JPH10158497A - Blow molding resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition suitable for use in blow molding which not only is excellent in blow-moldability and in the strength of a pinch off portion of a molded product, but also has excellent flame retardancy. SOLUTION: This composition comprises 100 pts.wt. composition comprising 30 to 90wt.% polycarbonate resin having a viscosity average molecular weight of 17,000 to 30,000, 5 to 68wt.% graft polymer prepared by graft polymerization of an aromatic vinyl compound and vinyl cyanide in the presence of a diene rubber and 2 to 50wt.% aromatic vinyl compound-vinyl cyanide copolymer having an intrinsic viscosity of 0.6 to 1.5; 3 to 40 pts.wt. halogen-containing flame-retardant and/or phosphorus-containing flame-retardant; and 0.05 to 5 pts.wt. polytetrafluoroethylene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a resin composition suitable for blow molding. More specifically, the present invention relates to a blow molding resin composition having excellent blow moldability, pinch-off strength, and excellent flame retardancy.

[0002]

2. Description of the Related Art The blow molding method has been developed mainly for a polyolefin resin such as polyethylene as a technique for molding a hollow container.
Engineering plastics such as polyphenylene oxide have been applied as large blow-molded products such as equipment, and the use of ABS resins as alternative materials has been attempted. As described above, in recent years, the applications to which blow molding is applied have been increasing more and more, and the performance required for materials for blow molding has been diversified accordingly. In particular, in applications to which such blow molding is applied, a material excellent in not only blow moldability but also flame retardancy and strength of a pinch-off portion (pinch-off strength) has not yet been obtained.

[0003]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and provides a blow molding resin composition which is excellent in blow moldability, pinch-off strength and flame retardancy. The purpose is to do so.

[0004]

According to the present invention, an aromatic vinyl and a vinyl cyanide are used in the presence of 30 to 90% by weight of a polycarbonate resin (A) having a viscosity average molecular weight of 17,000 to 30,000 and a diene rubber. 5 to 68% by weight of a graft polymer (B) obtained by graft polymerization and an intrinsic viscosity of 0.6
Per 100 parts by weight of a composition consisting of 2 to 50% by weight of an aromatic vinyl-vinyl cyanide copolymer (C) of from 1.5 to 1.5 parts by weight of 3 to 40 parts by weight of a halogen-based flame retardant and / or a phosphorus-based flame retardant (D) Parts and 0.05 to 5 parts by weight of polytetrafluoroethylene (E).

The polycarbonate resin (A) used in the present invention is obtained by a phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene, or a transesterification method in which a dihydroxydiaryl compound is reacted with a carbonate such as diphenyl carbonate. The obtained polymer is a typical example of a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane; "bisphenol A".

The dihydroxydiaryl compounds include bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl).
Butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4 -Hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane,
2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,
Bis (hydroxyaryl) alkanes such as 5-dichlorophenyl) propane, bis (hydroxyaryl) such as 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane Cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-
Dihydroxydiaryl ethers such as 3,3'-dimethyldiphenylether, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxy-3,
Dihydroxydiaryl sulfides such as 3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulphoxide, 4,4'-dihydroxy-
Dihydroxydiarylsulfoxides such as 3,3'-dimethyldiphenylsulfoxide; dihydroxydiarylsulfones such as 4,4'-dihydroxydiphenylsulfone; and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone. Can be

These may be used alone or as a mixture of two or more kinds. In addition, piperazine, dipiperidylhydroquinone, resorcin, 4,4'-dihydroxydiphenyl, and the like may be used in combination.

Further, the above dihydroxydiaryl compound and a phenol compound having three or more valences as shown below may be mixed and used. Phloroglucin, 4,6-dimethyl-2,4,6-tri-
(4-hydroxyphenyl) -heptene-2,4,6-
Dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -Ethane and 2,2-bis-
[4,4- (4,4′-dihydroxydiphenyl) -cyclohexyl] -propane and the like. In producing these polycarbonate resins, a molecular weight regulator, a catalyst and the like can be used as needed.

[0009] The viscosity average molecular weight of the polycarbonate resin used is 17,000 to 30,000. If it is less than 17,000, blow moldability and pinch-off strength are poor, and if it exceeds 30,000, blow moldability is poor. Preferably it is 18,000-26,000.

The graft polymer (B) used in the present invention is a graft polymer obtained by graft-polymerizing aromatic vinyl and vinyl cyanide in the presence of a diene rubber.

Examples of the diene rubber include polybutadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR) and the like. The gel content and weight average particle diameter of the diene rubber used are not particularly limited, but the gel content (solvent: toluene) is 50 to 95% by weight and the weight average particle diameter is 0.1 to 0.1%.
It is preferably 1.0 μm.

As the aromatic vinyl, styrene, α-methylstyrene, paramethylstyrene, chlorostyrene,
Bromostyrene and the like can be used, and one kind or two or more kinds can be used. Particularly, styrene and α-methylstyrene are preferred. Examples of vinyl cyanide include acrylonitrile, methacrylonitrile, and the like, and one or more kinds can be used. Acrylonitrile is particularly preferred. Further, in the present invention, a part of the aromatic vinyl can be substituted with another copolymerizable vinyl compound. Such other copolymerizable vinyl compounds include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, unsaturated carboxylic acid such as citraconic anhydride or unsaturated dicarboxylic anhydride, maleimide, methyl maleimide And maleimide compounds such as ethylmaleimide, N-phenylmaleimide, O-chloro-N-phenylmaleimide, and unsaturated carboxylic acid alkyl esters such as methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate. The above can be used. Particularly preferred are maleic anhydride, methyl methacrylate and N-phenylmaleimide.

The composition ratio of the above-mentioned aromatic vinyl (i), vinyl cyanide (ii) and other copolymerizable vinyl compound (iii) is not particularly limited, but (i) 50 to 95% by weight, ii) 5-50% by weight and (iii) 0-45% by weight
(I) 60 to 90% by weight, (i)
Particular preference is given to i) from 10 to 40% by weight and (iii) from 0 to 30% by weight.

The composition ratio of the diene rubber and the total of the compounds (aromatic vinyl, vinyl cyanide and other copolymerizable vinyl compounds) is not limited. Preferably, the content is 10 to 80% by weight and the total amount of the compounds is 90 to 20% by weight.

The above graft polymer (B) can be produced by a known polymerization method, for example, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a solution polymerization method, and a combination thereof.

The aromatic vinyl-vinyl cyanide copolymer (C) used in the present invention is a copolymer obtained by polymerizing aromatic vinyl and vinyl cyanide. The same aromatic vinyl and vinyl cyanide as those described in the section of the graft polymer can be used. Also,
In the present invention, a part of the aromatic vinyl can be replaced with another copolymerizable vinyl compound similar to that described in the section of the graft polymer.

The composition ratio of the aromatic vinyl (i), vinyl cyanide (ii) and other copolymerizable vinyl compound (iii) is not particularly limited, but (i) 50 to 95% by weight, ii) 5-50% by weight and (iii) 0-45% by weight
(I) 60 to 90% by weight, (i)
Particular preference is given to i) from 10 to 40% by weight and (iii) from 0 to 30% by weight.

The intrinsic viscosity (25 ° C., dimethylformamide) of the aromatic vinyl-vinyl cyanide copolymer (C) used must be 0.6 to 1.5. If the intrinsic viscosity is less than 0.6, blow moldability and pinch-off strength are poor, and if it exceeds 1.5, the pinch-off strength is poor, which is not preferable. The preferred intrinsic viscosity of the copolymer (C) is from 0.8 to 1.4.

The above copolymer (B) can be produced by a known polymerization method, for example, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a solution polymerization method, and a combination thereof.

As the halogen-based flame retardant used as the component (D) in the present invention, any one can be used as long as it is stable at the temperature at which the composition of the present invention is processed. In particular, tetrabromobisphenol A and derivatives thereof, tetrabromobisphenol S, polybromodiphenyl ether, brominated polycarbonate oligomers and modified products thereof, brominated epoxy oligomers and modified products thereof,
Preferred are brominated phenoxy resins, brominated polystyrene, brominated phenylene ether, tribromophenoxyethane, brominated triazine compounds, chlorinated condensed alicyclic compounds, and the like.

Examples of the phosphorus-based flame retardant include inorganic phosphorus compounds such as red phosphorus, phosphine, hypophosphorous acid, phosphorous acid, metaphosphoric acid, pyrophosphoric acid, and phosphoric anhydride,
(Wherein R1, R2, R3 and R4 are each independently selected from aryl, alkyl, alkylaryl groups,
Or an optionally halogenated aryl, halogenated alkyl, or halogenated alkylaryl group, X is an arylene group, and k, l, m
And n are each independently 0 or 1, and N is an integer of 0 to 10.) can be used.

[0022]

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Particularly, specific examples of the organic phosphate compound include the following compounds.

[0024]

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[0025]

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[0026]

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The polytetrafluoroethylene (E) used in the present invention is a fluorine-based polymer obtained by polymerizing tetrafluoroethylene as a main component, for example, polyflon (trade name) manufactured by Daikin Chemical Industry Co., Ltd. ,Mitsui·
Commercial products such as Teflon (trade name, manufactured by DuPont Fluorochemicals) and Hostaflon (trade name, manufactured by Hoechst) can be used.

The resin composition according to the present invention comprises 30 to 90% by weight of the polycarbonate resin (A), 5 to 68% by weight of the graft polymer (B) and 2 to 2 parts of the aromatic vinyl-vinyl cyanide copolymer (C). Composition 1 consisting of 50% by weight
Per 100 parts by weight, 3 to 40 parts by weight of a halogen-based flame retardant and / or phosphorus-based flame retardant (D) and 0.05 to 5 parts by weight of polytetrafluoroethylene (E) are blended. If the composition is out of the above range, the desired effects of the present invention cannot be obtained, which is not preferable. In particular, a polycarbonate resin (A) 40 to 80% by weight, a graft polymer (B)
Per 100 parts by weight of a composition comprising 10 to 57% by weight and 3 to 40% by weight of an aromatic vinyl-vinyl cyanide copolymer (C), 5 to 20 halogen-based flame retardants and / or phosphorus-based flame retardants (D) It is preferable to mix 0.1 parts by weight and 0.1 to 3 parts by weight of polytetrafluoroethylene (E).

The resin composition of the present invention comprises the above (A)
(B), (C), (D) and (E) components and, if necessary, various additives such as a lubricant, a dye / pigment, a filler, an antistatic agent, an antioxidant, and an ultraviolet absorber are mixed and melted. It can be obtained by kneading. For mixing and melt-kneading these various components, a ribbon blender, Henschel mixer, Banbury mixer, kneader, single screw extruder, twin screw extruder, or the like can be used.

Hereinafter, the present invention will be described in detail.
It should be noted that the present invention is not limited at all by this.

-Polycarbonate resin (A)-PC-1: a polycarbonate resin comprising phosgene and bisphenol A and having a viscosity average molecular weight of 22,100. PC-i: a polycarbonate resin composed of phosgene and bisphenol A and having a viscosity average molecular weight of 16,800. PC-ii: a polycarbonate resin composed of phosgene and bisphenol A and having a viscosity average molecular weight of 31,000.

-Graft polymer (B)-In a reactor purged with nitrogen, 50 parts (solid content) of polybutadiene latex (average particle diameter 0.35 µm, gel content 90%), 200 parts of water, disodium ethylenediaminetetraacetate 0.1 part, ferric sulfate 0.001 part, sodium formaldehyde sulfoxylate 0.4 part
After heating to ℃, a mixture consisting of 15 parts of acrylonitrile, 35 parts of styrene and 0.2 parts of cumene hydroperoxide was continuously added over 3 hours, and further polymerized at 60 ° C. for 2 hours. Then, after salting out and drying, a graft copolymer (B) was obtained.

-Copolymer C-1-A reactor purged with nitrogen was charged with 120 parts of pure water and 0.3 part of potassium persulfate, and then heated to 65 ° C with stirring. Thereafter, 30 parts of a mixed monomer solution consisting of 30 parts of acrylonitrile, 70 parts of styrene and 0.06 part of t-dodecyl mercaptan and 30 parts of an emulsifier aqueous solution containing 2 parts of disproportionated potassium rosinate were continuously added over 4 hours. The temperature of the polymerization system was raised to 70 ° C., and aging was performed for 2 hours to complete the polymerization. After salting out, dehydrating and drying, the intrinsic viscosity is 1.
Thus, a copolymer C-1 was obtained.

-Copolymer C-2- The same operation as copolymer C-1 was carried out except that the amount of t-dodecyl mercaptan used was changed to 0.16 parts, to obtain copolymer C having an intrinsic viscosity of 0.85. -2 was obtained.

-Copolymer C-I The same operation as for copolymer C-1 was carried out except that the amount of tert-dodecyl mercaptan used was changed to 0.35 part, to give copolymer C having an intrinsic viscosity of 0.50. -I was obtained.

-Copolymer C-ii- Copolymer C-1 having an intrinsic viscosity of 1.60 was prepared in the same manner as copolymer C-1 except that the amount of tert-dodecyl mercaptan was changed to 0.01 part. -Ii was obtained.

-Flame retardant (D)-D-1: Brominated epoxy oligomer (Platherm EC-20, manufactured by Dainippon Ink and Chemicals, Inc.) D-2: Condensed phosphate ester (CR-7, manufactured by Daihachi Chemical Co., Ltd.)
33S)

-Polytetrafluoroethylene (E)-E-1: Polytetrafluoroethylene (Polyflon FA-500, manufactured by Daikin Industries, Ltd.)

[0039]

EXAMPLES 1-5, COMPARATIVE EXAMPLES 1-10 Each of the above components was supplied at the mixing ratio shown in Table 1 to a vented extruder having a diameter of 40 mm and granulated at 230 ° C. to obtain pellets. Was. Using these pellets, blow moldability and pinch-off strength were evaluated.

Blow moldability Molding machine: B-30 manufactured by Nippon Steel Works Molding temperature (cylinder set temperature): 160 to 240 ° C Mold temperature: 80 ° C Various molding temperatures are changed (160 ° C, 200 ° C, 220) ℃,
240 ° C), length 200mm, width 200mm, height 3
The moldability when forming a prismatic bottle having a thickness of 00 mm and an average thickness of about 3 mm was evaluated. ：: A good parison was obtained, and a good molded product was obtained. X: Drawdown was severe, melt fracture occurred, and a parison having a uniform thickness could not be obtained.

Pinch-off strength A test piece of 150 mm × 30 mm was cut out from the surface having the pinch-off portion of the blow-molded product obtained above, and the pinch-off strength was measured. Unit kg / cm ² . Table 1 shows the results.

After drying the flame-retardant pellets at 100 ° C. for 3 hours, a test piece was prepared at 230 ° C. cylinder temperature and 50 ° C. mold temperature using an injection molding machine (clamping pressure: 90 tons), and the test was performed under US Subject 94 standardized by Writers Laboratories
No. (UL94), the flame retardancy of 1/16 inch was measured. In addition, about Comparative Example 7, the combustion was intense and was out of the standard.

[0043]

[Table 1]

[0044]

According to the present invention, a blow molding resin composition having excellent blow moldability and pinch-off strength and excellent flame retardancy can be obtained, and is preferably used as a material for blow molding. Can be.

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Claims (2)

[Claims] 1. A viscosity average molecular weight of 17,000 to 30,0.
00 to 30% by weight of a polycarbonate resin (A),
Graft polymer (B) 5-68 obtained by graft polymerization of aromatic vinyl and vinyl cyanide in the presence of diene rubber
Weight% and an aromatic vinyl having an intrinsic viscosity of 0.6 to 1.5.
Per 100 parts by weight of the composition comprising 2 to 50% by weight of the vinyl cyanide copolymer (C), the halogen-based flame retardant and / or
Alternatively, a resin composition for blow molding, comprising 3 to 40 parts by weight of a phosphorus-based flame retardant (D) and 0.05 to 5 parts by weight of polytetrafluoroethylene (E). 2. The resin composition for blow molding according to claim 1, wherein the aromatic vinyl-vinyl cyanide copolymer (C) has an intrinsic viscosity of 0.8 to 1.4.