JPH10279767A - Polybutylene terephthalate-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition useful for automobile parts, etc., improved in antistatic properties while maintaining heat resistance and mechanical physical properties, by compounding a polybutylene terephthalate with a specific block or graft copolymer in a specific ratio. SOLUTION: This composition comprises (A) 50-99.5 wt.% of a polybutylene terephthalate and (B) 0.5-50 wt.% of a block or graft copolymer which is composed of (i) 5-95 wt.% of a polyethylene oxide group-containing segment obtained by (co)polymerizing one or more of polyethylene oxide group-containing monomers and (ii) 5-95 wt.% of a vinyl-based polymer segment containing no polyethylene oxide group and has 1,000-1,000,000 number-average molecular weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polybutylene terephthalate resin composition used as an automobile part, an electric and electronic equipment part, an industrial part, etc., and more particularly to an antistatic property while maintaining heat resistance and mechanical properties. The present invention relates to an improved polybutylene terephthalate resin composition.

[0002]

2. Description of the Related Art Polybutylene terephthalate resins are used in many fields because of their excellent mechanical properties and heat resistance. However, polybutylene terephthalate resin is inferior in antistatic properties, and therefore its improvement is required. For example, Japanese Unexamined Patent Application Publication No.
No. 1201 discloses a method for improving the polybutylene terephthalate resin by adding a resin having a strong polarity such as polyethylene oxide.

[0003]

However, the resin composition disclosed in the above publication is not satisfactory in the improvement of antistatic properties. In addition, the polybutylene terephthalate resin and the highly polar resin such as polyethylene oxide have greatly different polarities, and thus have no compatibility at all. For this reason, there is a disadvantage that the mechanical properties and the appearance of the surface of the molded product are deteriorated, and improvement thereof is required.

The present invention has been made in view of such problems of the prior art. The purpose is to
An object of the present invention is to provide a polybutylene terephthalate resin composition having improved antistatic properties while maintaining heat resistance and mechanical properties.

[0005]

According to the present invention, there is provided a polybutylene terephthalate resin (I) comprising 50 to 99.5% by weight,
The present invention relates to a polybutylene terephthalate-based resin composition containing the following polyethylene oxide group-containing block or graft copolymer (II) at a ratio of 0.5 to 50% by weight. Polyethylene oxide group-containing block or graft copolymer (II): 5 to 95% by weight of a polyethylene oxide group-containing polymer segment obtained by (co) polymerizing one or more kinds of polyethylene oxide group-containing monomers. A block copolymer or a graft copolymer having a number average molecular weight of 1,000 to 1,000,000, comprising 5 to 95% by weight of a vinyl polymer segment containing no polyethylene oxide group.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The polyethylene oxide group-containing block or graft copolymer used in the present invention is a polyethylene oxide group-containing polymer segment obtained by (co) polymerizing one or more polyethylene oxide group-containing monomers, One or more vinyl monomers (co)
It is a block or graft copolymer comprising a vinyl polymer segment containing no polyethylene oxide group obtained by polymerization. Among these, a block copolymer bonded at the molecular chain terminals is more preferable than a graft copolymer bonded at the molecular chain from the viewpoint of dispersibility in the polybutylene terephthalate resin.

[0007] The polyethylene oxide group-containing monomer constituting the polyethylene oxide group-containing polymer segment is a compound having both a vinyl double bond and a polyethylene oxide group in the molecule. Equation (1)

[0008]

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(Wherein, R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms)
R ² represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 1 to 12 carbon atoms. m is 2 to 1
000. ) Or general formula (2)

[0010]

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(Wherein R ³ represents a hydrogen atom or a carbon atom
And an alkyl group of ⁴ , R ⁴ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 1 to 12 carbon atoms. n is 2 to 1
000. ). That is, the compound represented by the general formula (1) is an ester of (meth) acrylic acid and polyethylene glycol or a compound in which the terminal is substituted by the substituent represented by R ² , and represented by the general formula (2) The compound is an ether of (meth) allyl alcohol and polyethylene glycol or a compound in which the terminal is substituted with the substituent represented by R ⁴ . The compounds represented by the above general formula (1) or (2) may be used as a mixture of two or more kinds.

Examples of the vinyl monomer constituting the polymer segment containing no polyethylene oxide group include styrene, nucleus-substituted styrene such as methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene and chlorostyrene. An aromatic vinyl monomer such as α-substituted styrene such as α-methylstyrene, α-ethylstyrene, acrylic acid or methacrylic acid,
C1-C8 alkyl esters of acrylic acid or methacrylic acid, for example, methyl-, ethyl-, propyl-, butyl-, glycidyl-, (meth) acrylic acid;
(Meth) acrylate monomers such as 2-hydroxyethyl and 2-hydroxypropyl; vinyl cyanide monomers such as acrylonitrile or methacrylonitrile; vinyl ester monomers such as vinyl acetate and vinyl propionate; acrylamide And (meth) acrylamide monomers such as methacrylamide, maleimides such as maleic anhydride, phenylmaleimide and cyclohexylmaleimide, and vinyl monomers such as mono- and di-alkyl esters of maleic acid.

Of these, aromatic vinyl monomers, (meth) acrylate monomers, vinyl cyanide monomers and vinyl ester monomers are preferably used from the viewpoint of compatibility with the polybutylene terephthalate resin. Is done. The above monomers may be used as a mixture of two or more kinds.

The number average molecular weight of the polyethylene oxide group-containing block or graft copolymer is 1,000 to 100.
0000, preferably 3000 to 500000,
More preferably, it is 5,000 to 200,000. If the number average molecular weight is less than 1000, mechanical properties are reduced,
On the other hand, if it exceeds 1,000,000, the compatibility with the polybutylene terephthalate resin is reduced, and the appearance is deteriorated, which is not preferable.

The content of the polyethylene oxide group-containing polymer segment in the polyethylene oxide group-containing block or graft copolymer is 5 to 95% by weight, preferably 10 to 90% by weight. If the content of the polyethylene oxide group-containing segment is less than 5% by weight, the effect of improving the antistatic property is small, and if it exceeds 95% by weight, the compatibility with the polybutylene terephthalate resin is reduced, and the appearance becomes poor, which is not preferable.

The synthesis of the polyethylene oxide group-containing block or graft copolymer in the present invention can be carried out by a conventional method. Specifically, if it is a block copolymer, an anion living method, a sequential addition method, a polymer reaction method, a polymeric peroxide method, a polymeric azo compound method, and the like can be exemplified, but the most preferred is a polymeric peroxide from a production viewpoint. Is the law.

Polymeric peroxide is a compound having a plurality of peroxy bonds in one molecule, and a block copolymer is obtained by two-stage polymerization using this polymeric peroxide as an initiator. That is, for example, the following equation (3)

[0018]

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One or two or more kinds of polyethylene oxide group-containing monomers capable of forming a polyethylene oxide group-containing polymer segment are (co) polymerized using a polymeric peroxide as shown in the following. At that time, by stopping the polymerization when about 50% of the active oxygen of the polymeric peroxide remains, a polymer containing a peroxy bond can be obtained. Further, it can be synthesized by (co) polymerizing one or more kinds of vinyl monomers not containing a polyethylene oxide group using this as an initiator.

As the graft copolymer, a chain transfer method, an ionizing radiation irradiation method, a macromonomer method, a radically polymerizable peroxide method and the like can be exemplified. The peroxide method. Radical polymerizable peroxide is a compound having a radical polymerizable double bond and a peroxy bond in one molecule. A graft copolymer can be obtained by two-stage polymerization using this radical polymerizable peroxide. Can be. That is, for example, the following equation (4)

[0021]

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The radical-polymerizable peroxide is not decomposed by using a radical-polymerizable peroxide as described above and one or more vinyl monomers with a usual polymerization initiator such as a peroxide or an azo compound. Copolymerize at temperature. Thereby, a polymer containing a peroxy bond can be obtained. Further, a graft copolymer is synthesized by (co) polymerizing one or more of polyoxyethylene oxide group-containing monomers forming a polyethylene oxide group-containing polymer segment using this as an initiator. Can be.

In the present invention, the mixing ratio of the polybutylene terephthalate resin (I) and the block or graft copolymer (II) containing a polyethylene oxide group is such that the polybutylene terephthalate resin (I) is 50 to 99.5% by weight.
And preferably 70 to 90% by weight. Therefore, the content of the polyethylene oxide group-containing block or graft copolymer (II) is preferably 0.5 to 50% by weight, more preferably 10 to 30% by weight. When the content of the polyethylene oxide group-containing block or the graft copolymer is less than 0.5% by weight, the effect of improving the antistatic property is not sufficient,
If it exceeds 50% by weight, mechanical properties and heat resistance tend to decrease.

In the present invention, an ethylene-propylene polymer, a styrene-butadiene-styrene copolymer, a hydrogenated product thereof and a heat-treated product are used in an amount of 50 parts by weight or less based on 100 parts by weight of the total of the components (I) and (II). Thermoplastic elastomers such as plastic urethane elastomers, polyolefins such as polyethylene and polypropylene, polyethylene oxide, polypropylene glycol, polyetheramide,
Impact resistance, adhesion and antistatic properties can be improved by further adding a hydrophilic polymer such as polyetheresteramide, silicone oil and the like.
If the amount of these resins exceeds 50 parts by weight, the appearance of the molded article is undesirably deteriorated.

In the present invention, the component (I) + (II)
The inorganic filler can be further added in an amount of 100 parts by weight or less based on 100 parts by weight of the total. If the amount of the inorganic filler exceeds 100 parts by weight, the flowability of the polybutylene terephthalate-based resin composition is lowered and the appearance of a molded product is deteriorated.

As the inorganic filler, for example,
Examples of the shape include a plate shape, a scale shape, a needle shape, a spherical shape, a hollow shape, and a fibrous shape. Specifically, calcium sulfate, calcium silicate, clay, diatomaceous earth, talc, alumina, silica sand, glass powder, iron oxide, metal powder, graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon nitride, etc. Granular filler; glass plate, sericite,
Metallic foils such as pyrophyllite and aluminum flakes, and flat or flaky fillers such as graphite; hollow fillers such as shirasu balloons, metal balloons, glass balloons, pumice stones; glass fibers, carbon fibers, asbestos, westonite, etc. Mineral fibers and the like can be mentioned. The surface of the filler is surface-treated using stearic acid, oleic acid, palmitic acid or a metal salt thereof, paraffin wax, polyethylene wax, or a modified product thereof, an organic silane, an organic borane, an organic titanate, or the like. It is preferable to apply.

The polybutylene terephthalate resin composition of the present invention has a temperature of 120 to 350 ° C., preferably 15 to 350 ° C.
It is produced by melting and mixing a polybutylene terephthalate resin and a block or graft copolymer containing a polyethylene oxide group at 0 to 330 ° C. If the temperature is lower than 120 ° C., the melting is incomplete, the melt viscosity is high, the mixing becomes insufficient, and phase separation or delamination appears in the molded product, which is not preferable. 350 ° C
If the ratio exceeds the above, the resin to be mixed is decomposed or gelled, which is not preferable.

As a method for melting and mixing, a method using a commonly used kneader such as a Banbury mixer, a heating kneader, a kneading extruder, a twin-screw extruder, or a roll is employed. The polybutylene terephthalate resin composition of the present invention can be formed by any of injection molding, extrusion molding, vacuum molding, and blow molding.

In the present invention, an inorganic flame retardant such as magnesium hydroxide and aluminum hydroxide, an organic flame retardant such as a halogen type and a phosphorus type, and an organic filler such as wood powder may be used without departing from the gist of the present invention. Additives such as agents, antioxidants, ultraviolet inhibitors, lubricants, dispersants, antistatic agents, coupling agents, foaming agents, crosslinking agents, coloring agents, and other thermoplastic resins can be added.

[0030]

The present invention will be more specifically described below with reference to Production Examples, Examples and Comparative Examples. Production Example 1 (Production of polyethylene oxide group-containing block copolymer (IIA)) 2500 g of pure water was placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and 2.5 g of polyvinyl alcohol was further dissolved as a suspending agent. I let it. In this, the following formula (5)

[0031]

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1800 g of a polyethylene oxide group-containing monomer "Blemmer PME-4000" (trade name, manufactured by NOF Corporation) represented by the formula (1) and 50 g of the compound represented by the formula (3) as a polymerization initiator are charged. And stirred. Then the temperature was raised to 70 ° C., and after polymerization at that temperature for 2 hours,
Cooled to 40 ° C. 200g of ethyl acrylate
After stirring at 40 ° C. for 1 hour, the mixture was heated to 80 ° C., polymerized at that temperature for 4 hours, washed with water and dried to obtain a fine powder of a polyethylene oxide group-containing block copolymer (IIA). Was. The number average molecular weight measured by gel permeation chromatography (hereinafter abbreviated as GPC) was 150,000.

Production Example 2 (Preparation of Block Copolymer Containing Polyethylene Oxide Group (IIB)) A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 2500 g of pure water, and polyvinyl alcohol 2 was used as a suspending agent. 0.5 g was dissolved. In this, the above formula (5)
A polyethylene oxide group-containing monomer represented by the formula: 1800
g, a compound 5 represented by the formula (3) as a polymerization initiator
0 g was added and stirred. Subsequently, the temperature was raised to 70 ° C., polymerization was performed at that temperature for 2 hours, and then the temperature was cooled to 40 ° C. Further, 200 g of styrene was added, and the mixture was stirred at 40 ° C. for 1 hour, heated to 80 ° C., polymerized at that temperature for 4 hours, washed with water and dried to obtain a fine powder of polyethylene oxide group-containing block copolymer (IIB). A powder was obtained. The number average molecular weight measured by GPC was 160,000.

Production Example 3 (Production of Block Copolymer Containing Polyethylene Oxide Group (IIC)) A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 2500 g of pure water, and polyvinyl alcohol 2 was used as a suspending agent. 0.5 g was dissolved. In this, the following formula (6)

[0035]

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1,800 g of a polyethylene oxide group-containing monomer "Blemmer PE-350" (trade name, manufactured by NOF Corporation) represented by the following formula:
Was added and stirred. Next, the temperature was raised to 70 ° C., and polymerization was performed at that temperature for 2 hours.
And cooled. Further, 200 g of ethyl acrylate was added, and the mixture was stirred at 40 ° C. for 1 hour, heated to 80 ° C., polymerized at that temperature for 4 hours, washed with water and dried to obtain a polyethylene oxide group-containing block polymer (IIC). A fine powder was obtained. When the number average molecular weight was measured by GPC, 12
0000.

Production Example 4 (Production of polyethylene oxide group-containing block copolymer (IID)) Into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 2500 g of pure water was added, and polyvinyl alcohol 2 was used as a suspending agent. 0.5 g was dissolved. In this, the above formula (5)
A polyethylene oxide group-containing monomer represented by the formula: 1800
g, a compound 5 represented by the formula (3) as a polymerization initiator
0 g was added and stirred. Subsequently, the temperature was raised to 70 ° C., polymerization was performed at that temperature for 2 hours, and then the temperature was cooled to 40 ° C. Further, 140 g of styrene and 60 g of acrylonitrile were added, and the mixture was stirred at 40 ° C. for 1 hour, heated to 80 ° C., polymerized at that temperature for 4 hours, washed with water and dried, and subjected to polyethylene oxide group-containing block copolymer ( A fine powder of IID) was obtained. The number average molecular weight was measured by GPC.
60000.

Production Example 5 (Production of Polyethylene Oxide Group-Containing Graft Copolymer (IIE)) A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 2500 g of pure water, and polyvinyl alcohol 2 was used as a suspending agent. 0.5 g was dissolved. Among them, the polyethylene oxide group-containing monomer 1 represented by the formula (5)
800 g, 50 g of the radical polymerizable peroxide represented by the formula (4), and di-3,5,5 as a polymerization initiator.
-Trimethylhexanoyl peroxide "Perloyl 3"
10 g of "55" (trade name, manufactured by NOF Corporation) was added and stirred. Next, the temperature was raised to 70 ° C, polymerization was performed at that temperature for 2 hours, and then the temperature was cooled to 40 ° C. Further, 200 g of ethyl acrylate was added, and the mixture was stirred at 40 ° C. for 1 hour, then heated to 85 ° C., and polymerized at that temperature for 4 hours. Thereafter, the resultant was washed with water and dried to obtain a fine powder of a polyethylene oxide group-containing graft copolymer (IIE). The number average molecular weight measured by GPC was 170,000.

Examples 1 to 10 Ube Industries, Ltd. as polybutylene terephthalate resin
“UBE PBT1000SOH” (trade name) (abbreviated as PBT (IA) in the table) or “Toray PBT resin 1401X06” (trade name) (trade name abbreviated as PBT (IB) in the table) manufactured by Toray Industries, Inc. And the polyethylene oxide group-containing block copolymer obtained in Production Example 1 (abbreviated as block copolymer (IIA) in the table). Thereafter, the mixture was fed to a coaxial twin-screw extruder having a screw diameter of 30 mm set at a cylinder temperature of 270 ° C., and granulated after extrusion. After the granulated resin was dried at 110 ° C., the following test pieces were prepared by injection molding, and the following tests were performed. The results are shown in Tables 1 and 2.

Specimen size Specimen with weight deflection temperature: 13 mm × 130 mm × 6 m
m Test piece of bending strength: 10 mm × 130 mm × 4 mm Test piece of surface specific resistance value: 90 mm × 90 mm × 4 mm Each test method is based on the following test methods.

(1) Weight deflection temperature test: JIS K7
207 (2) Bending strength test: JIS K6758 (unit is kg
/ Cm ² and a) (3) Surface resistivity test: 24 hours moisture-conditioned specimen in 50% RH conditions, determined using Shibayama chemical Kikai Seisakusho Co., Ltd. electric conductivity measuring apparatus SS-608H did. (The unit is 10 ¹¹ Ω) (4) Appearance test of molded article: The appearance of the molded article was visually judged for the presence or absence of delamination, and ranked as follows. ◎: No delamination at all ○: Slight delamination ×: Delamination entirely

[0042]

[Table 1]

[0043]

[Table 2]

As shown in Tables 1 and 2, Example 1
The polybutylene terephthalate-based resins of Nos. 10 to 10 were excellent in mechanical properties as shown in the bending strength test, had a small surface specific resistance value, and were excellent in antistatic properties. Further, it was recognized that the antistatic effect was further improved by washing the test piece with water, and even after 3 months from the molding, no decrease in the antistatic performance was observed, and the durability of the effect was excellent. Further, as the amount of the block copolymer containing a polyethylene oxide group increases, the deflection temperature under load decreases somewhat, but does not significantly impair the thermal properties. Further, the compatibility between the polybutylene terephthalate resin and the block copolymer containing a polyethylene oxide group was good, and the appearance of the product was also good.

Examples 11 to 34 Instead of the polyethylene oxide group-containing block copolymer (IIA) of Examples 1 to 10, a polyethylene oxide group-containing block copolymer (IIB), (IIC), or (IID) Are shown in Tables 3 to 8.

[0046]

[Table 3]

[0047]

[Table 4]

[0048]

[Table 5]

[0049]

[Table 6]

[0050]

[Table 7]

[0051]

[Table 8]

As shown in Tables 3 to 8, Examples 11 to 13 were used.
The polybutylene terephthalate resin composition No. 4 had good mechanical properties, good heat resistance, excellent antistatic properties, and excellent effect continuity. The appearance of the product was also good.

Examples 35 to 44 Examples in which a polyethylene oxide group-containing graft copolymer (IIE) was used in place of the polyethylene oxide group-containing block copolymer (IIA) used in Examples 1 to 10 are shown in Table 9.
And Table 10.

[0054]

[Table 9]

[0055]

[Table 10]

As shown in Tables 9 and 10, even when the polyethylene oxide group-containing graft copolymer was used, the polybutylene terephthalate resin composition had good mechanical properties and also had excellent antistatic properties. In addition, the appearance of the product was good.

Comparative Examples 1 to 6 Comparative Examples 1 and 2 are examples in which the polyethylene oxide group-containing block or graft copolymer used in the present invention is not contained at all, and Comparative Examples 3 and 4 are ordinary polyethylene oxide [ "PEG4000" (trade name, manufactured by NOF Corporation)
Comparative Examples 5 and 6 are random examples of styrene and a polyethylene oxide group-containing monomer “Blenmer PME-4000” (trade name, manufactured by NOF Corporation). Copolymer (70/30) [Abbreviated as St / PME-4000 in the table. Here, the random copolymer has no polyethylene oxide group-containing polymer segment and is copolymerized with a statistical probability. ] Is used. Tables 11 and 12 show the formulation examples and test results.

[0058]

[Table 11]

[0059]

[Table 12]

From the above results, the polybutylene terephthalate resin composition of the present invention is a resin composition having improved antistatic properties while maintaining the appearance, mechanical properties and heat resistance, as compared with those of the comparative examples. I understood that.

Incidentally, technical ideas other than the claims are described below together with their effects. (1) A vinyl monomer not containing a polyethylene oxide group which forms a polyethylene oxide group-containing block or a graft copolymer is an aromatic vinyl monomer, (meth)
A polybutylene terephthalate-based resin composition which is an acrylate monomer, a vinyl cyanide monomer, or a vinyl ester monomer. According to this configuration, the polyethylene oxide group-containing block or the graft copolymer has improved compatibility with the polybutylene terephthalate resin. (2) A polybutylene terephthalate-based resin composition wherein the polyethylene oxide group-containing block copolymer is obtained by a two-stage polymerization method using polymeric peroxide as a polymerization initiator. With this configuration, a predetermined polyethylene oxide group-containing block copolymer can be easily produced. (3) The polyethylene oxide group-containing block copolymer is obtained by polymerizing a polyethylene oxide group-containing monomer using a polymeric peroxide, stopping the polymerization by leaving 50% of the active oxygen of the polymeric peroxide, and adding a vinyl monomer A polybutylene terephthalate resin composition obtained by copolymerizing a polymer. With such a configuration, a desired polyethylene oxide group-containing block copolymer can be efficiently produced.

[0062]

As described in detail above, according to the present invention, the polyethylene oxide group-containing block or the graft copolymer has a great effect on improving the antistatic property of the polybutylene terephthalate resin, and comprises a combination thereof. The polybutylene terephthalate-based resin composition can improve antistatic properties while maintaining heat resistance and mechanical properties. Further, the compatibility between the polybutylene terephthalate resin and the polyethylene oxide group-containing block or the graft copolymer is excellent, and the appearance of the molded article can be favorably maintained. Therefore, the polybutylene terephthalate-based resin composition of the present invention is widely used for automobiles, electrics, electronic parts, industrial parts and the like, and is industrially useful.

Claims (1)

[Claims] 1. Polybutylene terephthalate resin (I)
And a polyethylene oxide group-containing block or graft copolymer (II) shown below in an amount of 0.5 to 50% by weight, and a polybutylene terephthalate resin composition comprising: Stuff. Polyethylene oxide group-containing block or graft copolymer (II): one of polyethylene oxide group-containing monomers
A number-average molecular weight of 1,000 to 95% by weight of a polyethylene oxide group-containing polymer segment obtained by (co) polymerizing one or more kinds or two or more kinds and a 5-95% by weight of a vinyl-based polymer segment not containing a polyethylene oxide group
１０００1,000,000 block copolymers or graft copolymers.