JP2005281486A - Resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin composition which maintains an excellent flexibility inherent in a polyethylene terephthalate, has a high flame retardance and is suitable for use in items for which a high flexibility is required such as clips, fastener parts, electric and electronic parts or automobile parts particularly requiring flexibility. <P>SOLUTION: The resin composition comprises (A) a polybutylene terephthalate copolymer, (D) a powdery mixture containing an organic halogen compound, antimony trioxide and a polytetrafluoroethylene and (E) an organic sulfur compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a flame retardant resin composition having flexibility in which a halogen-based flame retardant is blended with a copolymerized polybutylene terephthalate resin composition. More specifically, it has excellent flexibility and fluidity, high flame retardancy, and flexibility using a halogen-based flame retardant suitable for clips, fastener parts, electrical and electronic parts, or automotive parts that particularly require flexibility. It is a flame retardant resin composition

  Polybutylene terephthalate resin (PBT) is utilized in a wide range of fields such as mechanical mechanism parts, electrical / electronic parts, and automobile parts by taking advantage of its excellent properties such as injection moldability and mechanical properties. Although PBT is inherently flammable, it is known that a high degree of flame retardancy can be obtained by selecting a flame retardant.

  Further, as disclosed in Document 1, the PBT copolymer product in which a part of PBT is replaced with other components has a lower melting point and crystallinity, and therefore has flexibility, flexibility, adhesiveness or solvent solubility. It is applied and used for adhesives and paints.

  Therefore, in order to widely use PBT copolymer products as the above-mentioned clips, fastener parts, electrical / electronic parts and automobile parts, it is difficult to mix halogen flame retardants in addition to the balance of general chemical and physical properties. It is desired to be a fuel material.

As a method of imparting flame retardancy to PBT and PBT copolymer products, halogen-based organic compounds as flame retardants, antimony compounds as flame retardant aids, and polytetrafluoroethylene as a compound to prevent dripping during combustion are compounded into resins. The method to do is common. For example, Document 2 discloses a technique for making PBT resin flame retardant, and includes flame retardant aids for main flame retardants such as brominated epoxy compounds, brominated polycarbonate oligomers, pentabromobenzyl polyacrylate, and brominated polystyrene. A technique of adding an antimony compound and adding polytetrafluoroethylene as an anti-drip agent is well known. Patent Document 1 discloses that a flame retardant resin composition having excellent fluidity and residence stability is obtained by blending PBT with a brominated polycarbonate oligomer, a brominated epoxy oligomer, an antimony compound, and a specific phosphorus compound. Technology is disclosed. Patent Documents 2 to 4 disclose technologies for imparting flame retardancy by blending a PBT with a flame retardant, a flame retardant aid, and specific polytetrafluoroethylene.
Edited by Kazuo Yuki, “Saturated Polyester Resin Handbook”, Nikkan Kogyo Shimbun, 1989, p. 562-573 “Environmentally Compatible New Flame Retardant / Flame Retardation Technology [Technical Documents Collection]”, Information Technology Association, 1999, p. 228-233 JP 62-172052 A (Claims) JP 10-310707 A (paragraphs [0011] to [0013], [0049] to [0059]) Japanese Patent No. 3066012 (paragraphs [0024] to [0026], [0036] to [0054]) JP 2000-297220 A (paragraphs [0024] to [0027], [0037] to [0043], [0046] to [0057])

  However, when imparting flame retardancy to a PBT copolymer product, it is necessary to add a large amount of a flame retardant, and there is a problem that the characteristic flexibility disappears. The present invention is a clip in which a polybutylene terephthalate copolymer is blended with an organic halogen flame retardant and antimony trioxide, has excellent flexibility, fluidity, and high flame retardancy, and particularly requires flexibility. Another object of the present invention is to obtain a resin composition suitable for fastener parts, electrical and electronic parts, or automobile parts.

  As a result of intensive studies in view of the above circumstances, the present inventors have blended a polybutylene terephthalate copolymer with an organic halogen compound, antimony trioxide, and a specific polytetrafluoroethylene-containing mixed powder. The present inventors have found that a resin composition having excellent flame retardancy and high flexibility can be obtained by adding a small amount of the organic sulfur compound.

  In the present invention, the present inventors have succeeded in obtaining a resin composition excellent in both flexibility and flame retardancy, which are particularly contradictory performances.

In order to solve the above problems, the present invention has the following configuration.
That is, the present invention
(1) Polybutylene terephthalate copolymer (A) 68.0-84.8% by weight, organic halogen compound (B) 10-20% by weight, antimony trioxide (C) 5-10% by weight, polytetrafluoro A resin composition comprising 0.1 to 1.0% by weight of an ethylene-containing mixed powder (D) and 0.1 to 1.0% by weight of an organic sulfur compound (E), and a copolymer of the copolymer (A) A resin composition characterized in that the polymerization component is dodencandioic acid,
(2) The resin composition according to (1), wherein dodencandioic acid of the copolymer component is 10 to 30 mol%,
(3) The resin composition according to any one of (1) and (2), wherein the organic halogen compound (B) is a brominated polycarbonate oligomer or a brominated epoxy oligomer,
(4) The polytetrafluoroethylene-containing mixed powder (D) is composed of polytetrafluoroethylene and an organic polymer, and the organic polymer is a methyl methacrylate-butyl acrylate copolymer (1) It is a resin composition in any one of-(3).

The present invention has excellent flexibility and fluidity and high flame retardancy by blending an organic halogen flame retardant and antimony trioxide with a polybutylene terephthalate copolymer, and particularly requires flexibility. It can be suitably used for clips, fastener parts, electrical / electronic parts or automobile parts.

  Embodiments of the present invention will be described below.

  In the present invention, the polybutylene terephthalate copolymer (A) (hereinafter also referred to as component (A)) is terephthalic acid (or an ester-forming derivative such as dimethyl terephthalate) and 1,4-butanediol (or an ester thereof). And other dicarboxylic acids (or ester-forming derivatives thereof) or other diols (or ester-forming derivatives thereof) copolymerizable therewith, among which the third component A copolymer obtained by copolymerizing other dicarboxylic acid (or an ester-forming derivative thereof) is preferable.

  The copolymerization ratio of the other dicarboxylic acid (or ester-forming derivative thereof) is preferably in the range of 10 to 30 mol% in the total dicarboxylic acid component from the viewpoint of imparting flexibility, and in the range of 15 to 25 mol%. It is more preferable that When the copolymerization component is less than 10 mol%, flexibility is not exhibited, while when it exceeds 30 mol%, the melting point is remarkably lowered and the moldability is deteriorated.

  In addition, the copolymerization ratio of other diols (or ester-forming derivatives thereof) is preferably in the range of 3 to 30 mol% in the total diol component from the viewpoint of moldability, and in the range of 3 to 20 mol%. More preferably.

  Examples of other dicarboxylic acids include isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, and 4,4′-diphenyl ether dicarboxylic acid. Acids, aromatic dicarboxylic acids such as 5-sodiumsulfoisophthalic acid, aromatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc. And decanoic acid is particularly preferable from the viewpoint of imparting flexibility.

  The viscosity is not particularly limited as long as melt kneading is possible, but it is preferable that the relative viscosity is 25 to 50 dl / g when measured at 25 ° C. using an 8% o-chlorophenol solution.

  The organic halogen compound (B) (hereinafter also referred to as component (B)) in the present invention is a brominated epoxy oligomer obtained by reaction of tetrabromobisphenol A and epihalohydrin, and tetrabromobisphenol A as a constituent component. Examples thereof include brominated polycarbonate oligomers and pentabromobenzyl polyacrylate. Among them, brominated epoxy oligomers and brominated polycarbonate oligomers are preferable in terms of fluidity and cost. The molecular weight of the brominated epoxy oligomer is not particularly limited, but is preferably in the range of 2,000 to 10,000 from the viewpoint of compatibility with the polybutylene terephthalate copolymer. The molecular weight of the brominated polycarbonate oligomer is not particularly limited, but is preferably 10,000 to 20,000 from the viewpoint of compatibility like the brominated epoxy oligomer. (B) The compounding quantity of a component is 10-20 weight%, Preferably it is 12-18 weight%. When the blending amount is less than 10% by weight, flame retardancy is not exhibited, and when it exceeds 20% by weight, flexibility is lowered.

  The average particle size of antimony trioxide (C) (hereinafter also referred to as component (C)) of the present invention is not particularly limited, but is preferably 1.0 to 2.0 μm, more preferably 1. 0 to 1.5 μm. When the particle size of the component (C) is within the above range, high flame retardancy can be obtained. Moreover, a compounding quantity is 5 to 10 weight%, Preferably it is 6 to 9 weight%. When the blending amount is less than 5% by weight, flame retardancy is not exhibited, and when it exceeds 10% by weight, flexibility is lowered.

  The polytetrafluoroethylene-containing mixed powder (D) referred to in the present invention (hereinafter also referred to as component (D)) suppresses melting and dropping of the resin composition during combustion, and improves flame retardancy. I can do it. Specifically, it is composed of polytetrafluoroethylene particles having a particle diameter of 10 μm or less and an organic polymer. From the viewpoint of dispersibility when blended, polytetrafluoroethylene having a particle diameter of 0.05 to 1.0 μm. It is obtained by polymerizing a vinyl monomer in a dispersion liquid in which a dispersion and an organic polymer dispersion are mixed, and then pulverizing by solidification or the like. As the vinyl monomer, from the viewpoint of compatibility with the polybutylene terephthalate copolymer, an aromatic vinyl monomer, a (meth) acrylate monomer, and a vinyl cyanide monomer are preferable. Methyl methacrylate and butyl acrylate are preferred. (D) The compounding quantity of a component is 0.1 to 1.0 weight%, More preferably, it is 0.3 to 0.7 weight%. When the blending amount is less than 0.1% by weight, flame retardancy is not exhibited, and when it exceeds 1.0% by weight, the mechanical properties are deteriorated.

  The organic sulfur compound (E) (hereinafter also referred to as the component (E)) referred to in the present invention has an antioxidant function, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipro. It is an organic sulfur compound having a specific structure such as piionate, and dilauryl-3,3′-thiodipropionate is preferable. By adding this component (E), flame retardancy is dramatically improved, and the amount of the flame retardant component can be suppressed. By suppressing the amount of the flame retardant component, flexibility is impaired. Therefore, the polybutylene terephthalate copolymer which is easily flammable can be made flame retardant. (E) The compounding quantity of a component is 0.1 to 1.0 weight%, More preferably, it is 0.2 to 0.6 weight%. When the blending amount is less than 0.1% by weight, flame retardancy is not exhibited, and when it exceeds 1.0% by weight, mold contamination occurs.

  The resin composition of the present invention includes a release agent, an antioxidant and a stabilizer other than the component (D), a lubricant, a crystal nucleating agent, a terminal blocking agent, an ultraviolet absorber, and the like within a range not impairing the effects of the present invention. Conventional additives such as colorants and small amounts of other polymers can be added.

  Examples of mold release agents include montanic acid waxes, metal soaps such as lithium stearate and aluminum stearate, higher fatty acid amides such as ethylene bisstearyl amide, and ethylenediamine / stearic acid / sebacic acid polycondensates. Among them, montanic acid waxes and ethylene bisstearylamide are preferable.

  Specific examples of the antioxidant include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3 5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3 5-di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-tert-butyl-4-hydroxybenzyl) benzene, bis or tris (3-tert-butyl-6-methyl-4-hydroxy) Phenyl) propane, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), N, N′-trimethylenebis (3,5-di-t-) Butyl-4-hydroxy-hydrocinnamamide) and the like. The phosphite antioxidants include tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, and trisnonylphenyl. Examples thereof include phosphites, alkylallyl phosphites, trialkyl phosphites, triallyl phosphites, and pentaerythritol phosphite compounds.

  Examples of stabilizers include benzotriazole-based compounds including 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, as well as benzophenone-based compounds such as 2,4-dihydroxybenzophenone, mono- or distearyl phosphate, Examples thereof include phosphate esters such as trimethyl phosphate.

  Examples of the crystal nucleating agent include, for example, sodium stearate, barium stearate, sodium montanate, barium montanate, a partial sodium salt of montanate ester, or an organic carboxylic acid metal salt such as barium salt, ionomer, talc, etc. Examples of the crystallization accelerator include polyalkylene glycol derivatives such as polyethylene glycol, polyethylene glycol dibenzoate, neopentyl glycol dibenzoate, and polyethylene glycol bis (2-ethylhexanote), benzoic acid esters, polylactones, and N-substituted. Toluenesulfamide and the like can be used in combination. By adding these crystal nucleating agents, the crystallization speed (solidification speed) is increased and the molding cycle can be shortened.

  Examples of the end-capping agent include aliphatic and aromatic glycidyl esters or glycidyl ethers.

  These various additives may have a synergistic effect by combining two or more kinds, and may be used in combination.

  For example, the additive exemplified as the antioxidant may act as a stabilizer or an ultraviolet absorber. Some of those exemplified as stabilizers also have an antioxidant action and an ultraviolet absorption action. In other words, the classification is for convenience and does not limit the action.

  Examples of the method for producing the resin composition of the present invention include a method of supplying and kneading from the upstream side of the extruder at a cylinder temperature of 230 to 300 ° C. using a twin screw extruder. It may be melt kneaded at a temperature of 200 to 350 ° C. using a known melt mixer such as a machine, a Banbury mixer, a kneader, or a mixing roll, and each component is mixed in advance and then melted. You may knead. Furthermore, for a small amount of additive components such as 1 part by weight or less with respect to 100 parts by weight of the total amount of the components (A) to (E), the other components are kneaded and pelletized by the above method or the like. It may be added before molding. In addition, although it is better that the moisture adhering to each component is small and it is desirable to dry in advance, it is not always necessary to dry all components.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of these examples. Moreover, all the addition mixture ratios shown in the Examples and Comparative Examples are% by weight.

  The material property evaluation method of an Example and a comparative example is shown below.

(1) Flame Retardancy Evaluation Using an injection molding machine (Nissei 60E9ASE), a flame retardant evaluation test piece is injection molded under molding conditions of a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. Flame retardancy was evaluated in accordance with established evaluation criteria. Flame retardancy falls and ranks in the order of V-0>V-1>V-2>. The thickness of the test piece was 1/16 inch (about 1.59 mm, hereinafter abbreviated as 1/16 ").

(2) Evaluation of mold contamination The above-mentioned (1) is performed continuously under the same molding conditions as above, and the contamination level when the mold surface and gas vent after 1000 shots are wiped with an alcoholic solvent is visually observed. “◯” and marked contamination as “X”. The number of tests is three.

(3) Tensile strength Using an injection molding machine (Nissei 60E9ASE), a test piece of ASTM No. 1 type (thickness 3.2 mm) was produced under molding conditions of a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. Evaluation was carried out by a method based on ASTM D638.

(4) Flexural modulus (= flexibility evaluation)
A test piece having a thickness of 6.4 mm was produced under the same molding conditions as in (3) above. Evaluation was performed by a method based on ASTM D790.

(5) Impact strength A test piece having a width of 12.7 mm was produced under the same molding conditions as in (3) above. Evaluation was performed by a method based on ASTM D256 (notched).

(6) Deflection temperature under load A test piece having a thickness of 6.4 mm was produced under the same molding conditions as in (3) above. Evaluation was performed by a method based on ASTM D648. The load stress was 1.82 MPa.

[Reference Example 1] (A-1) Production method of polybutylene terephthalate copolymer 65.6 parts by weight of terephthalic acid, 17.8 parts by weight of dodecanedioic acid, 61.4 parts by weight of 1,4-butanediol and catalyst Charge 0.05 parts by weight of tetrabutyl titanate and 0.04 parts by weight of monobutyltin oxide to a reaction can with a rectifying column and a stirrer, raise the temperature to 150 to 235 ° C. over 4 hours under normal pressure, The reaction was allowed to proceed. The produced water and tetrahydrofuran were distilled off through a rectifying column to obtain a tetrahydrofuran-containing product. Next, 0.02 part by weight of phosphoric acid as an anti-coloring agent and 0.05 part by weight of tetrabutyl titanate as a polycondensation catalyst were added to the resulting esterification reaction product, which was then transferred to a polycondensation reaction can and subjected to atmospheric pressure. The pressure was gradually reduced from 50 to 67 Pa over 50 minutes, the temperature was raised to 245 ° C. at the same time, and a polycondensation reaction was performed for 2 hours and 50 minutes to obtain a 13 mol% copolymerized polybutylene terephthalate resin of dodecanedioic acid. The relative viscosity of the obtained copolymer was 32 dl / g.

[Reference Example 2] (A-2) Production method of polybutylene terephthalate copolymer 60.4 parts by weight of terephthalic acid, 20.9 parts by weight of dodecanedioic acid, 61.4 parts by weight of 1,4-butanediol and catalyst 0.05 parts by weight of tetrabutyl titanate and 0.04 parts by weight of monobutyltin oxide were charged into a reaction vessel equipped with a rectifying column and a stirrer, heated to 150-235 ° C. under normal pressure over 4 hours, and esterified. The reaction was allowed to proceed. The produced water and tetrahydrofuran were distilled off through a rectifying column to obtain a tetrahydrofuran-containing product. Next, 0.02 part by weight of phosphoric acid as an anti-coloring agent and 0.05 part by weight of tetrabutyl titanate as a polycondensation catalyst were added to the resulting esterification reaction product, which was then transferred to a polycondensation reaction can and subjected to atmospheric pressure. The pressure was gradually reduced from 50 to 67 Pa over 50 minutes, the temperature was raised to 245 ° C. at the same time, and a polycondensation reaction was performed for 2 hours and 50 minutes to obtain 20 mol% dodecanedioic acid copolymerized polybutylene terephthalate resin. The relative viscosity of the obtained copolymer was 45 dl / g.

(B-1) Brominated epoxy oligomer: Etototo YDB16 manufactured by Tohto Kasei Co., Ltd. (molecular weight: about 3,000)
(B-2) Brominated epoxy oligomer: Sakamoto Yakuhin Kogyo Co., Ltd. SR-T5000 (molecular weight: about 10,000)
(B-3) Brominated polycarbonate oligomer: BC-58 (molecular weight: 10,000) manufactured by Great Lakes.

(C-1) Antimony trioxide: PATOX-A manufactured by Nippon Seiko Co., Ltd.
(C-2) Antimony trioxide: AT-3 manufactured by Suzuhiro Chemical Co., Ltd.

(D-1) Polytetrafluoroethylene-containing mixed powder: METABRENE A-3000 manufactured by Mitsubishi Rayon Co., Ltd.
(D-2) Polytetrafluoroethylene-containing mixed powder: Metablene A-3800 manufactured by Mitsubishi Rayon Co., Ltd.

(E-1) Organic sulfur compounds: Sumitizer TPS manufactured by Sumitomo Chemical Co., Ltd.
(E-2) Organic sulfur compound: Sumitizer TPM manufactured by Sumitomo Chemical Co., Ltd.

[Examples 1 to 6], [Comparative Examples 1 to 9]
As the component (A), any of the polybutylene terephthalate / dodecanedioic acid copolymers (A-1) to (A-2) produced in the reference example, and the component (B) (organic halogen compound) described below (B- 1) to (B-3), (C) any of the following (C-1) to (C-2) as component (antimony trioxide), (D) component (polytetrafluoroethylene-containing mixed powder) Any of the following (D-1) to (D-2) was used as the body, and any of the following (E-1) to (E-2) was used as the component (E) (organic sulfur compound). Using a twin screw extruder having a screw diameter of 57 mm set at a cylinder temperature of 250 ° C., the components (A) to (E) are supplied from the original loading section and melt kneaded, and the strand discharged from the die is placed in the cooling bath. After cooling, the resin composition was obtained by pelletizing with a strand cutter. The obtained pellets were dried with a hot air dryer at 130 ° C. for 3 hours, and then molded and evaluated. The evaluation results are shown in Table 1. The resin composition obtained in this example exhibited excellent flexibility and high flame retardancy (V-0), both of which had a flexural modulus of less than 1.0 GPa, and had little mold contamination. It was. On the other hand, since the resin compositions obtained in Comparative Examples 1 and 2 have a lower amount of organic sulfur compound than the scope of claims, they exhibit flexibility but have insufficient flame retardancy. It was. In the resin composition obtained in Comparative Example 3, the amount of the organic sulfur compound added is larger than that of the present invention, so that flexibility and flame retardancy are exhibited, but the mold contamination is severe and the moldability is poor. there were. The resin composition obtained in Comparative Example 4 does not exhibit flame retardancy because the addition amount of the polytetrafluoroethylene-containing powder is less than the scope of the claims, while Comparative Example 5 contains polytetrafluoroethylene. Since the amount of powder added is large, flame retardancy is exhibited, but impact resistance is reduced. Since the resin composition obtained in Comparative Example 6 contains less antimony trioxide than in the present invention, flexibility is exhibited but flame retardancy is insufficient. On the other hand, Comparative Example 7 is antimony trioxide. Because of the large amount of blended, the flexibility was lowered. The resin composition obtained in Comparative Example 8 does not exhibit flame retardancy because the blending amount of the organic halogen compound is less than that of the present invention, while Comparative Example 9 has a large blending amount of the organic halogen compound. Therefore, although the flame retardancy is exhibited, the flexibility is lowered.

  The resin composition of the present invention is generally molded by a known thermoplastic resin molding method such as injection molding, extrusion molding, blow molding, transfer molding, vacuum molding, etc., and among them, it is preferably used for injection molding. In addition, the molded product comprising the flexible flame retardant resin composition of the present invention has high safety against electric flame inside the device and fire against the fire of the molded product itself, and further excellent flexibility. Therefore, clips, fasteners, cables It is useful for parts such as general household electric parts, electric / electronic parts and automobile parts.

Claims (4)

Polybutylene terephthalate copolymer (A) 68.0-84.8% by weight, organic halogen compound (B) 10-20% by weight, antimony trioxide (C) 5-10% by weight, polytetrafluoroethylene-containing mixture A resin composition comprising 0.1 to 1.0% by weight of powder (D) and 0.1 to 1.0% by weight of organic sulfur compound (E), wherein the copolymer component of copolymer (A) is A resin composition characterized by being dodencandioic acid. The resin composition according to claim 1, wherein dodencandioic acid as the copolymer component is 10 to 30 mol%. The resin composition according to claim 1, wherein the organic halogen compound (B) is a brominated polycarbonate oligomer or a brominated epoxy oligomer. The polytetrafluoroethylene-containing mixed powder (D) is composed of polytetrafluoroethylene and an organic polymer, and the organic polymer is a methyl methacrylate-butyl acrylate copolymer. The resin composition in any one.