JPS6234074B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to thermoplastic resin compositions. More specifically, the present invention relates to an aromatic polycarbonate resin composition having excellent thermal stability, moldability, thermal discoloration resistance, and impact resistance. 4,4-dihydroxydiphenylalkane-based polycarbonate resin (hereinafter simply referred to as aromatic polycarbonate resin) has excellent mechanical properties, particularly impact strength and thermal properties, but its high melt viscosity makes it difficult to injection mold. It has the disadvantage that it is accompanied by some difficulty in molding and is prone to solvent cracking after molding. Also, in terms of impact strength, there is a drawback that as the thickness of the molded piece is increased, the impact strength is extremely reduced. For example, the impact strength with isotto notches according to the ASTM-256 test method is as high as approximately 90 kg·cm/cm for a 1/8 inch rod, but it is significantly lower at only 15 kg·cm/cm for a 1/4 inch rod. In order to improve these drawbacks, blends of aromatic polycarbonate resins and polybutadiene copolymers have been proposed (for example, in
Publication No. 15225, Special Publication No. 31-71, Special Publication No. 42-
11496 and Japanese Patent Publication No. 48-72249). Such aromatic polycarbonate resin compositions have excellent moldability and especially impact strength, but double bonds of the diene rubber remain in the diene rubber-containing copolymer, which is one component of the composition. As a result, thermal stability is insufficient, and pellets and molded products undergo significant thermal discoloration due to dry heat, and furthermore, physical properties are significantly deteriorated. As a result of intensive research aimed at improving the thermal stability of the above-mentioned thermoplastic resin composition, that is, thermal discoloration and physical property deterioration due to dry heat, the present inventor found that the thermoplastic resin composition has the following specific structure. When formulas (1) and (2) are combined or, if necessary, a compound represented by general formula (3) and/or (4) is added and blended, the thermoplastic resin composition The present invention was completed based on the finding that stability can be significantly improved. That is, the present invention provides the following features: [1] (A) 10 to 95 parts by weight of aromatic polycarbonate resin (B) The copolymer component is one or more of aromatic vinyl component, vinyl cyanide component, and methacrylic acid ester component and diene rubber. (C) 0 to 60 parts by weight of a copolymer consisting of an aromatic vinyl component and a vinyl cyanide component (D) 0 to 60 parts by weight of an aromatic polyester resin A thermoplastic resin composition comprising 0.01 to 10 parts by weight of a compound represented by the following general formulas (1) and (2) per 100 parts by weight of the thermoplastic resin composition. (Here, R ₁ is an alkyl group having 8 or more carbon atoms, R ₂
is H or a methyl group, X is a tris(2-hydroxyethyl)isocyanurate residue, trimethylolethane residue, trimethylolpropane residue, or pentaerythritol residue, and X is tris(2-hydroxyethyl)isocyanurate. residue, trimethylolethane residue, trimethylolpropane residue, l is an integer of 1 to 3,
m represents an integer from 0 to 2, and l+m is 3; when X is a pentaerythritol residue, l represents an integer from 1 to 4, m represents an integer from 0 to 3, and l
+m is 4. ) (Here, Y is H, an alkyl-substituted or unsubstituted hydroxybenzyl group, and at least one is an alkyl-substituted or unsubstituted hydroxybenzyl group.) [2] The following general formula (3) and/or (4) 2. The thermoplastic resin composition according to claim 1, wherein 0.01 to 10 parts by weight of a compound represented by the following formula is added. (Here, M is an alkaline earth metal, zinc, or aluminum, R is an alkyl group having 5 to 30 carbon atoms, and n is an integer representing the valence of M.) Various types of aromatic polycarbonate resins (A) can be used in the present invention, but in particular, 2-2bis(4-hydroxyphenyl)
An aromatic polycarbonate resin obtained by a transesterification method or a phosgene method using propane as a dihydric phenol is preferred. 2.2 more
Part or all of bis(4-hydroxyphenyl)propane may be replaced with other divalent phenols such as 4,4' dihydroxydiphenyl, bis(4-hydroxyphenyl)alkane, bis(4-hydroxyphenyl)cycloalkane, Compounds such as bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) ether, or 2-2bis(3,5-dibromo-4-hydroxyphenyl)
It may be substituted with a halogenated bisphenol such as propane, or two or more aromatic polycarbonate resins may be mixed. Specific examples of the copolymer (B) used in the present invention include ABS resin and MBS resin. Examples of the diene rubber component in the copolymer include polybutadiene, acrylonitrile-butadiene copolymer, and styrene-based rubber component.
Examples include butadiene copolymers. Examples of aromatic vinyl components include styrene, α-
Examples include styrene units such as methylstyrene, dimethylstyrene, vinyltoluene, and alkoxystyrene, and vinylpyridine units, with styrene and α-methylstyrene units being particularly preferred. As vinyl cyanide components, acrylonitrile,
Examples include methacrylonitrile and chloroacrylonitrile units. Examples of the methacrylic acid ester component include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, and butyl methacrylate units. Specific examples of the copolymer (C) used in the present invention include AS resin. Examples of the aromatic vinyl component in the copolymer include styrene units such as styrene, α-methylstyrene, dimethylstyrene, vinyltoluene, and alkoxystyrene, and vinylpyridine units. The vinyl cyanide component is
Examples include acrylonitrile, methacrylonitrile, and chloroacrylonitrile units. The above copolymers (B) and (C) may be produced by any polymerization method such as emulsion polymerization, bulk-suspension polymerization, or emulsion-suspension polymerization, or may be a mixture of these polymerization methods. . The aromatic polyester resin (D) used in the present invention includes polyethylene terephthalate,
Examples include polybutylene terephthalate. All of these are 70 mol% or more, preferably 80 mol%
A copolymer consisting of polyethylene terephthalate or polybutylene terephthalate units,
This also includes blends. In the present invention, the method for preparing the thermoplastic resin composition by blending the resins (A), (B), (C), and (D) may be any method of mixing solid substances, such as a Banbury mixer, a heating roll, etc. , a method using a single-screw or multi-screw extruder, etc. can be applied. In addition, as a blending method for obtaining a thermoplastic resin composition, the above (A), (B), (C) and
A method in which the resin (D) is simultaneously blended and granulated through an extruder is preferred, but there is no particular limitation. In the above preparation method, the mixing ratio of the resins (A), (B), (C) and (D) is 10% for the aromatic polycarbonate resin (A).
-95 parts by weight, preferably 30-90 parts by weight, copolymer (B) 5-90 parts by weight, preferably 10-80 parts by weight,
The copolymer (C) is 0 to 60 parts by weight, preferably 0 to 40 parts by weight.
The amount of aromatic polyester resin (D) is 0 to 60 parts by weight, preferably 0 to 40 parts by weight. In the thermoplastic resin composition of the present invention, the thermoplastic resin is stabilized by adding stabilizers represented by general formulas (1) and (2). The compound represented by general formula (1) is tris(2-
A compound obtained by dehydration condensation of hydroxyethyl) isocyanurate, trimethylolethane, trimethylolpropane, or pentaerythritol and β-alkylthiopropionic acid or α-methyl-β-alkylthiopropionic acid, such as β - ester of 4 moles of (lauryl)propionic acid and 1 mole of pentaerythritol, ester of 3 moles of β-(2-ethylhexylthio)propionic acid and 1 mole of pentaerythritol, 3 moles of β-(dodecylthio)propionic acid and tris( ester with 1 mole of 2-hydroxyethyl)isocyanurate, 2.5 moles of α-methyl-β-(laurylthio)propionic acid with tris(2
ester with 1 mole of -hydroxyethyl)isocyanurate, ester with 3 moles of β-(2-ethylhexio)propionic acid and 1 mole of trimethylolethane, ester with 3 moles of α-methyl-β-(dodecylthio)propionic acid with trimethylolethane. Esters with 1 mol of β-(lauryl)propionic acid 3
Examples include esters of 1 mole of trimethylolpropane and 2.5 moles of α-methyl-β-(stearylthio)propionic acid and 1 mole of trimethylolpropane. Moreover, the compound represented by general formula (2) is, for example, etc. In the thermoplastic resin composition of the present invention, the stabilizers of general formula (3) and/or (4) may be used as the stabilizers of the above (1) and (2).
It is used in combination with a stabilizer for thermal stabilization. M in the compounds represented by general formulas (3) and (4) is an alkaline earth metal, aluminum or zinc, and R
is an alkyl group having 5 to 30 carbon atoms, and n is an integer representing the valence of M. Examples of alkaline earth metals include magnesium, calcium, barium, and strontium. Carbon number 5
~30 alkyl groups include, for example, pentyl, hexyl, heptyl, octyl, noryl, decyl,
Examples include undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, tetracosyl, hexacosyl, and the like. Among these, alkyl having 8 to 18 carbon atoms is preferred. Examples of compounds represented by general formula (3) include:

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[Formula] etc. In addition, examples of compounds represented by general formula (4) include:

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Examples include [Formula]. In the present invention, the amount of the stabilizer represented by general formulas (1) and (2) to be used is based on 100 parts by weight of the thermoplastic resin composition consisting of the above (A), (B), (C) and (D). The amount is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight. Also, the mixing ratio of (1) and (2) is
(1) 95 to 5% by weight, (2) 5 to 95% by weight, preferably (1) 80
(2) 20 to 95% by weight. Furthermore, the amount of the stabilizer represented by general formula (3) and/or (4) is 0.01 to 0.01 to 100 parts by weight of the thermoplastic resin composition.
The amount is 10 parts by weight, preferably 0.05 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight. Further, the mixing ratio of (3) and (4) is arbitrary. The stabilizer used in the present invention may be added at any stage of the preparation of the thermoplastic resin composition, and any method of addition may be employed. When using ingredients (1) and (2) together with ingredients (3) and/or (4), the ratio of ingredients (3) and/or (4) to ingredients (1) and (2) is (1). ) and (2) components are at least 30% by weight, preferably at least 40% by weight. Glass fibers can be added to the thermoplastic resin composition of the present invention. The amount of glass fiber used is 0.1 to 100 parts by weight of the thermoplastic resin composition.
The amount is 100 parts by weight, preferably 1 to 70 parts by weight. Glass fibers can be used either in the form of long fibers or short fibers. Any method can be used to add the glass fibers; for example, short fibers can be simply mixed into the above composition and molded, but generally a single or multi-screw extruder or kneader is used. A method of kneading and pelletizing is used. The thermoplastic resin composition of the present invention can be molded using equipment and conditions used for ordinary resin molding. Further, various additives such as a flame retardant, a mold release agent, and an inorganic filler may be added to the thermoplastic resin composition of the present invention. Examples will be described below, but the present invention is not limited thereto in any way. The middle part of the example shows parts by weight. Thermal stability was evaluated using the following method. That is, dry heat treatment of injection molded pieces (Examples 1 to 12 and Comparative Examples 1 to 4 were carried out in a gear oven aging tester)
(Examples 13 and 14 and Comparative Examples 5 and 6 were left at 130°C for 7 days) Measure the impact strength with 1/8 inch isotto notch according to ASTMD-256 and compare the changes in strength. did. In addition, the hue (Lab) before and after the dry heat treatment was measured using a color difference meter (manufactured by Suga Test Instruments KK), and the whiteness was determined as W (whiteness) = 100−√(100−).
² + a ² + b ² and the changes in whiteness were compared. Examples 1 to 6 and Comparative Examples 1 to 3 Panlite L-1250 (manufactured by Teijin Kasei KK) was used as the aromatic polycarbonate resin (PC resin), and a graft copolymer of methyl methacrylate-butadiene-styrene (MBS resin) was used. is money ace
BB-28 (manufactured by Kanekabuchi Kagaku KK), acrylonitrile-
Sevian V (Daicel KK) is a butadiene-styrene graft copolymer (ABS resin).
), acrylonitrile-styrene copolymer (AS
Tyril 767 (manufactured by Asahi Dow KK) was used as the resin), and the amounts of each resin shown in Table 1 were mixed in a tumbler-type blender, and at the same time, the amounts shown in Table 1 were mixed for 100 parts by weight of this thermoplastic resin composition. After adding the indicated amount and mixing thoroughly, use a 30mmφ extruder.
It was extruded into pellets at 240°C. The pellets were molded into 1/8-inch Izot impact test pieces and hue measurement test pieces using an injection molding machine at 250°C, and evaluated using the thermal stability evaluation method described above. The results are shown in Table 1.

【table】

TABLE Examples 7-12 and Comparative Example 4 Examples 1-6 were repeated using the stabilizers shown in Table 2. The results are shown in Table 2.

[Table] Examples 13 and 14 and Comparative Examples 5 and 6 Aromatic polycarbonate resins (PC resins) include Panlite L-1250J (manufactured by Teijin Kasei KK);
The methyl methacrylate-butadiene-styrene graft copolymer (MBS resin) is Kaneace BB-28 (manufactured by Kanebuchi Kagaku KK), and the acrylonitrile-styrene copolymer (AS resin) is Tyril 767 (manufactured by Asahi Dow KK). , aromatic polyester resin (PET resin) is TR-4500 (Teijin KK
Same as Examples 1 to 6 except that glass chopped strand FES-03-1290H (manufactured by Fuji Fiber Glass KK) was used as the glass fiber (GF), and the stabilizer shown in Table 3 was used. I went to The results are shown in Table 3.

【table】

[Table] As is clear from the results in Tables 1 to 3, the thermoplastic resin composition according to the present invention has excellent thermal stability during dry heat treatment.

Claims (1)

[Scope of Claims] 1 (A) 10 to 95 parts by weight of an aromatic polycarbonate resin (B) The copolymer component is an aromatic vinyl component, a vinyl cyanide component, and a methacrylic acid ester component.
5 to 90 parts by weight (C) of a copolymer consisting of an aromatic vinyl component and a vinyl cyanide component (D) Aromatic For 100 parts by weight of a thermoplastic resin composition consisting of 0 to 60 parts by weight of polyester resin
A thermoplastic resin composition containing 0.01 to 10 parts by weight of compounds represented by the following general formulas (1) and (2). (Here, R ₁ is an alkyl group having 8 or more carbon atoms, R ₂ is H or a methyl group, and X is a tris(2-hydroxyethyl) isocyanurate residue, trimethylolethane residue, trimethylolpropane residue, or penta It represents an erythritol residue, and X is tris(2-
In the case of hydroxyethyl) isocyanurate residue, trimethylolethane residue, and trimethylolpropane residue, l is an integer of 1 to 3, m is an integer of 0 to 2, and l+m is 3, and In the case of an erythritol residue, l is an integer of 1 to 4, m is an integer of 0 to 3, and l+m is 4. ) (Here, Y is H, an alkyl-substituted or unsubstituted hydroxybenzyl group, and at least one is an alkyl-substituted or unsubstituted hydroxybenzyl group.) 2 Represented by the following general formula (3) and/or (4) The thermoplastic resin composition according to claim 1, characterized in that 0.01 to 10 parts by weight of the compound is added. (Here, M is an alkaline earth metal, zinc or aluminum, R is an alkyl group having 5 to 30 carbon atoms, and n is an integer representing the valence of M.)