JP3055162B2 - Polybutylene terephthalate resin composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a polybutylene terephthalate resin composition capable of providing a molded product having excellent mechanical properties, particularly improved impact resistance, and relates to an electric and electronic device. It can be used in a wide range of fields such as parts and automobile parts.

(Prior Art) Polybutylene terephthalate resin is excellent in heat resistance and mechanical properties, but has been improved due to poor impact resistance, particularly notched impact strength. Among them,
Consisting of monomers such as α-olefin and α, β-unsaturated glycidyl ester shown in JP-A-51-144452, JP-A-52-32045, and JP-A-53-117049. Method for blending a copolymer, JP-A-60-40154
JP-A No. 2000-131, etc., a method comprising blending a copolymer comprising an α-olefin and a non-conjugated diene with a modified polymer obtained by grafting a monomer such as glycidyl ester of α, β-unsaturated acid, or No. 60-3101, a method of independently blending an acrylic elastomer, or as disclosed in JP-A-63-312313, a vinyl-based epoxy-containing olefin polymer comprising a vinyl monomer. There is a method of blending the polymer alone or the like, which is excellent in improving impact resistance.

However, the modified α-olefin polymer as an impact resistance improver has insufficient dispersibility, and has a drawback that the tensile elongation is lowered even though the impact resistance is improved. Further, even if the acrylic elastomer and the vinyl polymer are blended independently, the blending amount is increased in order to sufficiently improve the impact resistance, and therefore, the heat resistance and the heat resistance characteristic of the polybutylene terephthalate resin are increased. There was a drawback that the chemical property was reduced.

(Problems to be Solved by the Invention) The present invention has improved impact resistance while maintaining heat resistance and chemical resistance by blending a specific vinyl-based graft polymer and an acrylic-based elastic material with polybutylene terephthalate resin. An object of the present invention is to provide a polybutylene terephthalate resin composition.

(Means for Solving the Problems) The present invention particularly relates to a graft obtained by graft-polymerizing a vinyl monomer to (I) 50 to 99% by weight of a polybutylene terephthalate resin, and (II) an epoxy group-containing olefin copolymer. 25-0.5% by weight, (III) Acrylic elastic body 25-0.5% by weight [However, the total of (I), (II) and (III) is 100% by weight. And the polybutylene terephthalate resin (I) has an intrinsic viscosity
The present invention relates to a polybutylene terephthalate resin composition comprising a polybutylene terephthalate resin of 0.70 to 0.92 dl / g and a polybutylene terephthalate resin having an intrinsic viscosity of 0.93 to 1.40 dl / g.

The polybutylene terephthalate resin used in the present invention is terephthalic acid as an acid component and 1,4-
It is a polymer obtained by a condensation reaction containing butanediol as a component.

If the acid component is 20 mol% or less, isophthalic acid: phthalic acid: 2,6-naphthalenedicarboxylic acid: 1,5-naphthalenedicarboxylic acid: bis (P-carboxyphenyl)
Methane: anthracene carboxylic acid: 4,4-diphenyl carboxylic acid: 4,4, -diphenyl ether carboxylic acid: 1,2-bis (phenoxy) ethane-4,4-dicarboxylic acid: or terephthalates such as ester-forming derivatives thereof An acid component other than an acid may be used. If the diol component is 20 mol% or less, an aliphatic diol having 2 to 10 carbon atoms, that is, ethylene glycol: propylene glycol: neopentyl glycol: 1,5-pentane Diol:
1,6-hexanediol: decamethylenediol: cyclohexanediol, or a long-chain glycol having a molecular weight of 400 to 6000, ie, polyethylene glycol: poly
1,3-Propylene glycol: A diol component other than 1,4-butanediol such as polytetramethylene glycol and a mixture thereof may be used.

In the present invention, the intrinsic viscosity number of the polybutylene terephthalate resin is 0.70 to 0.92 dl / g, and the intrinsic viscosity number is a polybutylene terephthalate resin having an intrinsic viscosity of 0.93 to 1.40 dl / g. Excellent flowability during molding due to use
In addition, a polybutylene terephthalate resin composition having excellent impact resistance can be provided.

The grafted product obtained by graft polymerization of a vinyl monomer to an epoxy group-containing olefin copolymer (hereinafter abbreviated as grafted product) in the present invention is an ethylene / glycidyl methacrylate copolymer: ethylene / vinyl acetate / glycidyl methacrylate copolymer. Copolymer: ethylene / glycidyl methacrylate copolymer: ethylene / carbon monoxide / glycidyl methacrylate copolymer: ethylene / glycidyl acrylate copolymer:
An epoxy group-containing olefin copolymer typified by an ethylene / vinyl acetate / glycidyl acrylate copolymer;
Vinyl aromatic monomers such as styrene and α-methylstyrene: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, etc. (Meta)
Acrylic ester monomer: (meth) acrylonitrile ;: Obtained by graft polymerization of at least one vinyl monomer represented by vinyl esters such as vinyl acetate and veova.

The grafted product in the present invention can be obtained by a known production method. For example, there is a production method described in JP-A-63-313313, but the present invention does not particularly limit this.

Representative examples of the grafted product used in the present invention include, for example, a mixture of an ethylene / glycidyl methacrylate copolymer and a polymer containing styrene as a monomer and / or a grafted product (NODIPER A4100 manufactured by NOF Corporation). ,
A mixture and / or grafted product of ethylene / glycidyl methacrylate copolymer and methyl methacrylate monomer (Nippon Oil & Fat Co., Modiper A4200);
Examples include a mixture and / or a grafted product of ethylene / glycidyl methacrylate copolymer and acrylonitrile as a monomer (Nippon Oil & Fats Co., Ltd., Modiper A4400). Among them, a mixture and / or a grafted product of a polymer containing ethylene / glycidyl methacrylate copolymer and methyl methacrylate as a monomer are most preferable.

The amount of the grafted product used in the present invention is 25 to 0.5% by weight, preferably 15 to 2% by weight, based on the total 100% by weight of the polybutylene terephthalate resin, the grafted product and the acrylic elastic body. . 25 such usage
When it is in the range of 0.5% by weight, the effect of improving chemical resistance, heat resistance and impact resistance is sufficient.

The acrylic elastomer used in the present invention is obtained by polymerizing or copolymerizing at least one acrylate ester represented by the following formula: CH 2 ＝ CHCOOR (where R: alkyl of C 1 to 8) A rubber-like elastic body having a content of an acid ester monomer of 75% by weight or more is generally called an acrylic rubber or a polyacrylate rubber. A preferred acrylic elastic body has an elastic modulus of 3000 kg / cm ² or less. Specifically, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, or glycidyl methacrylate containing an epoxy group, or the like, preferably those containing butyl acrylate as a main component It is.

The acrylic elastic body used in the present invention may be a monomer obtained by copolymerizing a monomer composed of a monomer for crosslinking and a monomer for graft bonding with other monomers such as the acrylate ester as other monomers. Absent.

The crosslinking monomer that can be used in the present invention is a butylene diacrylate: dimethacrylate: divinylbenzene: trimethylolpropane having a plurality of double bonds, all of which are polymerized at substantially the same rate. Polyethylenically unsaturated monomers such as triacrylate and trimethacrylate, and similar compounds. Of these, butylene diacrylate is most preferred.

The graft-linking monomer that can be used in the present invention has a plurality of double bonds, at least one of which is a polyethylene-based unsaturated monomer that is polymerized at a polymerization rate substantially different from other double bonds. Is a monomer. Examples of these are allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate, allyl acid maleate, allyl acid fumarate, allyl acid fumarate. Preferred graft bonding monomers are allyl methacrylate,
It is diallyl maleate.

Further, in the present invention, in the presence of the acrylic elastic body, C1
-C16 alkyl acrylate, styrene, acrylonitrile, lower acrylic acrylate and allyl methacrylate obtained by polymerizing a monomer system selected from the group consisting of an acrylic layer composed of a multilayer composite copolymer having a hard thermoplastic layer on the outermost layer obtained An elastic body may be used.

Representative examples of these acrylic elastomers include, for example, Paraloid KM330 (manufactured by Rohm & Haas), Paraloid EXL3386 (manufactured by Rohm & Haas), and Paraloid EXL3303.
(Made by ROHM & Haas), Paraloid EXL3330 (ROHM &
Haas), KCA-301 (Kureha Chemical), Knoxtite A-1095 (Nippon Oil Seal), Hycar4021 (BFGoo
drich).

The amount of the acrylic elastomer used in the present invention is 25 to 0.5% by weight, preferably 15 to 2% by weight, based on 100% by weight of the total of the polybutylene terephthalate resin, the grafted product, and the acrylic elastomer. It is. When the use amount of the acrylic elastic body is 25 to 0.5% by weight, heat resistance and chemical resistance do not decrease, and a sufficient impact resistance improving effect can be obtained.

In the present invention, the above-described grafted product and the acrylic elastomer must be used together with the polybutylene terephthalate resin, and the grafted product or the acrylic elastomer alone is blended with the polybutylene terephthalate resin. However, no sufficient impact resistance improving effect can be obtained.
In order to improve the impact resistance of polybutylene terephthalate resin by using a grafted product or an acrylic elastomer alone, a large amount of these modifiers must be blended, and the inherent characteristics of polybutylene terephthalate resin Heat resistance and chemical resistance are significantly reduced.

In the present invention, the blend ratio of the grafted product and the acrylic elastic material is (grafted product / acrylic elastic material) = (98% by weight / 2% by weight) to (2% by weight / 98% by weight).
And preferably (grafted product / acrylic elastic body) = (70% by weight / 30% by weight) to (30% by weight / 70% by weight)
It is.

The resin composition of the present invention is such that the polybutylene terephthalate resin, the grafted product, and the acrylic-based elastic body total 100% by weight, and the polybutylene terephthalate resin is 50 to 99%.
% By weight, and the total amount of the grafted product and the acrylic elastomer blended at the blend ratio specified above is 50 to 1
%, Preferably 30 to 95% by weight of the polybutylene terephthalate resin, and 30 to 5% by weight of the total amount of the grafted product and the acrylic elastic body. When the total amount of the grafted product and the acrylic elastomer is 50 to 1% by weight, heat resistance and chemical resistance are excellent, and the effect of improving impact resistance is great.

A general method is used as the production method of the present invention. The most common method is to uniformly mix the compound of the present invention with a suitable mixer such as a tumbler, Henschel mixer, tumbler, etc., supply it to an extruder, melt and knead it, cool the extruded strand. Then, it is cut and supplied as a molding material. More simply, a method in which the extrusion step is omitted and the compound of the present invention is directly melted and kneaded in a molding machine to form the mixture can be used, but this is not particularly limited.

In the present invention, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, halogen-based, organic flame retardants such as phosphorus-based, metal powder, and the like, within a range not departing from the gist of the present invention.
Addition of organic or inorganic fillers such as talc, glass fiber, carbon fiber, wood flour, and aramid fiber, antioxidants, UV inhibitors, lubricants, dispersants, coupling agents, foaming agents, crosslinking agents, colorants, etc. An agent and another thermoplastic resin such as polyolefin resin, polyamide, polycarbonate, ABS resin, polyphenylene ether, polyphenylene sulfide, etc. may be added.

(Examples) Further, the present invention will be described with reference to examples. The limiting viscosity used in the present invention is phenol (60) / carbon tetrachloride (4
0) Polybutylene terephthalate 1 in 10 ml of mixed solvent
00mg was dissolved at 80 ° C and measured using an Ostwald viscometer in a thermostatic water bath set at 30 ± 0.05 ° C.

Synthesis Example 1 2.5 g of polyvinyl alcohol and 25 water in an autoclave
Then, 700 g of an ethylene / glycidyl methacrylate copolymer (15% by weight of glycidyl methacrylate), 1.5 g of benzoyl peroxide, 6 g of t-butylperoxymethacryloyloxyethyl carbonate, and 0.6 g of n-dodecyl mercaptan were added. A solution dissolved in 300 g of styrene was added. Then, raise the temperature to 60-65 ° C to dissolve, then 80-85
The reaction was performed at 7 ° C. for 7 hours. The obtained polymer was grafted at 200 ° C. to obtain a grafted product A. This was a thermoplastic resin having a multiphase structure in which true spherical resins having a particle diameter of 0.1 to 0.2 μm were uniformly dispersed.

Synthesis Example 2 In Synthesis Example 1, a polymer was obtained using 300 g of methyl methacrylate instead of 300 g of styrene. This resin was subjected to a grafting reaction in the same manner as in Synthesis Example 1 to obtain a grafted product B. This was a thermoplastic resin having a multiphase structure in which true spherical resins having a particle diameter of 0.3 to 0.4 μm were uniformly dispersed.

Synthesis Example 3 In Synthesis Example 1, styrene was used instead of 300 g of styrene.
A polymer was obtained using 210 g and 90 g of acrylonitrile.
A grafting reaction was performed on this resin in the same manner as in Synthesis Example 1 to obtain a grafted product C. This has a particle size of 0.3 to 0.4
It was a thermoplastic resin having a multi-phase structure in which μm spherical resin was uniformly dispersed.

Examples 1 to 6, Comparative Examples 1 to 4 PBT resin (PBT-B) having an intrinsic viscosity of 0.85 dl / g, PBT resin (PBT-C) having an intrinsic viscosity of 1.00 dl / g, and grafted as a graft copolymer B, KCA301 as acrylic elastic body
(Kureha Chemical Co., Ltd.) and the blending amounts shown in Table 1 were uniformly blended using a tumbler. This blend was extruded into a strand using a 50 mm diameter vented single screw extruder, solidified by cooling, and then cut into a length of 3 mm to obtain a molding material. Inline screw type injection molding machine (Nissei Plastic Industry, PS
60E9ASE), a 1/4 inch thick Izod test specimen was molded and subjected to the Izod test. Further, a dumbbell for ASTM No. IV tensile test was molded, and as a chemical resistance test, the tensile strength after being immersed in toluene for 500 hours was measured. The results are shown in Table 1.

As is apparent from Table 1, when the total amount of the graft copolymer and the acrylic elastomer exceeds 50% by weight, the solvent resistance is remarkably reduced, and when the total amount is less than 1% by weight, the impact resistance is improved. I couldn't.

Examples 7 to 10, Comparative Examples 5 to 8 PBT with intrinsic viscosity of 1.13 dl / g (PBT-D), intrinsic viscosity of 0.84 dl
/ g of PBT (PBT-E), grafted product B as a graft copolymer, KCA301 (made by Kureha Chemical) as an acrylic elastomer
A test piece for an Izod test was molded in the same manner as in Examples 1 to 6, and an Izod test was performed. ASTM IV
A dumbbell for tensile test was molded, and its heat aging at 180 ° C for 200 hours was examined.

Table 2 shows the results. As is clear from Table 2, the present invention can obtain high impact resistance with a small amount of compounding, and does not impair long-term heat resistance.

Examples 11 to 13 and Comparative Examples 9 and 10 PBT resin having an intrinsic viscosity of 0.85 dl / g (PBT-F), PBT resin having an intrinsic viscosity of 1.13 dl / g (PBT-G), grafted as a graft copolymer B, KCA301 as acrylic elastic body
(Kureha Chemical Co., Ltd.) and the blending amounts shown in Table 3 were uniformly blended using a tumbler. This blend was extruded into a strand using a 50 mm diameter vented single screw extruder, solidified by cooling, and then cut into a length of 3 mm to obtain a molding material. Using an injection molding machine (PS60E9ASE, manufactured by Nissei Plastics Industries) set at 250 ° C using this molding material,
A 4 inch thick Izod test specimen was molded and subjected to an Izod test. In addition, using an injection molding machine (PS60E9ASE, manufactured by Nissei Plastics Industries) set at a cylinder temperature of 250 ° C,
At a mold temperature of 60 ° C., the injection pressure required to mold a molded product having a length of 127 mm, a width of 12.7 mm, and a thickness of 1.6 mm was measured. Example
PBT-F and PBT-G were used alone in place of using a mixture of PBT-F and PBT-G in 11 to 13, and otherwise, molding materials were obtained in the same manner as in Examples 11 to 13. .

The results are shown in Table-3. As is clear from the results, the composition of the present invention has good fluidity during molding and is excellent in impact resistance.

Comparative Example 9 has excellent fluidity during molding, but has low impact resistance. In Comparative Example 10, although the impact resistance was satisfied, the fluidity during molding was poor.

(Effect of the Invention) The polybutylene terephthalate resin composition of the present invention is excellent in heat resistance, chemical resistance, molding fluidity, and can improve impact resistance with a small amount of addition, and can be used for home electric parts, electricity,
Useful as electronic parts and mechanical parts.

Claims (3)

(57) [Claims] (1) 50-99% by weight of a polybutylene terephthalate resin; (II) 25-0.5% by weight of a grafted product obtained by graft-polymerizing a vinyl monomer onto an olefin copolymer containing an epoxy group; ) Acrylic elastic body 25 to 0.5% by weight [However, the total of the above (I), (II) and (III) is 100% by weight. And the polybutylene terephthalate resin (I) has an intrinsic viscosity
A polybutylene terephthalate resin composition comprising a polybutylene terephthalate resin having a viscosity of 0.70 to 0.92 dl / g and a polybutylene terephthalate resin having an intrinsic viscosity of 0.93 to 1.40 dl / g. 2. The blend ratio of the grafted product and the acrylic elastic material is (grafted product / acrylic elastic body) = (70
2. The polybutylene terephthalate resin composition according to claim 1, wherein the amount of the polybutylene terephthalate resin composition is from 30% by weight / 30% to 30% by weight / 70% by weight. 』 3. A polybutylene terephthalate resin, a grafted product and an acrylic elastomer in a total amount of 100% by weight.
70 to 95% by weight of polybutylene terephthalate resin, 30 to 5% by weight of the total amount of grafted product and acrylic elastic body
The polybutylene terephthalate resin composition according to claim 1 or 2, wherein