JPH08165390A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE: To prepare a thermoplastic resin compsn. which has excellent impact resistance, heat distortion resistance, chemical resistance, and moldability and, when molded, causes no delamination and can provide a molding having matte appearance. CONSTITUTION: This thermoplastic resin compsn. comprises 100 pts.wt. resin mixture of 3 to 40 pts.wt. graft copolymer (A) prepd. by graft-polymerizing 5 to 60 pts.wt. group of vinyl compds. of 0.1 to 40wt.% vinyl compd. having an epoxy group and 99.9 to 60wt.% vinyl compd. copolymerizable with a rubbery polymer onto 95 to 40 pts.wt. rubbery polymer, 8 to 70 pts.wt. vinyl copolymer (B) prepd. by polymerizing at least two vinyl monomers selected from the group consisting of arom. vinyl compds., vinyl cyanide compds., alkyl methacrylate compds., and N-substd. maleimide compds., and 5 to 85 pts.wt. polycarbonate resin (C); and 0.5 to 50 pts.wt. modified polyolefin resin (D) contg. a group reactive with an epoxy group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is excellent in impact resistance, heat distortion resistance, chemical resistance, and moldability, has no delamination when molded, and has a matte appearance. The present invention relates to a thermoplastic resin composition that gives a molded product.

[0002]

2. Description of the Related Art ABS resins and polycarbonate resins are thermoplastic resins having excellent heat resistance, impact resistance and moldability, and are used in machines, automobiles, home appliances, OA equipment, electric parts, electronic parts, etc. Widely used. 2. Description of the Related Art In recent years, in fields such as automobile inner layer parts and light electric parts, there is an increasing demand for parts whose surface gloss is suppressed in order to maintain a calm feeling, a sense of quality, and safety by suppressing light reflection. As a method of suppressing the surface gloss and obtaining a part having a matte appearance, mold surface treatment and matte coating are used. However, the surface treatment of the mold requires repair and management of the mold, and the matte coating has a problem that a separate step of applying the coating after obtaining the parts is required.

In Japanese Patent Publication No. 23661/1992, a resin compound containing an ABS resin obtained by copolymerizing a glycidyl ester of α, β-unsaturated acid with a rubber-like polymer and a polycarbonate resin is used. A method of solving the problem is disclosed. The resin obtained using this method is highly matte and can impart a matte appearance to parts molded from this resin composition.

However, the resin composition containing the ABS resin and the polycarbonate resin has insufficient chemical resistance when used without coating. In order to improve chemical resistance, many methods of blending a resin composition containing an ABS resin and a polycarbonate resin with a crystalline resin such as polyolefin and polyester have been studied. The mattness of the molded product obtained is not very good. As described above, a resin composition excellent in both chemical resistance and matting property has not yet been obtained.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned conventional problems, and its objects are impact resistance, heat distortion resistance, chemical resistance, and molding process. It is an object of the present invention to provide a thermoplastic resin composition which has excellent properties, does not cause delamination when molded, and gives a molded product having a matte appearance.

[0006]

The present inventors have made diligent efforts to solve the above-mentioned conventional problems, and as a result, the graft copolymer (A) containing a specific component and the vinyl copolymer (B). The present invention has been completed by finding that the above object can be achieved by blending a specific modified polyolefin resin (D) with a resin containing a) and a polycarbonate resin (C).

The thermoplastic resin composition of the present invention comprises the following graft copolymer (A) 3 to 40 parts by weight, vinyl copolymer (B) 8 to 70 parts by weight, and polycarbonate resin (C) 5 To 85 parts by weight of the resin mixture and 0.5 to 50 parts by weight of the modified polyolefin resin (D), whereby the above object can be achieved: (A) Epoxy group-containing vinyl Compound (a.1.1)
5 to 60 parts by weight of a vinyl compound group (a.1) consisting of 0.1 to 40% by weight and 99.9 to 60% by weight of a vinyl compound (a.1.2) copolymerizable with a rubber-like polymer. , A graft copolymer obtained by graft-polymerizing 95 to 40 parts by weight of a rubber-like polymer (a.2), (B) an aromatic vinyl compound, a vinyl cyanide compound, an acrylic acid alkyl ester compound or a methacrylic acid alkyl ester compound. ,
And a vinyl-based copolymer obtained by polymerizing at least two vinyl-based monomers selected from the group of copolymerizable vinyl-based compounds (b) consisting of N-substituted maleimide compounds, (C) a polycarbonate-based resin, and (D) A modified polyolefin resin containing a group reactive with an epoxy group.

In a preferred embodiment, the vinyl compound (a.1.2) copolymerizable with the rubber-like polymer is
At least one selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, acrylic acid alkyl ester compounds and methacrylic acid alkyl ester compounds.
It is a vinyl monomer of a kind.

In a preferred embodiment, the vinyl compound having an epoxy group (a.1.1) is α, β-
Glycidyl ester compound of unsaturated acid, and general formula
(I)

[0010]

Embedded image

It is at least one compound having a glycidyl group represented by: wherein Ar is an aromatic hydrocarbon group having 6 to 23 carbon atoms and having at least one glycidyloxy group, and R is hydrogen. It is an atom or a methyl group.

In a preferred embodiment, the vinyl copolymer (B) comprises an aromatic vinyl compound of 40 to 90% by weight, a vinyl cyanide compound of 40% by weight or less, an acrylic acid alkyl ester compound or a methacrylic acid alkyl ester compound. 40% by weight or less and 40% by weight or less of N-substituted maleimide compound.

In a preferred embodiment, the modified polyolefin resin (D) is a carboxylic acid anhydride residue,
And having at least one of the carboxyl groups.

The present invention will be described in detail below.

The graft copolymer (A) used in the present invention comprises 5 to 60 parts by weight of the vinyl compound group (a.1),
Preferably 10 to 55 parts by weight, more preferably 1
5 to 55 parts by weight of rubbery polymer (a.2) 95 to 40
It is obtained by graft polymerization in an amount of 90 parts by weight, preferably 90 to 45 parts by weight, and more preferably 85 to 45 parts by weight. When the vinyl compound group (a.1) is more than 60 parts by weight and the rubbery polymer (a.2) is less than 40 parts by weight, the impact resistance of the obtained resin composition is lowered and the vinyl compound group (a. 1) is less than 5 parts by weight, and the rubber-like polymer (a.
When 2) exceeds 95 parts by weight, the moldability of the obtained resin composition is deteriorated.

The above-mentioned vinyl compound group (a.1) includes an epoxy group-containing vinyl compound (a.1.1) 0.1 to 40.
% By weight, preferably 0.5 to 35% by weight, more preferably 1 to 35% by weight, and a vinyl compound (a.1.2) 99.9 to 60 which is copolymerizable with the rubbery copolymer. %, Preferably 99.5 to 65% by weight, more preferably 99 to 65% by weight. In the vinyl compound group (a.1), the amount of the vinyl compound (a.1.1) having an epoxy group is less than 0.1% by weight, and the vinyl compound (a If the amount of 1.1.2) exceeds 99.9% by weight, the matting property of the molded product using the obtained composition is insufficient, and the resulting molded product peels off. When the amount of the vinyl compound (a.1.1) having an epoxy group exceeds 40% by weight and the amount of the vinyl compound (a.1.2) copolymerizable with the rubber-like polymer falls below 60% by weight, Molding processability and impact resistance decrease,
Furthermore, the epoxy group reacts during the polymerization with the rubber-like polymer (a.2) to make stable polymerization difficult, which is not preferable.

Among the vinyl compound group (a.1), as the vinyl compound (a.1.1) having an epoxy group, a glycidyl ester compound of α, β-unsaturated acid and the following general formula ( I)

[0018]

Embedded image

At least one of the compounds having a glycidyl group represented by: is preferred. Here, Ar is a C6 to C23 aromatic hydrocarbon group having at least one glycidyloxy group, and R is a hydrogen atom or a methyl group.

As the glycidyl ester compound of α, β-unsaturated acid, glycidyl acrylate and glycidyl methacrylate can be used.

The compound having a glycidyl group represented by the above general formula (I) is preferably a compound having at least one acrylamide group and at least one glycidyl group in the molecule. Here, the acrylamide group includes an acrylamide group and a methacrylamide group.

The compound represented by the above general formula (I) can be prepared, for example, by the method described in JP-A-60-130580. According to this method, an aromatic hydrocarbon having at least one phenolic hydroxyl group is condensed with N-methylol acrylamide or N-methylol methacrylamide in the presence of an acidic catalyst. Then, the compound represented by the general formula (I) is obtained by glycidylating the hydroxyl group with epihalohydrin.

As the above-mentioned aromatic hydrocarbon having at least one phenolic hydroxyl group, a C6 to C23 phenol compound can be used. Examples of such a phenol compound include phenol, cresol, xylenol, carvacrol, thymol, naphthol, resorcin, hydroquinone, pyrogallol, and phenanthrol. Particularly, a monohydric phenol having an alkyl substituent is preferable.

According to the above method, for example, when 2,6-xylenol and N-methylolacrylamide are used as starting materials, the following structural formula (II)

[0025]

[Chemical 4]

The compound of formula is obtained.

Alternatively, using orthocresol and N-methylolacrylamide as starting materials, the following structural formula (III)

[0028]

Embedded image

A compound represented by:

The vinyl compound (a.1.1) having an epoxy group may be used alone or in combination of two or more kinds.

The vinyl compound (a.1.2) copolymerizable with the rubbery polymer is selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, acrylic acid alkyl ester compounds or methacrylic acid alkyl ester compounds. At least one vinyl-based monomer is preferred. Monomers other than these may cause problems such as a reduction in the balance of impact resistance and molding processability, coloring of the resin, and difficulty in polymerization. Preferably,
The vinyl compound group (a.1) contains an aromatic vinyl compound in a proportion of 90% by weight or less as the vinyl compound (a.1.2) copolymerizable with the rubber-like polymer.

Among the vinyl compounds (a.1.2) copolymerizable with the rubber-like polymer, examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene and p-methylstyrene. , Chlorostyrene, etc. may be used. Of these, α-methylstyrene and styrene are preferable. As the vinyl cyanide compound, for example, acrylonitrile, methacrylonitrile, etc. can be used. As the acrylic acid alkyl ester compound or the methacrylic acid alkyl ester compound, for example,
Methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate and the like can be used. Furthermore, if necessary, another vinyl compound, such as N-phenylmaleimide, which is copolymerizable with the rubber-like polymer, can be copolymerized.

The rubber-like copolymer (a.2) is
For example, polybutadiene, styrene-butadiene copolymer (SBR), acrylonitrile-butadiene copolymer (NBR), butyl acrylate-butadiene copolymer, styrene-butadiene-styrene copolymer (SB
Diene rubbers such as S); acrylic rubbers such as polybutyl acrylate; polyolefin rubbers such as ethylene-propylene-non-conjugated diene copolymer (EPDM) may be used. These may be used alone or in combination of two or more.

The graft polymer (A) comprises the vinyl compound group (a.1) and the rubber-like polymer (a.2),
It can be prepared by graft polymerization using any method. For example, emulsion polymerization, suspension polymerization, bulk polymerization, emulsion-
Bulk polymerization, emulsion-suspension polymerization, bulk-suspension polymerization and the like can be used. If desired, two or more graft copolymers prepared using different methods can be used for preparing the thermoplastic resin composition of the present invention.

The vinyl copolymer (B) used in the present invention is a copolymer composed of an aromatic vinyl compound, a vinyl cyanide compound, an acrylic acid alkyl ester compound or a methacrylic acid alkyl ester compound, and an N-substituted maleimide compound. It is formed by polymerizing two or more vinyl-based monomers selected from the group of possible vinyl compounds (b). As the copolymerizable vinyl compound (b), a polymerizable vinyl compound other than the above may be used.

The composition of the vinyl-based copolymer (B) is such that the aromatic vinyl compound is 45 to 80% by weight, preferably 40.
-80% by weight, more preferably 45-80% by weight,
40% by weight or less of vinyl cyanide compound, preferably 3
5 wt% or less, more preferably 30 wt% or less, acrylic acid alkyl ester compound or methacrylic acid alkyl ester compound 40 wt% or less, preferably 3
It is 5% by weight or less, more preferably 30% by weight or less, and the N-substituted maleimide compound is 40% by weight or less, preferably 35% by weight or less, more preferably 30% by weight or less. If the amount of the aromatic vinyl compound is less than 40% by weight, the molding processability will be lowered, and if it exceeds 90% by weight, the impact resistance will be lowered. If the amount of the vinyl cyanide compound exceeds 40% by weight, the resin will be colored during molding. If the amount of the acrylic acid alkyl ester compound or the methacrylic acid alkyl ester compound exceeds 40% by weight, the impact resistance decreases.
If the N-substituted maleimide compound exceeds 40% by weight, impact resistance and molding processability deteriorate.

Examples of the method for preparing the vinyl copolymer (B) include emulsion polymerization, suspension polymerization, bulk polymerization, emulsion-bulk polymerization, emulsion-suspension polymerization, and bulk-suspension polymerization. To be If desired, two or more copolymers prepared using different methods can be used for preparing the thermoplastic resin composition of the present invention.

The intrinsic viscosity of each of the graft copolymer (A) and the vinyl copolymer (B) is not particularly limited. However, in order to develop desired impact resistance, chemical resistance, rigidity, moldability and the like in the finally obtained thermoplastic resin, the above graft copolymer (A) is used.
The methyl ethyl ketone-soluble component of the mixture of the vinyl copolymer (B) and the vinyl copolymer (B) has an intrinsic viscosity in the range of 0.2 to 1.5 dl / g (N, N′-dimethylformamide solution, 30 ° C.).
It is preferable to have More preferably, this intrinsic viscosity is in the range of 0.25 to 1.2 dl / g. 0.2
If it is less than dl / g or exceeds 1.5 dl / g, impact resistance, chemical resistance, rigidity, moldability and the like are deteriorated.

The polycarbonate resin (C) used in the present invention is a thermoplastic aromatic polycarbonate,
Preferred is an aromatic polycarbonate prepared by reacting a dihydric phenol compound with phosgene or a carbonic acid diester.

The dihydric phenol compound is preferably bisphenol. More preferably, 2,
2-bis (4-hydroxyphenyl) propane, bisphenol A, and bisphenol A partially substituted with other functional groups. A fixed amount or total amount of these bisphenol A can be replaced with another dihydric phenol compound. Furthermore, divalent phenol compounds other than bisphenol A, such as hydroquinone, 4,4-dihydroxydiphenyl, bis (4-hydroxyphenyl)
Compounds such as cycloalkanes, bis (4-hydroxyphenyl) sulfides, bis (4-hydroxyphenyl) sulfones, and bis (4-hydroxyphenyl) ketones can be used.

As the polycarbonate resin (C), a homopolymer of one dihydric phenol compound selected from the group of the dihydric phenols, a copolymer of two or more dihydric phenol compounds, or a copolymer thereof. Mixtures of can also be used. Furthermore, in order to improve flame retardancy, a polycarbonate resin copolymerized with a phosphorus compound or a polycarbonate resin end-capped with a phosphorus compound can be used. Polymers copolymerized with dihydric phenols having benzotriazole groups can be used to increase weather resistance.

The viscosity average molecular weight of the above polycarbonate resin is 10,000 to 60,000, preferably 120.
00-55000, and more preferably 1500
It is 0 to 50,000. If the average molecular weight is less than 10,000, the impact resistance will decrease, and if it exceeds 60,000, the moldability will decrease. If necessary, two or more kinds of polycarbonate resins having different viscosity average molecular weight distributions may be used.

The modified polyolefin resin (D) used in the present invention contains a group having reactivity with an epoxy group.

The modified polyolefin resin (D) is
(i) Copolymerization of a monomer having a group having reactivity with an epoxy group, and an olefin monomer capable of constituting an olefin resin, (ii) a monomer or macromer having a group having reactivity with the epoxy group, Block polymerization or graft polymerization with an olefin resin, and (ii
i) It can be prepared by modifying the olefin resin with a compound having a group reactive with the epoxy group (for example, oxidizing the olefin resin with a peroxide or the like). Other methods may also be used if desired.

The group having reactivity with the epoxy group includes
Epoxy groups, primary-, secondary-, tertiary amino groups, amide groups, carboxyl groups, acid anhydride groups, hydroxyl groups and the like can be mentioned. An epoxy group, a carboxyl group, an acid anhydride group, and a hydroxyl group are preferable because they do not accelerate the decomposition of the polycarbonate resin. Considering the reactivity of the modified polyolefin resin obtained and the physical property balance of the thermoplastic resin composition finally obtained, a carboxyl group and an acid anhydride group are particularly preferable.
These groups may be used alone or in combination of two or more.

Examples of the monomer having a group reactive with the epoxy group include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, dimethylaminoethyl methacrylate, vinyl pyridine, t-butylaminoethyl methacrylate, acrylamide, methacrylamide, Maleimide, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, allyl alcohol, 2-hydroxyethyl methacrylate,
2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate and the like may be mentioned. Particularly preferred is a monomer having a carboxyl group or an acid anhydride group.

The amount of the group reactive with the epoxy group contained in the modified polyolefin resin (D) is 0 as the total amount of the monomers capable of forming the resin (D) as the amount of the monomer having these groups. 0.01 to 40% by weight, preferably 0.05 to 30% by weight, more preferably 0.1 to 40% by weight.
It is 1 to 20% by weight. When the amount of the monomer is less than 0.01% by weight, the molded product obtained by using the obtained thermoplastic resin composition is likely to peel off, and when it exceeds 40% by weight, the chemical resistance is deteriorated.

In the method (i), a modified polyolefin resin (D) is obtained by copolymerizing these olefinic monomers with the epoxy group-containing monomer.

Among the raw materials for the modified polyolefin resin (D), the olefinic monomers used in the above method (i) include ethylene, propylene, 1-butene,
1-pentene, isobutene, butadiene, isoprene,
Chloroprene, phenylpropadiene, cyclopentadiene, 1,5-norbornadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, 1,3-cyclooctadiene, and α, ω- Examples include non-conjugated dienes. (ii) and (iii)
Examples of the olefin resin used in the above method include homopolymers or copolymers of the above olefin monomers. Mixtures of at least two of these may also be utilized. Preferably, polypropylene or a copolymer of propylene and at least one other monomer, low density polyethylene, medium density polyethylene, high density polyethylene, or a copolymer of ethylene and at least one other monomer. is there. These olefin resins can be prepared by any known polymerization method.

In the method (ii), the olefin resin and the monomer or macromer having reactivity with the epoxy group are subjected to block polymerization or graft polymerization to form a modified polyolefin resin (D). .

In the method (iii), these olefin resins are modified by means such as oxidation to form the modified polyolefin resin (D).

The molecular weight of the modified polyolefin resin (D) can be in a wide range and is not particularly limited.

The thermoplastic resin composition of the present invention contains 3 to 40 parts by weight of the graft copolymer (A), 8 to 70 parts by weight of the vinyl copolymer (B), and 5 to 5 parts of the polycarbonate resin (C). It contains 100 parts by weight of a resin mixture consisting of 85 parts by weight and 0.5 to 50 parts by weight of the modified polyolefin resin (D). Preferably, the graft copolymer (A)
100 parts by weight of a resin mixture consisting of 3 to 40 parts by weight, 10 to 70 parts by weight of the vinyl copolymer (B), and 10 to 80 parts by weight of the polycarbonate resin (C), and the modified polyolefin resin (D) 1 to And 45 parts by weight. More preferably, 100 parts by weight of a resin mixture consisting of 5 to 35 parts by weight of the graft copolymer (A), 15 to 65 parts by weight of the vinyl copolymer (B) and 15 to 75 parts by weight of the polycarbonate resin (C). In contrast, modified polyolefin resin (D)
2 to 40 parts by weight. Graft copolymer (A)
If it is less than 3 parts by weight, the matting property, impact resistance and chemical resistance are poor, and if it exceeds 40 parts by weight, the heat distortion resistance and molding processability are poor. If the vinyl copolymer (B) is less than 8 parts by weight, the moldability and heat distortion resistance will be poor, and if it exceeds 70 parts by weight, the impact resistance and the matting property will be poor. If the amount of the polycarbonate resin (C) is less than 5 parts by weight, impact resistance and heat distortion resistance will be poor, and if it exceeds 90 parts by weight, matteness and molding processability will be poor. If the modified polyolefin resin (D) is less than 0.5 parts by weight, moldability, matteness and chemical resistance are poor, and if it exceeds 50 parts by weight,
Inferior in impact resistance and heat distortion resistance.

In addition to the above resins (A) to (D),
One or two or more optional thermoplastic resins may be contained in the composition as long as the object of the present invention is not impaired. Furthermore, if necessary, an antioxidant, a heat stabilizer, a lubricant, a plasticizer, a flame retardant, a flame retardant aid, an ultraviolet absorber, a pigment,
One or more known additives such as antistatic agents, nucleating agents, dispersants, and compatibilizers may be included. Further, as a filler, organic or inorganic fillers and reinforcing agents such as glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica and the like may be contained.

The resin composition of the present invention can be molded into various molded products. For example, the above components (A) to (D), and optionally other additives and fillers may be mixed by an arbitrary method and melted to form an arbitrary molded body. For example, mixing with a Henschel mixer, melt kneading using a single-screw extruder, a twin-screw extruder, a kneader, etc., injection molding, blow molding, extrusion molding, sheet molding, roll molding, press molding, lamination molding, etc. Can be molded by a molding method generally used for thermoplastic resins.

[0056]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. In the present specification, "parts" means "parts by weight" and "%" means "% by weight" unless otherwise specified. The following abbreviations respectively indicate the following compounds: ST = styrene; αST = α-methylstyrene; A
N = acrylonitrile; MMA = methyl methacrylate; PMI = N-phenylmaleimide; PBD = polybutadiene rubber; PBA = polybutyl acrylate rubber;
EPR = ethylene propylene rubber; GMA = glycidyl methacrylate; AXE = a compound represented by the following structural formula (II).

[0057]

[Chemical 6]

The evaluation items of the examples of the present invention are as follows.

Impact resistance Using the test evaluation samples (ASTM No. 1 dumbbell type having a thickness of 3 mm) obtained in the following Examples and Comparative Examples, A
Evaluated by the IZOD test at 1/8 "notch and 23 ° C according to STM D-256.

Heat Deformation Resistance Using the test evaluation samples (ASTM No. 1 dumbbell shape having a thickness of 3 mm) obtained in the following Examples and Comparative Examples, A
According to STM D-648, the heat distortion temperature (HDT) under a load of 18.6 kg / cm ² was measured.

Moldability Using the uncolored pellets obtained in the following Examples and Comparative Examples, a mosquito coiled spiral mold having a flow groove having a depth of 3 mm and a width of 10 mm, and an injection molding machine,
Set temperature of cylinder and nozzle at the tip of molding machine 250
° C., mold temperature 40 ° C., and subjected to molding in an injection molding machine maximum injection pressure 1000 kg / cm ^2, and was measured flow length of the resulting molded product.

Matting property Using the uncolored pellets obtained in the following Examples and Comparative Examples, a plate-shaped molded body having a mirror surface of 80 mm × 40 mm × 3 mm was molded. The 60-degree reflectance was measured at a predetermined position in the central portion of the surface of the maximum area portion of this plate-shaped body.

Chemical resistance A chemical resistance test having an arcuate surface was prepared as follows by using the test evaluation samples (ASTM No. 1 dumbbell shape having a thickness of 3 mm) obtained in the following Examples and Comparative Examples. It was placed along the jig for use and fixed at both ends. This jig is
As shown in FIG. 1, a strip-shaped plate having a thickness of 3 mm and a length of 180 mm was used, the distance L ₁ between the end portions a and a ′ of the arc jig was 176 mm, and the end portion b of the back surface was b. , B '
The strain is 1% by curving so that the distance L ₃ between the midpoint of the line segment L ₂ connecting the _two and the midpoint M in the longitudinal direction of the back surface of the arcuate jig is 18 mm. The fragrance of automobile air freshener New Honey Kiss Lime (manufactured by SOFT99 Corporation) was sufficiently applied to the entire surface of the test evaluation sample, and the temperature was kept at 23 ° C. until the cracks were generated on the surface of the test piece. It was measured. O in Table 4 indicates that cracking does not occur even after 1 week from application.

Peelability 1 m was obtained by making a notch with a cutter knife at the surface end of the test evaluation sample (ASTM No. 1 dumbbell shape with a thickness of 3 mm) obtained in the following Examples and Comparative Examples.
a checkerboard-like grid of m ² was made 100. Using this, a tape peeling test was performed according to JIS-K5400, and the number of masses remaining without peeling out of 100 pieces was evaluated.

Reference Example 1 Preparation of Graft Copolymer (A1) In a reaction vessel equipped with a stirrer and a cooler, in a nitrogen stream,
Water, sodium formaldehyde sulfoxylate, ferrous sulfate, disodium ethylenediaminetetraacetate, and latex of rubber-like polymer were added at the ratios shown in Table 1 (units are parts), and the mixture was stirred until the temperature reached 60 ° C. Heated.
Next, the vinyl compound group and cumene hydroperoxide mixed in the types and ratios of the monomers shown in Table 1 were continuously added dropwise over 3.5 hours. After the dropwise addition was completed, the mixture was further stirred at 60 ° C. for 1 hour to complete the polymerization, and a latex of the graft copolymer (A1) was obtained.

Reference Example 2 Graft copolymer (A2-A
Preparation of 9 and A ′) A latex of a graft copolymer (A2 to A9 and A ′) was obtained in the same manner as in Reference Example 1 except that the rubber polymer and the monomers were changed to the types and ratios shown in Table 1. It was However, (A ') is a graft polymer not containing the vinyl compound (a.1.1) having an epoxy group.

Reference Example 3 Preparation of Vinyl Copolymer (B1) In a reaction vessel equipped with a stirrer and a cooler, in a nitrogen stream,
Water, sodium formaldehyde sulfoxylate, ferrous sulfate, disodium ethylenediaminetetraacetate, and sodium dioctylsulfosuccinate were added at the ratios (units are parts) shown in Table 2 and heated to 65 ° C. with stirring. . Then, the monomer mixture having the types and ratios of the monomers shown in Table 2 was continuously added dropwise over 6.5 hours. After the dropping was completed, the mixture was further stirred at 65 ° C. for 1 hour to terminate the polymerization, and a latex of vinyl copolymer (B1) was obtained.

Reference Example 4 Vinyl Copolymer (B2-B
Preparation of 6) Vinyl-based copolymers (B2-B) were prepared in the same manner as in Reference Example 3 except that the types and proportions of the monomers shown in Table 2 were used.
A latex of 6) was obtained.

Reference Example 5 Preparation of Blend of Graft Copolymer (A1) and Vinyl Copolymer (B1) Graft copolymer (A1) obtained in Reference Example 1 and Reference Example 2 The latex of the obtained copolymer (B1)
The mixture was mixed at a ratio shown in Table 3 and homogenized so that the total number of parts was 30, 50, and 80, and after adding a phenolic antioxidant, coagulation was performed with calcium chloride. The obtained coagulated product was washed with water, dehydrated and further dried to obtain a blended product of the graft copolymer (A1) and the copolymer (B1). Among the obtained blends, a blend having a total weight of 50 was used in Examples 1 to 6 below, and a blend having a total weight of 30 was used in Example 7 below, and a blend having a total weight of 80 was used. Was used in Example 8 below.

Reference Example 6 Graft copolymer (A1 to A)
9 and A ′) and preparation of a blend containing one kind of each of the copolymers (B1 to B6). Reference example 5 except that the kinds and proportions of the graft copolymer and the copolymer are shown in Table 3. In the same manner as above, various total parts by weight of blends were obtained, each consisting of one kind of the graft copolymer (A1 to A9 and A ′) and one kind of the copolymer (B1 to B6) obtained in Reference Example 2. The resulting blend was used in Examples 9-21 below.

Reference Example 7 Preparation of Modified Polyolefin Resin (D) Polypro Highball J-60 as polypropylene resin
0 (manufactured by Mitsui Petrochemical Co., Ltd.), 3 parts maleic anhydride, and Perhexin 2-5B as peroxide.
0.5 part (made by Nippon Oil & Fats Co., Ltd.) was used. These components were melt-kneaded at 220 ° C. using a TEX44 twin-screw vent extruder manufactured by Japan Steel Works, Ltd. to obtain pellet-shaped maleic anhydride-modified polypropylene resin (D1). When the neutralization titration method was used, the content of maleic anhydride in the obtained resin was 2.4%.

Instead of polypropylene resin, ethylene-propylene resin EP-02P (Japan Synthetic Rubber Co., Ltd.)
Manufactured in the same manner as in Reference Example 4, except that an ethylene-propylene resin (D2) modified with maleic anhydride was obtained. Using a neutralization titration method, the maleic anhydride content of this resin was 2.3%.

Furthermore, the modified polyolefin resin (D
As 3), Hoechst wax PED522 (manufactured by Hoechst Japan Ltd.) which is an oxidized polyethylene wax was used. The acid value of this wax is 22-28 mgKOH
/ G.

Reference Example 8 Aromatic Polycarbonate Resin (C) As the aromatic polycarbonate resin (C1), Tufflon FN2500A (manufactured by Idemitsu Petrochemical Co., Ltd.), which is a polycarbonate resin, was used. The viscosity average molecular weight of this polycarbonate resin was about 23,500.

As the aromatic polycarbonate resin (C2), Tufflon FN30, which is a polycarbonate resin, is used.
00A (manufactured by Idemitsu Petrochemical Co., Ltd.) was used. The viscosity average molecular weight of this resin was about 29000.

Example 1 The composition shown in Table 3 was used, and Reference Example 5 was used.
The graft copolymer (A1) and the copolymer (B
1) blended with the above polycarbonate resin (C
1) and the modified polyolefin resin (D1) obtained in Reference Example 7 were placed in a mixing container, and a hindered phenol antioxidant and a phosphite stabilizer were added in an amount of 0.
After adding 5 parts, the mixture was thoroughly stirred and mixed using a super mixer. Then, the obtained mixture was heated at 260 ° C. using a TEX44 twin-screw vented extruder manufactured by Japan Steel Works, Ltd.
By melt-kneading with, a thermoplastic resin composition of the present invention in pellet form was obtained. The obtained resin composition was dried at 110 ° C. for 5 hours using a hot air drier, and then used in each test at a cylinder temperature of 260 ° C. using a J150E-P injection molding machine manufactured by Japan Steel Works, Ltd. A sample for use was obtained. This sample was subjected to the above tests. The results are shown in Table 3.

(Examples 2 to 21) Blends of various graft copolymers (A) and vinyl copolymers (B) obtained in Reference Examples 5 and 6 and the above polycarbonate resin (C1). ) And (C2) and the modified polyolefin resins (D1) and (D1) obtained in Reference Example 7.
2) and any of (D3) were blended in the proportions shown in Table 3, and pellets were obtained in the same manner as in Example 1. Molded in the same manner as in Example 1 using this,
The test was conducted. Table 3 shows the results.

(Comparative Examples 1 to 10) The composition shown in Table 4 was used, and either the graft copolymer (A1) obtained in Reference Example 1 or the graft copolymer (A ') obtained in Reference Example 2 was used. Table 4 shows the copolymer (B1) obtained in Reference Example 3, the polycarbonate resin (C1), and any of the modified polyolefin resin (D1) obtained in Reference Example 7.
Blended in the proportion shown in, and using the same method as in Example 1,
Pellets were obtained. However, in Comparative Example 4, (D
Polypro Highball J-600 (manufactured by Mitsui Petrochemical Co., Ltd.), which is a polypropylene resin, was used instead of 1) (shown as D'in Table 4). The pellets thus obtained were molded in the same manner as in Example 1 and tested. The results are shown in Table 4.

[0079]

[Table 1]

[0080]

[Table 2]

[0081]

[Table 3]

[0082]

[Table 4]

As shown in Tables 3 and 4, Examples 1 to 1
It can be seen that No. 21 is excellent in impact resistance, heat distortion resistance, molding processability, matting property, and chemical resistance, and is hard to peel off.

From the comparison between Examples 1 to 3 and Comparative Example 1; the comparison between Example 7 and Comparative Example 2; and the comparison between Example 8 and Comparative Example 3, the book containing the modified polyolefin resin (D) was obtained. It can be seen that the thermoplastic resin composition of the invention is excellent in moldability, matteness and chemical resistance.

In Example 2 and Comparative Example 4,
The mixing ratios of the components (A) to (D) are the same, but (D)
In the thermoplastic resin composition of the present invention obtained in Example 2 using the modified polyolefin resin as a component, peeling did not occur in the obtained molded product. On the other hand, in the resin of Comparative Example 4 using the unmodified polyolefin resin as the component (D), peeling occurred in the obtained molded product.

Since the resin composition of Comparative Example 5 does not contain the polycarbonate resin (C), it is inferior in impact resistance and thermal deformation resistance.

The resin composition of Comparative Example 6 did not contain the graft copolymer (A) and the vinyl copolymer (B), and therefore was inferior in moldability and matteness, and
Peeling occurred in the obtained molded product.

Since the resin composition of Comparative Example 7 does not contain the vinyl copolymer (B), it is inferior in heat distortion resistance and moldability.

Since the resin composition of Comparative Example 8 did not contain the graft copolymer (A), it was inferior in impact resistance and matting property, and peeling occurred in the obtained molded article.

In the resin composition of Comparative Example 9, the content of the graft copolymer (A) is out of the range of the present invention, and therefore the heat distortion resistance and the moldability are poor.

In the resin composition of Comparative Example 10, since the graft copolymer (A ') does not contain the vinyl compound (a.1.1) having an epoxy group, it is inferior in impact resistance and matting property, and The resulting molded product was peeled off.

From the above results, the thermoplastic resin composition of the present invention is excellent in impact resistance, heat distortion resistance, chemical resistance, and moldability, and does not cause delamination when molded. It was found that a molded product having high mattness was obtained.

[0093]

The resin composition obtained by the present invention is
Since it has excellent impact resistance, heat distortion resistance, chemical resistance, and moldability, it does not cause delamination when molded, and gives a molded body with a matte appearance Useful for.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a chemical resistance test jig.

[Explanation of symbols]

a a front end of the arc jig a'a front end of the arc jig b a back end of the arc jig b'a back end of the arc jig M a back surface of the arc jig Midpoint in the longitudinal direction L ₁ Distance between the ends a and a ′ on the front surface of the arcuate jig L ₂ Line segment connecting the ends b and b ′ on the back surface of the arcuate jig L ₃ L _{2 and} the midpoint Distance from M

Front page continuation (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C08L 33/06 LJE 33/18 LJN LJP 35/00 LJW 51/04 LLB 69/00 LPN

Claims (5)

[Claims] 1. The following graft copolymer (A) 3-40
100 parts by weight of a resin mixture consisting of 8 to 70 parts by weight of vinyl copolymer (B) and 5 to 85 parts by weight of polycarbonate resin (C), and 0.5 to 50 parts of modified polyolefin resin (D). And a thermoplastic resin composition containing: (A) an epoxy group-containing vinyl compound (a.1.1)
5 to 60 parts by weight of a vinyl compound group (a.1) consisting of 0.1 to 40% by weight and 99.9 to 60% by weight of a vinyl compound (a.1.2) copolymerizable with a rubber-like polymer. , A graft copolymer obtained by graft-polymerizing 95 to 40 parts by weight of a rubber-like polymer (a.2), (B) an aromatic vinyl compound, a vinyl cyanide compound, an acrylic acid alkyl ester compound or a methacrylic acid alkyl ester compound. ,
And a vinyl-based copolymer obtained by polymerizing at least two vinyl-based monomers selected from the group of copolymerizable vinyl-based compounds (b) consisting of N-substituted maleimide compounds, (C) a polycarbonate-based resin, and (D) A modified polyolefin resin containing a group reactive with an epoxy group. 2. A group in which the vinyl compound (a.1.2) copolymerizable with the rubber-like polymer comprises an aromatic vinyl compound, a vinyl cyanide compound, an acrylic acid alkyl ester compound and a methacrylic acid alkyl ester compound. The thermoplastic resin composition according to claim 1, which is at least one vinyl-based monomer selected from the group consisting of: 3. The vinyl compound (a.1.1) having an epoxy group is a glycidyl ester compound of an α, β-unsaturated acid and a compound represented by the general formula (I): Is at least one compound having a glycidyl group represented by, wherein Ar is an aromatic hydrocarbon group having 6 to 23 carbon atoms and having at least one glycidyloxy group, and R is a hydrogen atom or methyl. It is a group, Claim 1
Alternatively, the thermoplastic resin composition according to claim 2. 4. The vinyl copolymer (B) comprises 40 to 90% by weight of an aromatic vinyl compound, 40% by weight or less of a vinyl cyanide compound, 40% by weight or less of an acrylic acid alkyl ester compound or a methacrylic acid alkyl ester compound. And a thermoplastic resin composition according to any one of claims 1 to 3, which is a copolymer containing 40% by weight or less of an N-substituted maleimide compound. 5. The modified polyolefin resin (D)
The thermoplastic resin composition according to any one of claims 1 to 4, wherein is a modified polyolefin resin having at least one of a carboxylic acid anhydride group and a carboxyl group.