JPH04279657A - Polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition consisting of an aromatic polyester and a specific ethylene-based multicomponent copolymer, having excellent impact resistance at low temperature and moldability and readily obtained by these components under melting thereof. CONSTITUTION:(A) 65-99wt.% aromatic polyester is blended with (B) 1-35wt.% ethylene-based multicomponent copolymer consisting of 95-99.8mol% ethylene monomer unit, 0.1-4.9mol% glycidyl (meth)acrylate and 0.1-4.9mol% of monomer unit of a (meth)acrylic acid ester. As necessary, (C) 5-50 pts.wt. copolymer selected from a group of an ethylene-alpha-olefin copolymer having 0.86-0.96g/cm<3> density, a copolymer of ethylene-unsaturated carboxylic acid or derivative thereof and/or an ethylene-vinylester copolymer are further blended with the above- mentioned components.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin composition having excellent impact resistance including low-temperature impact resistance, and particularly excellent moldability.

0002

[Prior Art] Aromatic polyester resins such as polyethylene terephthalate and polybutylene terephthalate are used in automobile parts, electrical and electronic equipment, etc. due to their excellent mechanical properties, electrical properties, heat resistance, chemical resistance, and moldability. It is used in a wide range of fields, mainly parts. However, aromatic polyester resins have a problem of low impact resistance, particularly notched impact resistance, and there has been a strong desire to improve this. Many improvement methods have been proposed in response to this problem. Among these, for example,
A copolymer containing an α-olefin such as ethylene and an unsaturated monomer having an epoxy group such as glycidyl (meth)acrylate in an aromatic polyester resin disclosed in Publication No. 19, Japanese Patent Publication No. 59-28223, etc. Resin compositions with added coalescence are relatively superior in improving the impact resistance of aromatic polyester resins under normal conditions of use. However, this resin composition has a problem of decreasing moldability (fluidity).

0003

[Problems to be Solved by the Invention] An object of the present invention is to provide a polyester resin composition that has improved moldability (fluidity) and impact resistance including low-temperature impact resistance of aromatic polyester resin. be.

0004

[Means for Solving the Problems] In view of the above-mentioned problems, the inventors of the present invention have made extensive studies and have developed the method of adding ethylene, glycidyl (meth)acrylate, and (meth)acrylic esters to aromatic polyester resin. It has been found that it is effective to blend a specific amount of a specific ethylene-based multi-component copolymer containing a specific molar fraction, and the present invention has been completed.

[0005] That is, the first invention of the present invention is: A)
aromatic polyester
65 to 99% by weight B) Ethylene-based multi-component copolymers 1 to 1 consisting of the following (a) to (c)
35% by weight (a) Ethylene monomer unit
95-99.8
mol% (b) Glycidyl (meth)acrylate monomer unit 0.1 to 4.9 mol% (c) Monomer unit of (meth)acrylic esters 0.1 to 4.
A polyester resin composition consisting of 9 mol%,

[0006] The second invention of the present invention is: A) aromatic polyester
65-99% by weight
B) 1 to 35% by weight of an ethylene-based multi-component copolymer consisting of the following (a) to (c) (a) Ethylene monomer unit
95-9
9.8 mol% (b) Glycidyl (meth)acrylate monomer unit 0.1 to 4.9 mol% (
c) (meth)acrylic acid ester monomer unit 0.
Resin composition (A+B) 1 consisting of 1 to 4.9 mol%
C) Density 0.86 to 0.94 g/c based on 00 parts by weight
m3 of ethylene/α-olefin copolymer, ethylene-unsaturated carboxylic acid or its derivative copolymer and/or
or a polyester resin composition containing 5 to 50 parts by weight of at least one selected from the group of ethylene-vinyl ester copolymers,

[0007] A third aspect of the present invention is D) based on 100 parts by weight of the polyester resin composition according to claim 1 or 2.
This is a polyester resin composition characterized in that it contains 5 to 150 parts by weight of an inorganic filler.

A) Aromatic polyester resin used in the present invention is a polyester having an aromatic ring in the chain unit of the polymer, and is composed of an aromatic dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative). ) is a polymer or copolymer obtained by a condensation reaction containing as a main component. The aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, phthalic acid,
, 6-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, bis(p-carboxyphenyl)methane,
Examples thereof include anthracene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 1,2-bis(phenoxy)ethane 4,4'-dicarboxylic acid, and ester-forming derivatives thereof.

[0009] The diol component has 2 to 1 carbon atoms.
0 aliphatic diols i.e. ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-
Hexanediol, decamethylene diglycol, cyclohexanediol, etc., or molecular weight 400-600
Examples include long chain glycols such as polyethylene glycol, poly1,3-propylene glycol, polytetramethylene glycol, etc. and mixtures thereof.

Preferred aromatic polyesters used in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene-2,6-naphthalate, polyethylene-1,
Examples include 2-bis(phenoxy)ethane-4,4-dicarboxylate. More preferred are polyethylene terephthalate and polybutylene terephthalate. The intrinsic viscosity of these aromatic polyesters in 100 ml of trifluoroacetic acid (25)/methylene chloride (75) is
Measured at 25±0.1° C. as a concentration of 0.32 g. Preferably, the intrinsic viscosity is 0.4 to 4.0 dl/g. If it is less than 0.4 dl/g, the aromatic polyester will not be able to exhibit sufficient mechanical strength, which is not preferable. Also 4.0d
If it exceeds 1/g, the fluidity during melting will decrease and the surface gloss of the molded product will decrease, which is not preferable.

B) The ethylene-based multicomponent copolymer used in the present invention is, in part, composed of ethylene, glycidyl (meth)acrylate monomer, and (meth)acrylic acid ester monomer obtained by high-pressure radical polymerization. or a ternary or multicomponent copolymer with other unsaturated monomers, and the copolymer contains ethylene 95 to 99.8 mol%, preferably 95.5 to 98 mol%, Glycidyl (meth)acrylate monomer unit 0.1 to 4.9 mol%
, preferably 0.2-4 mol%, monomer units of (meth)acrylic esters 0.1-4.9 mol%
, preferably 0.5 to 4.3 mol%.

[0012] Examples of the above-mentioned glycidyl (meth)acrylate monomer include glycidyl acrylate and glycidyl methacrylate, with glycidyl methacrylate being particularly preferred.

Examples of (meth)acrylic acid ester monomers include methyl, ethyl, and acrylic acid or methacrylic acid.
Esters such as propyl, butyl, 2-ethylhexyl, cyclohexyl, dodecyl, and octadecyl can be mentioned.

Other unsaturated monomers include at least one monomer selected from olefins, vinyl esters, α,β-ethylenically unsaturated carboxylic acids or derivatives thereof, etc. are olefins such as propylene, butene-1, hexene-1, decene-1, octene-1, styrene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, acrylic acid, methacrylic acid, maleic acid, Examples include maleic anhydride, itaconic acid, fumaric acid, maleic acid monoesters and diesters, vinyl ethers such as vinyl chloride, vinyl methyl ether, and vinyl ethyl ether, and acrylamide-based compounds.

Specific examples of the above B) ethylene-based multi-component copolymer include ethylene/ethyl acrylate/glycidyl methacrylate copolymer, ethylene/butyl acrylate/glycidyl methacrylate copolymer, and ethylene/methyl acrylate/glycidyl methacrylate copolymer. Glycidyl methacrylate copolymer, ethylene/
Ethyl acrylate/glycidyl acrylate copolymer, ethylene/methyl acrylate/glycidyl acrylate copolymer, ethylene/ethyl acrylate/methyl acrylate/glycidyl methacrylate copolymer, ethylene/ethyl acrylate/methyl acrylate /glycidyl acrylate copolymer, ethylene/ethyl acrylate/vinyl acetate/
Examples include glycidyl methacrylate copolymer. Among these, preferred are ethylene/ethyl acrylate/glycidyl methacrylate copolymer and ethylene/butyl acrylate/glycidyl methacrylate copolymer. These B) ethylene-based multi-component copolymers can be used even if mixed.

B) The method for producing the ethylene-based multicomponent copolymer by high-pressure radical polymerization uses the above-mentioned ethylene 95 to 99.8
mol%, glycidyl (meth)acrylate monomer 0.
1 to 4.9 mol%, (meth)acrylic acid ester monomers 0.1 to 4.9 mol%, or even a mixture of other unsaturated monomers to the total weight of all those monomers. Polymerization pressure 500-4000 kg/cm2 in the presence of radical polymerization initiator of 0.0001-1% by weight based on
, preferably 1000 to 3500 kg/cm2, and a reaction temperature of 50 to 400°C, preferably 100 to 350°C, in the presence of a chain transfer agent and optionally an auxiliary agent in a tank or tubular reactor. This is a method in which monomers are contacted and polymerized simultaneously or in stages. Examples of the radical polymerization initiator include common initiators such as peroxides, hydroperoxides, azo compounds, amine oxide compounds, and oxygen.

Chain transfer agents include hydrogen, propylene, butene-1, C1 to C20 or higher saturated aliphatic hydrocarbons, and halogen-substituted hydrocarbons, such as ethane, propane, butane, isobutane, n-hexane, n-heptane, cycloparaffins, chloroform, and carbon tetrachloride, C1 to C20 or higher saturated aliphatic alcohols such as methanol, ethanol, propanol and isopropanol, C1 to C2
Included are zero or more saturated aliphatic carbonyl compounds such as carbon dioxide, acetone and methyl ethyl ketone, and aromatic compounds such as toluene, diethylbenzene and xylene.

B) Another example of the ethylene-based multi-component copolymer of the present invention is obtained by adding the above-mentioned glycidyl (meth)acrylate or (meth)acrylic ester to a conventional ethylene homopolymer or copolymer. It is a modified form. The above olefin polymers include homopolymers such as low-density, medium-density, and high-density polyethylene, ethylene-propylene copolymers, ethylene-butene-1 copolymers, ethylene-hexene-1 copolymers, etc.
copolymers, copolymers with other α-olefins containing ethylene as a main component such as ethylene-4-methylpentene-1 copolymers, ethylene-octene-1 copolymers, ethylene-vinyl acetate copolymers , ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, copolymers of ethylene and esters of acrylic acid or methacrylic acid such as methyl, ethyl, propyl, isopropyl, butyl,
Ethylene-maleic acid copolymer, ethylene-glycidyl (meth)acrylate copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, liquid polybutadiene, ethylene-vinyl acetate-vinyl chloride copolymer Combinations and mixtures thereof are also encompassed by the invention.

The composition of the first aspect of the present invention comprises A) 65 to 99% by weight of the aromatic polyester resin and B) 1 to 35% by weight of the epoxy group-containing ethylene multi-component copolymer. If the content of component B) exceeds the upper limit, moldability (fluidity) will decrease, which is not preferable.

The composition of the second invention of the present invention further contains, as component C), an ethylene/α-olefin copolymer, an ethylene-unsaturated carboxylic acid, or a derivative thereof having a density of 0.86 to 0.94 g/cm3. A polyester resin composition containing 5 to 50 parts by weight of at least one selected from the group of polymers and/or ethylene-vinyl ester copolymers. Specific examples of the above component C) include ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, ultra-low density polyethylene, linear low-density polyethylene, and ethylene-(meth)
Examples include ethyl acrylate copolymer and ethylene-vinyl acetate copolymer. The blending amount of the component C) is the same as the above-mentioned A).
+B) It is possible to add up to 5 to 50 parts by weight based on a total of 100 parts by weight of component. If the amount added exceeds 50 parts by weight, heat resistance decreases, which is not preferable.

The third invention of the present invention is a polyester characterized in that D) 5 to 150 parts by weight of an inorganic filler is blended with 100 parts by weight of the polyester resin composition of the first invention or the second invention. It is a resin composition. Examples of the above-mentioned inorganic fillers include powder-like, tabular, scaly, acicular, spherical or hollow, and fibrous fillers, and specifically, calcium sulfate, calcium silicate, clay, diatom filler, etc.
Talc, alumina, silica sand, glass powder, iron oxide, metal powder,
Powder-like fillers such as graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, and carbon black; metal foils such as mica, glass plates, sericite, pyrolite, and aluminum flakes, and flat or scaly materials such as graphite. Hollow fillers such as glass balloons, metal balloons, glass balloons, and pumice: glass fibers,
carbon fiber, graphite fiber, whisker, metal fiber,
Examples include silicon carbide fibers, asbestos, and mineral fibers such as wollastonite. If the blending amount of the filler is less than 5 parts by weight, the blending effect will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength such as impact strength of the molded article will decrease, which is not preferable. In addition, the surface of the inorganic filler is treated with stearic acid, oleic acid, palmitic acid or their metal salts, paraffin wax, polyethylene wax or modified products thereof, organic silane, organic borane, organic titanate, etc. It is preferable to apply

The polyester resin composition of the present invention is produced by melt-mixing at a temperature of 150 to 350°C, preferably 180 to 320°C. If the temperature is lower than 150° C., melting may be insufficient or the melt viscosity may be high, resulting in insufficient mixing, which is not preferable because phase separation or delamination may occur in the molded product. Further, if the temperature exceeds 350°C, the resin to be mixed will decompose and the molded product will be colored, which is not preferable. The melt-mixing method can be carried out using a commonly used kneading machine such as a Banbury mixer, a pressure kneader, a kneading extruder, a twin-screw extruder, or a roll.

In the present invention, other thermoplastic resins, such as polyolefin resins, polyvinyl chloride resins, polyvinylidene chloride resins, polycarbonate resins, polyamide resins, polyphenylene resins, etc., may also be used within the scope of the invention. Thermoplastic resins such as ether resin, polyphenylene sulfide resin, polysulfone resin,
Natural rubber, synthetic rubber, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, organic flame retardants such as halogen-based and phosphorus-based, antioxidants, ultraviolet inhibitors, lubricants, dispersants, foaming agents, crosslinking agents, Additives such as colorants may be added.

[0024]

[Examples] Examples and comparative examples of the present invention will be shown below, but the present invention is not limited to the examples unless it departs from the gist of the present invention. [Resin used] A) Component polybutylene terephthalate (abbreviated as PBT) [Product name: Toray PBT Resin 1401 manufactured by Toray Industries, Inc.] B) Component ethylene-glycidyl methacrylate-(meth)acrylic acid ester copolymer (E- GMA-EA) [GMA content 5% by weight, EA content 10% by weight, product name: Nisseki Rexpar RA4050A2 manufactured by Nippon Petrochemicals Co., Ltd.] Ethylene-glycidyl methacrylate-(meth)acrylic acid ester copolymer (E-GMA-EA) [GMA content 5
Weight%, EA content 20% by weight, product name: Nisseki Rexpar, manufactured by Nippon Petrochemicals Co., Ltd.] Ethylene-glycidyl methacrylate-(meth)acrylic acid ester copolymer (E-GMA-EA) [GMA-containing Amount: 3% by weight, nBA content: 15% by weight, Product name: Nisseki Rexpar, manufactured by Nippon Petrochemical Co., Ltd.]

Ethylene-glycidyl methacrylate-(meth)acrylic acid ester copolymer (E-GMA-EA) [GMA content 6% by weight, nBA content 12% by weight, trade name: Nisseki Lexpar Nippon Petrochemical Co., Ltd.] Ethylene-glycidyl methacrylate-(meth)acrylic acid ester copolymer (E-GMA-EA) [GMA content 9% by weight, nB
A content: 9% by weight, trade name: Nisseki Rexpar, manufactured by Nippon Petrochemicals Co., Ltd.] Ethylene-glycidyl methacrylate-(meth)acrylic acid ester copolymer (E-GMA-EA) [GMA content: 3% by weight %, nBA content 9% by weight, product name: Nisseki Rexpar, manufactured by Nippon Petrochemicals Co., Ltd.] Ethylene-glycidyl methacrylate-(meth)acrylic acid ester copolymer (E-GMA-EA) [GMA content 3% by weight, nBA content 17% by weight, product name: Nisseki Rexpar, manufactured by Nippon Petrochemicals Co., Ltd.] Component C) Ethylene-propylene copolymer rubber (abbreviated as EPR) [
Product name: JSP EPO2P Japan Synthetic Rubber Co., Ltd.
Made〕

(Examples 1 to 5) The pellets of each of the above resins were molded into AS by an injection molding machine [Model IS-90 manufactured by Toshiba Machinery Co., Ltd.] set at a cylinder temperature of 250°C and a mold temperature of 65°C.
A test piece for the physical property test of the TM test was prepared. As a physical property test, a notched Izod impact test [test piece thickness 1/
For 4 inch and 1/8 inch, room temperature (24°C)
, -20°C, -30°C, -40°C]. Further, as an evaluation of processability (fluidity), the apparent viscosity (poise) at a shear rate of 103 during melting was measured, and the results are shown in Table 1.

(Reference Example 1) A test similar to Example 1 was conducted using polybutylene terephthalate alone. The results are shown in Table 1.

(Comparative Examples 1 to 3) Ethylene-based multi-component copolymers in which the content of glycidyl methacrylate and (meth)acrylic acid ester is outside the claimed content range of component B) used in the present invention Table 1 shows the results of evaluating the PBT composition using.

[Table 1]

[0029]

[Effects of the Invention] The polyester resin composition of the present invention has excellent moldability (fluidity) and high impact strength, and can be easily produced by simply mixing while melting. Therefore, the thermoplastic resin composition of the present invention can be used in a wide range of applications, such as automobile parts, electric/electronic parts, heat-resistant containers, and industrial parts.

Claims (3)

[Claims] [Claim 1] A) Aromatic polyester
65-99% by weight
B) 1 to 35% by weight of an ethylene-based multi-component copolymer consisting of the following (a) to (c) (a) Ethylene monomer unit
95-9
9.8 mol% (b) Glycidyl (meth)acrylate monomer unit 0.1 to 4.9 mol% (
c) (meth)acrylic acid ester monomer unit 0.
A polyester resin composition consisting of 1 to 4.9 mol%. [Claim 2] A) Aromatic polyester
65-99% by weight
B) 1 to 35% by weight of an ethylene-based multi-component copolymer consisting of the following (a) to (c) (a) Ethylene monomer unit
95-9
9.8 mol% (b) Glycidyl (meth)acrylate monomer unit 0.1 to 4.9 mol% (
c) (meth)acrylic acid ester monomer unit 0.
Resin composition (A+B) 1 consisting of 1 to 4.9 mol%
C) Density 0.86 to 0.94 g/c based on 00 parts by weight
m3 of ethylene/α-olefin copolymer, ethylene-unsaturated carboxylic acid or its derivative copolymer and/or
or a polyester resin composition containing 5 to 50 parts by weight of at least one selected from the group of ethylene-vinyl ester copolymers. 3. A polyester resin composition comprising 5 to 150 parts by weight of D) an inorganic filler per 100 parts by weight of the polyester resin composition according to claim 1 or 2.