was measured in m ² . (5) Rigidity: Thickness of 1/4 "according to ASTM D-790
The flexural modulus was measured using the test piece of.

(6) Elongation: According to ASTM D-638,
It was measured using a test piece having a thickness of ⅛ ″. (7) Flowability: Melt flow rate (MFR) was measured at a temperature of 265 ° C. and a load of 10 kgf in accordance with ASTM D-1238.

The copolymers, resins and weatherproofing agents used in the test are as follows. (1) Copolymer consisting of aromatic vinyl monomer, vinyl cyanide monomer and vinyl monomer containing epoxy group (A) Polymerization ratio (weight ratio) of styrene, acrylonitrile and glycidyl methacrylate is 75 / 24/1 (a-1),
74/24/2 (a-2), 66/22/12 (a-
The copolymer of 3) was used. For example, a-2 was copolymerized by using an autoclave having a volume of 60 liters and adding water, each monomer, a catalyst and the like at the following compounding ratio so that the volume was about 70% of 60 liters. That is, 100 parts by weight of pure water, 0.25 parts by weight of tribasic calcium phosphate, and 0.005 parts by weight of potassium persulfate were added, and then 74 parts by weight of styrene, 24 parts by weight of acrylonitrile, 2 parts by weight of glycidyl methacrylate, and a half-life were added under stirring. 0.5 parts by weight of 2,2′-azobisisobutyronitrile having a decomposition temperature of 82 ° C. for obtaining 1 hour was added, and the inside of the autoclave was replaced with nitrogen gas and then sealed. Then, the polymerization temperature was set to 80 ° C., and the mixture was polymerized for 7 hours and then cooled. Next, the copolymer was obtained by neutralization, dehydration and drying according to a conventional method. Other copolymers were polymerized under the same conditions as in a-2 except that the weight ratio of styrene, acrylonitrile and glycidyl methacrylate was changed to the above weight ratio.

(2) Copolymer of aromatic vinyl monomer and vinyl cyanide monomer (B) The polymerization ratio (weight ratio) of styrene and acrylonitrile is 75.
A copolymer of / 25 (b-1) was used.

(3) Modified Polyolefin Copolymer (C) The weight ratio of ethylene / propylene copolymer to maleic anhydride is 100/0 (c-1), 99.5 / 0.5 (c-).
2), 99.1 / 0.9 (c-3), 98.0 / 2.0
The polymer which is (c-4). For example, c-3 is 8.0 kg of ethylene / propylene copolymer pellets having an ethylene content of 80 mol%, 96 g of powdered maleic anhydride, and 2,5-
8.0 g of dimethyl-2,5-di (t-butylperoxy) hexane-3 was charged into a 20 liter Henschel mixer in which nitrogen was passed, and the mixture was stirred for 5 minutes to be blended uniformly. , L /
T-28, dullage type) to form pellets. The cylinder temperature was adjusted so that the polymer temperature was 240 degrees Celsius to obtain a graft reaction product. The other modified polyolefin-based copolymers were polymerized under the same conditions as in c-3 except that the compounding amount was changed so that the weight ratio of the ethylene / propylene copolymer and maleic anhydride would be the value shown above. went.

(4) Aromatic polyester resin (D) The aromatic polyester resin is a commercially available PB.
T resin, Novadul 5010S (manufactured by Mitsubishi Kasei) (d-1) and PET resin, Unipet RT533
(Manufactured by Nippon Unipet Co., Ltd.) (d-2) was used.

(5) Weathering agent (E) 2- (5-methyl-2-hydroxyphenyl) benzotriazole as an ultraviolet absorber and bis (2,2,6,6-tetramethyl-4-) as a light stabilizer. Piperidyl)
Sebacate and octadecyl-3-as antioxidant
(3,5-di-t-butyl-4-hydroxyphenyl)
A mixture (e-1) of propionate mixed at a weight ratio of 45/45/10 was used.

Example 1 Copolymer of aromatic vinyl monomer, vinyl cyanide monomer and vinyl monomer containing epoxy group (a-2 of A)
1.28 kg, 1.28 kg of a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer (b-1 of B), and 1.44 kg of a modified polyolefin-based polymer (c-3 of C) are used. Add to liter Henschel and blend, then TEM3
Extruded pellets were obtained at a temperature of 230 degrees Celsius with a 5B extruder (manufactured by Toshiba Machine Co., Ltd., twin-screw same-direction extruder). 3 kg of the obtained pellets and aromatic polyester resin (d-1 of D)
Add 3 kg to 20 liter Henschel and blend,
Pellets were obtained by extrusion with a TEM35B extruder at a temperature of 250 degrees Celsius. Using these pellets, test pieces for measuring physical properties were prepared by an injection molding machine, and various physical properties were measured. The results are shown in Table 1.

Examples 2 to 11 Except that the copolymer (A), the copolymer (B), the modified polyolefin polymer (C) and the aromatic polyester resin (D) were blended as shown in Tables 1 and 2. The same operation as in Example 1 was performed. The measurement results of various physical properties are shown in Tables 1 and 2.

Example 12 Copolymer of aromatic vinyl monomer, vinyl cyanide monomer and vinyl monomer containing epoxy group (a-2 of A)
0.96 kg, 0.96 kg of a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer (b-1 of B), and 1.08 kg of a modified polyolefin polymer (c-3 of C),
And aromatic polyester resin (d-1 of D)) 3.00
Add 20 kg to 20 liter Henschel, blend, and then
Extruded pellets were obtained using an EM35B extruder at a temperature of 250 degrees Celsius. Using these pellets, test pieces for measuring physical properties were prepared by an injection molding machine, and various physical properties were measured. The results are shown in Table 2.

Example 13 Copolymer of aromatic vinyl monomer, vinyl cyanide monomer and vinyl monomer containing epoxy group (a-2 in A)
1.28 kg, 1.28 kg of copolymer of aromatic vinyl monomer and vinyl cyanide monomer (b-1 of B) and 1.44 kg of modified polyolefin-based polymer (c-3 of C)
Add to a 20 liter Henschel and blend, then TEM
It was extruded and pelletized using a 35B extruder at a temperature of 230 degrees Celsius. 3.00 kg of the pellets, 3.00 kg of the aromatic polyester resin (D) and 69 of the weatherproofing agent (E)
g into 20 liter Henschel and blended, then TE
Extruded at a temperature of 250 degrees Celsius using an M35B extruder,
Pellets were obtained. Using these pellets, test pieces for measuring physical properties were prepared by an injection molding machine, and various physical properties were measured. The results are shown in Table 2. The weather resistance agent (E) was used in an amount of 2.3 parts by weight per 100 parts by weight of the total amount of (A), (B) and (C) in the composition of (I).

[0053]

[Table 1]

[0054]

[Table 2]

Comparative Examples 1 to 7 Copolymer (A) of aromatic vinyl monomer, vinyl cyanide monomer and vinyl monomer containing epoxy group, aromatic vinyl monomer and vinyl cyanide monomer The copolymer (B), modified polyolefin-based polymer (C) and aromatic polyester resin (D) of the monomer were blended as shown in Tables 3 and 4, and the same operation as in Example 1 was performed except for blending, Various physical properties were measured. The results are shown in Tables 3 and 4. In addition,
Comparative Examples-1 and 2 are out of the range of the amount of the epoxy group-containing vinyl monomer, Comparative Examples-3 and 4 are out of the range of the modified polyolefin copolymer, and Comparative Example-5 is the modified. The modification amount of the polyolefin-based copolymer was out of the range, Comparative Examples-6 and 7
Was an example in which the amount of the aromatic polyester resin was outside the range.

Comparative Example 8 3 kg of a commercially available AES resin (JSR AES110 manufactured by Japan Synthetic Rubber Co., Ltd.) and 3 kg of an aromatic polyester resin (d-1 of D) were charged into a 20 liter Henschel and blended, followed by TEM35B extrusion. Extruded pellets were obtained with a machine at a temperature of 250 degrees Celsius. Using these pellets, test pieces for measuring physical properties were prepared by an injection molding machine, and various physical properties were measured. The measurement results are shown in Table 4.

Comparative Example 9 3 kg of ABS resin having a polymerization ratio (weight ratio) of styrene, acrylonitrile and butadiene of 55/21/24,
20 kg of 3 kg of aromatic polyester resin (d-1 of D)
Add to liter Henschel and blend, then TEM35B
Extruded pellets were obtained in an extruder at a temperature of 250 degrees Celsius. Using these pellets, test pieces for measuring physical properties were prepared by an injection molding machine, and various physical properties were measured. The measurement results are shown in Table 4.

Comparative Example 10 3 kg of ABS resin having a polymerization ratio (weight ratio) of styrene, acrylonitrile and butadiene of 55/21/24, 3 kg of aromatic polyester resin (d-1 of D) and 69 g of weathering agent (E) were added. After being placed in a liter Henschel and blended, extruded pellets were obtained with a TEM35B extruder at a temperature of 250 ° C. Using these pellets, test pieces for measuring physical properties were prepared by an injection molding machine, and various physical properties were measured. The measurement results are shown in Table 4. The weather resistance agent (E) was 2.3 parts by weight with respect to 100 parts by weight of the ABS resin.
In the examples and comparative examples up to now, the injection molding temperature at which the test pieces for measuring physical properties were prepared was set to 250 ° C. as a standard, and some modifications were made depending on the condition of the molded product.

[0059]

[Table 3]

[0060]

[Table 4]

From the results of Examples and Comparative Examples, the following is clear. From the example and the comparative example-1, the impact value is low when the vinyl monomer containing the epoxy group is not included. Further, as in Comparative Example-2, when the amount of the vinyl monomer containing an epoxy group is too large, the impact value and the fluidity are lowered.

From Examples and Comparative Example-3, the impact value is low when the amount of the modified polyolefin polymer is small. Comparative Example-
When the amount of the modified polyolefin-based polymer is too much as shown in 4, heat resistance, rigidity and fluidity are lowered. Examples and Comparative Examples-
From 5, the impact value is low when the unmodified polyolefin-based polymer is used.

From Examples and Comparative Example-6, if the amount of the aromatic polyester resin is too much, the impact value is low. In addition, Comparative Example-7
As described above, when the amount of the aromatic polyester resin is too small, the chemical resistance becomes poor.

From the example and the comparative example-8, the impact value is low when using the AES resin which is generally commercially available. From Examples and Comparative Examples 9 and 10, when the commercially available ABS resin is used, the impact value is low and the weather resistance is poor.

As described above, the epoxy group-containing copolymer contains an appropriate amount of epoxy groups, and the modified polyolefin polymer is an unsaturated dicarboxylic acid anhydride monomer group or unsaturated carboxylic acid monolayer. It can be seen that the thermoplastic resin composition has excellent physical properties and a good balance of physical properties when it contains an appropriate amount of body groups and the amounts of the aromatic polyester resin and the modified polyolefin-based polymer are appropriate.

[0066]

INDUSTRIAL APPLICABILITY The thermoplastic resin composition of the present invention is excellent in impact resistance and weather resistance, has a good balance of physical properties such as chemical resistance, heat resistance, rigidity and elongation, and has good moldability and is an industrial material. It has extremely high practical value.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C08L 25/04 LEB // (C08L 25/04 67:00)

Claims (2)

[Claims] 1. A copolymer (A) comprising (I-1) an aromatic vinyl monomer, a vinyl cyanide monomer and a vinyl monomer containing an epoxy group, or the copolymer (A). 50 to 95 parts by weight of a composition of a copolymer (B) composed of an aromatic vinyl monomer and a vinyl cyanide monomer, and (I-2) an unsaturated dicarboxylic acid in the modified polyolefin-based polymer. A copolymer (A) comprising 5 to 50 parts by weight of the modified polyolefin-based polymer modified in an amount of 0.1 to 10% by weight of an anhydride monomer group or an unsaturated carboxylic acid monomer group. The amount of the vinyl monomer containing a copolymerized epoxy group in the copolymer is 100 parts by weight of the copolymer (A) when the copolymer (B) is not contained, and when the copolymer (B) is contained. In 100 parts by weight of the total amount of the copolymer (A) and the copolymer (B), 0. A 10 parts by weight, the composition 1 consisting of more (I-1) and (I-2)
A thermoplastic resin comprising 10 to 70% by weight of a resin composition containing 0 to 5 parts by weight of a weathering agent, and 90 to 30% by weight of (II) an aromatic polyester resin with respect to 00 parts by weight. Fat composition. 2. A method of melt-mixing the composition comprising (I-1) and (I-2) according to claim 1, further adding only a weathering agent and (II) or (II), and performing melt-mixing. A method for producing a thermoplastic resin composition, comprising: