JPH0320352A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition excellent in impact resistance, strengths, etc., by mixing a thermoplastic polyester resin with a polycarbonate, a specified graft polymer and an ethylene/alpha-olefin copolymer in a specified weight ratio. CONSTITUTION:A thermoplastic resin composition desirable for automobile members, electrical components, etc., is produced by mixing 90-20wt.% thermoplastic polyester resin (elastomer) (A) with 10-80wt.% polycarbonate (E), a polymer (C) prepared by grafting a vinyl (co)polymer onto a copolymer based on an unsaturated compound unit having both an olefin unit and a functional group selected from among carboxyl, acid anhydride, oxazoline and epoxy groups and an ethylene/alpha-olefin copolymer (D) (e.g. ethylene/propylene copolymer) in such amounts that 1-600 pts.wt. total of components C and D is present per 100 pts.wt. total of components A and B and that the weight ratio of component C to component D is (1-90)/(99-10).

Description

[Detailed Description of the Invention] a. INDUSTRIAL APPLICATION FIELD The present invention relates to a thermoplastic resin composite having excellent impact resistance, mechanical strength, heat resistance, and surface appearance of molded products.

b. Conventional technology Thermoplastic polyester resins, represented by polybutylene terephthalate and polyethylene terephthalate, are used as molded products in a wide range of fields such as home appliance manufacturing and electronic device parts due to their excellent properties. It has the disadvantages of low impact strength and low heat distortion temperature under high loads. For this reason, its use in large molded products has been limited. As a method to improve the high load heat distortion temperature of polybutylene terephthalate,
A method of blending aromatic polycarbonate has been proposed. However, the notched Izod impact strength was still insufficient. In order to improve this drawback, ethylene-propylene copolymer rubber was blended, but the compatibility was poor and the impact strength was reduced.

On the other hand, thermoplastic polyester elastomers have excellent thermal, mechanical, and chemical properties.
It is widely used in everything from sporting goods to industrial products such as tubes and packing, and is expected to grow in the future, but there are some applications where it is difficult to use due to its high hardness. For the purpose of reducing hardness, a method of blending plasticizers and rubbers has been adopted, but there are problems such as oozing of plasticizers when used in large amounts, and there are limits to the amount of plasticizers used. On the other hand, when rubber is blended, it generally has poor compatibility with polyester. We have blended ethylene-propylene copolymer rubber, but the surface appearance of the molded product was poor and only a product with low mechanical strength was obtained.

C. Problems to be Solved by the Invention The object of the present invention is to improve the impact resistance, mechanical strength, and heat resistance of thermoplastic polyester, and to provide a material with excellent surface appearance of molded products.

d. Means for Solving the Problems The present inventors have created an unprecedented solution by blending a polymer with a specific structure with a specific functional group, an ethylene-α-olefin copolymer rubber, and a polycarbonate into a thermoplastic polyester. It has been discovered that a thermoplastic resin composition with excellent performance can be obtained, and the present invention has been accomplished based on this finding.

That is, the present invention comprises (a) 90 to 20% by weight of thermoplastic polyester resin and/or thermoplastic polyester elastomer, (b) 10 to 80% by weight of polycarbonate, (a) +
(b) A copolymer mainly consisting of an olefin unit and an unsaturated compound unit having at least one functional group selected from a carboxyl group, an acid anhydride group, an oxazoline group, and an epoxy group based on 100 parts by weight of the total amount of components. The total amount of the polymer (c), in which a vinyl (co)polymer made of at least one vinyl monomer is grafted to the polymer, and the ethylene-α-olefin copolymer (d), 1 to 6OO weight parts, and the weight ratio of components (c)/(d) is 1 to 90/
9 9 to 10 is provided.

The thermoplastic polyester resin as component (a) used in the present invention is composed of a dicarboxylic acid and a diol compound, and is a relatively high molecular weight, substantially linear thermoplastic polymer. Preferred are polymeric glycol esters of terephthalic acid and isophthalic acid.

Some of these polymers are already commercially available, but they can also be manufactured using known manufacturing techniques (U.S. Pat. No. 2,465,319, U.S. Pat. No. 3,047,539, etc.). .

In other words, it can be produced by alcoholysis of phthalate ester with glycol and subsequent polymerization reaction.Also, it can be produced by polymerization reaction by heating free phthalic acid or its halide derivative and glycol, and similar methods thereof. It can also be manufactured by the manufacturing method.

Preferred thermoplastic polyester resins used in the present invention are:
It is composed of a high molecular weight polymeric glycol terephthalate having a repeating unit of the following formula, or a mixture of glycol isophthalate and these esters.

Here, n is preferably an integer of 2 to 10, and particularly preferably 2 to 4 in view of the physical properties of the composition.

A copolymer of terephthalic acid and isophthalic acid containing up to 30% of isophthalic acid units can also be suitably used. ．． As particularly preferred polyesters, polyethylene terephthalate and poly1,4-butylene terephthalate can be used. Branched polyethylene terephthalate and branched poly 1,4-butylene terephthalate can also be used. Such fractionated polymers can: contain a small amount of a fractionated component having at least three ester-forming groups, for example up to 5 mol % based on the terephthalic acid units.

The branching component may form a branch on the polyol unit in addition to the acid unit of the polyester, or may be a mixture of both. Examples of such branching components include tri- or tetracarboxylic acids, such as trimesic acid, trimellitic acid, pyromellitic acid and their lower alkyl esters, or polyols, preferably tetrols, such as pentaerythritol and triols. eg trimethylolpropane or dihydroxydicarboxylic acids and hydroxydicarboxylic acids and derivatives thereof, such as dimethyl hydroxyterephthalate. These branched polyesters can be manufactured by a method similar to that of the branched poly(1,4-butylene terephthalate) resin described in, for example, US Pat. No. 3,953,404.

Examples of the thermoplastic polyester elastomer used in the present invention include those described in U.S. Patent No. 3.651.014,
U.S. Pat. No. 3,763,109 and 3,
As described in the specification of the publication No. 766,146,
It is a segmented copolyester having a large number of repeating ether ester and/or ester units, in which hard segments and soft segments are combined in a block manner. Particularly preferred hard segments are poly 1,4-butylene terephthalate (including those partially copolymerized with isophthalic acid), and particularly preferred soft segments are polyethers, such as polyethylene glycol, polyester, etc. (1,2-
propylene oxide) glycol, poly(1,3-propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide)
Glycol, a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydrofuran are used. Among these, polyethylene glycol is preferred.

The number average molecular weight of these poly(alkylene oxide) glycols is preferably in the range of 200 to 6,000, particularly preferably 250 to 3,000.

The above thermoplastic polyester resin and thermoplastic polyester elastomer may be used alone or in combination of two or more, or may be used in combination.

As the polycarbonate component (b), those represented by the following general formula (I) or (If) are used.

(wherein Ar is phenylene or a phenylene group substituted by alkyl, alkoxy, halogen or nitro, and A is a carbon-carbon bond or alkylidene, cycloalkylidene, alkylene, cycloalkylene, alkylene, cycloalkylene, azoimino, sulfur ,
It represents an oxygen or sulfoxide group, and n is at least 2. ) Preferred polycarbonates for use in the present invention are those in which Ar is P-phenylene and A is isopropylidene.

The usage amount of component (a) and component (b) is (a) component/(b)
) component = 90-20/10-80% by weight, preferably 90-30/10-70% by weight, more preferably 80-30/20-70% by weight, use of component (a) Region where the amount exceeds 90% by weight (component (b) is 10% by weight)
% by weight), the heat resistance is poor. Furthermore, in the region where the amount of component (a) used is less than 20% by weight (component (b) exceeds 80% by weight), the surface appearance of the shaped product is poor.

Olefin units and carboxyl groups, acid anhydride groups, oxazoline groups in the polymer used for component (c) of the present invention,
A copolymer mainly composed of unsaturated compound units having at least one functional group selected from epoxy groups is, for example, a copolymer formed by high-pressure radical polymerization of an olefin and the above unsaturated compound monomer or other unsaturated monomer. The olefin in the copolymer is preferably ethylene or propylene, with ethylene being particularly preferred. Among the above copolymers, preferred are ethylene-glycidyl methacrylate copolymers and ethylene-maleic anhydride copolymers, and particularly preferred are ethylene-glycidyl methacrylate binary copolymers. The amount of olefin in the above copolymer is 60 to 9
9.5% by weight, 0.0% by weight of functional group-containing unsaturated compound monomer.
5-40% by weight, other unsaturated monomers 0-39.5% by weight
A copolymer consisting of is preferred. Examples of unsaturated compounds containing carboxyl groups include acrylic acid, methacrylic acid, and maleic acid; examples of unsaturated compounds containing acid anhydride groups include maleic anhydride and itaconic anhydride; and unsaturated compounds containing oxazoline groups. Examples include vinyl oxazoline, and further examples of epoxy group-containing unsaturated compounds include glycidyl methacrylate and allyl glycidyl ether. Preferred functional groups are epoxy groups and acid anhydride groups.

Specifically, the vinyl-based (co)polymer in the polymer (c) used in the present invention includes styrene, methylstyrene, dimethylstyrene, ethylstyrene, isoprobylstyrene, chlorstyrene, α-methylstyrene, Aromatic vinyl monomers such as α-ethylstyrene, methylethyl (meth)acrylate, probyl, isopropyl, butyl, 2-
Esters such as ethylhexyl, cyclohexyl, dodecyl, and octadecyl, vinyl ethers such as vinyl methyl ether and vinyl ethyl ether, vinyl cyan compounds and acrylic acid amide compounds such as acrylonitrile and methacrylonitrile, and maleimides such as phenyl maleimide and cyclohexyl maleimide. These compounds may be used alone or in combination of two or more.

The polymer (c) in the present invention is a thermoplastic composition resin having a multiphase structure, and has a structure in which a vinyl (co)polymer is dispersed in a specific functional group-containing olefin copolymer. Or it consists of one having a structure in which a specific functional group-containing olefin copolymer is dispersed in a vinyl-based (co)polymer.

The particle size of the dispersed polymer is 0.001 to 10 μm1
Preferably it is 0.01 to 5 μm.

When the dispersed resin particle size is less than 0.001 μm or more than 10 μm, the mechanical strength of the resulting composition is undesirably reduced. The number average degree of polymerization of the vinyl (co)polymer in the polymer (c) of the present invention is in the range of 5 to 10,000, preferably 10 to 5,000. The thermoplastic resin with a multiphase structure of the present invention achieves the object of the present invention when the specific functional group-containing olefin copolymer is in a range of 5 to 95% by weight, preferably 20 to 90% by weight. Yes, it is preferable.

The grafting method for producing component <c> of the present invention may be any generally well-known method such as chain transfer method or ionizing radiation irradiation method, but the most preferable method is JP-A-64 This is the method described in JP-A-48856. In component (c) of the present invention, the amount of vinyl (co)polymer grafted to the functional group-containing olefin copolymer, that is, the grafting ratio, is preferably at least 1% by weight or more.

The ethylene-α-olefin copolymer which is the component (d) of the present invention includes an ethylene-α-olefin copolymer and an ethylene-α-olefin-polyene copolymer. The α-olefin used here has 3 to 3 carbon atoms.
It is an unsaturated hydrocarbon compound having 20 atoms, and specific examples include propylene, butene-1, pentene-1, hexene-1, heptene-1, 4-methylbutene-1,4-
Examples include methylpentene-1, but preferred are propylene and butene-1,4-methylpentene-1, and particularly preferred is propylene. Examples of polyene compounds include 1,4-pentadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene, 3.
3-dimethyl-1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 6-methyl-1,5-hexadiene, 1,4-hexadiene, 7-methyl-1,
6-octadiene, 9-methyl-1,9-undecane,
Isoprene, 1,3-pentadiene, 1,4.9-decatriene, 4-vinyl-1-cyclohexane, cyclopentadiene, 2-methyl-2.5-norbornadiene,
5-methyl-2-norbornene, 5-ethylidene-2-
Examples include norbornene, 5-isopropylidene-2-norbornene, 5-isopropenyl-2-norbornene, dicyclopentadiene, tricyclopentadiene, and the like.

Ethylene-α-olefin-polyene copolymer is particularly preferred from the viewpoint of the impact resistance of the resulting composition, the surface appearance of the molded product, and the impact strength after coating.

The weight ratio of ethylene and α-olefin is 95:5 to 5:9.
5, preferably 95:5 to 20:80, more preferably 92:8 to 60:40, particularly preferably 85:15
~70:30.

In order to achieve the above object of the present invention, the ethylene-α-olefin-polyene copolymer preferably has an iodine value of 2 to 2.
A range of 40 is preferred.

(d) Mooney viscosity of component (ML1+4.100'C)
ranges from 5 to 200 in terms of impact resistance.

The total usage amount of components (c) + (d) of the present invention is (a)
+ (b) 1 to 600 parts per total 100 parts by weight of component
parts by weight, preferably 5 to 500 parts by weight, more preferably 5 to 400 parts by weight, particularly preferably 5 to 300 parts by weight; if the amount used is less than 1 part by weight, impact resistance will be poor;
If it exceeds 0 parts by weight, the mechanical strength, heat resistance, and surface appearance of the shaped product will be poor.

The ratio of component (c) and component (d) to be used is determined from the impact resistance and surface appearance of the molded product, and the weight ratio of component (c)/component (d) is 1 to 9 0/9 9 to 10, preferably 5 ~80/9
5-20, more preferably 10-5 0/9 0-5
0% by weight, particularly preferably 10-4 5/9 0-55
Weight%.

In obtaining the thermoplastic resin composition of the present invention, component (c) and/or component (d) can be crosslinked by a known crosslinking method. As the crosslinking method used here, peroxide crosslinking, resin crosslinking, sulfur crosslinking, etc., which are used for ordinary rubber, are used. As for specific crosslinking agents, for example, the crosslinking agents, crosslinking aids, crosslinking accelerators, etc. described in "Crosslinking Agent Handbook (written by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha)" are used.

The crosslinking method includes a static crosslinking method in which components (a), (b), (c), and (d) are melt-mixed, the crosslinking agent is added, the mixture is further kneaded, and crosslinking is performed using a hot press or the like. Although there is a dynamic crosslinking method in which a crosslinking agent is added and crosslinking is performed while continuing the melt-mixing state, the dynamic crosslinking method is preferred because of its excellent performance.

In the dynamic crosslinking method, the crosslinking agents are (a), (b), (c)
, all the components in (d) may be added at the same time, any component or part thereof may be mixed with the crosslinking agent, and the remaining components may be added later, or all or part of each component may be melted. After mixing and adding the remaining components, a crosslinking agent may be added for crosslinking.

・Preferable compositions suitable for crosslinking by adding the above crosslinking agent are (a)+'(b) 10(c)+
The amount of (a) + (b) components in (d) component is 50% by weight
The content is preferably 45% by weight or less.

The composition of the present invention can be obtained by kneading the above-mentioned components using various extruders, Banbury mixers, kneaders, rolls, or combinations thereof. The order of addition of each component during melt-kneading is not particularly limited, but methods include a method of mixing and kneading all the components, a method of kneading arbitrary components, and then adding and kneading the remaining components.

Various fillers can be added to the compositions of the present invention.

For example, glass fiber, carbon fiber, metal fiber, glass beads, asbestos, glass flakes, wollastonite,
Fillers such as calcium carbonate, talc, barium sulfate, miyuki, potassium titanate whisker fluororesin, molybdenum disulfide, carbon black, and titanium oxide can be used alone or in combination. Among these fillers, those in the form of fibers such as glass fiber and carbon fiber are 6
Those having a fiber diameter of ~60 μm and a fiber length of 30 μm or more are preferred.

These fillers can be used in an amount of 5 to 150 parts by weight based on 100 parts by weight of the composition of the present invention.

In addition, known additives such as flame retardants (especially preferably halogen-based), antioxidants (especially preferably phenol-based), blowing agents, lubricants, plasticizers, pigments, and dyes can be used. .

Further, phosphorus compounds are preferred as heat stabilizers, and particularly preferred are those described in Japanese Patent Publication No. 48630/1983.

Furthermore, depending on the required performance, other polymers, such as AB
S resin, AES resin, MBS resin, AS resin, HIPS
, polystyrene, polyamide resin, polyamide elastomer, polyethylene, polypropylene, polysulfone,
Polyether sulfone, polyimide, pps, polyether ether ketone, fluororesin, polyphenylene ether, crosslinked particles, etc. can be blended as appropriate.

The composition of the present invention can be used for injection molding, sheet extrusion, vacuum forming,
It can be used as various shaped products by different molding, foaming, stampable molding, etc. The various molded products obtained by the above-mentioned molding method can be used for the exterior and interior parts of automobiles, various electrical and electronic related parts, housings, etc. by taking advantage of their excellent performance.

e. Examples The present invention will be explained in more detail by Examples, but these are merely illustrative and do not limit the content of the present invention.

In each of the following examples, parts and % indicate parts by weight and % by weight, respectively.

(a) and (b) of the present invention used in Examples and Comparative Examples of the present invention
), (c), and (d) components are shown below.

1. (a) Component (1) Polymers A-1 to A-3 Polybutylene terephthalate with the following ■ value (measured at 25°C using 0-chlorophenol) obtained from dimethyl terephthalate and butanediol was used. .

Polymer A-I IV value 1.0 Polymer A-2 IV value 0.85 Polymer A-3 IV value 0.75 (2) Polymer A-4 (thermoplastic polyester elastomer) PIBIPLEX 4BCM2. manufactured by DUTRAL.
(b) Component (polycarbonate) Polycarbonate manufactured by Idemitsu A2200 (Weight average molecular weight 25.900
) was used.

3. (c) Component (1) Polymer C-1 Add 250 parts of distilled water and 0.25 parts of polyvinyl alcohol to a stainless steel autoclave, and add ethylene-glycidyl methacrylate/copolymer (glycidyl methacrylate content 10%) while stirring. 70 parts were added and dispersed. Penzoyl peroxide 0 as a radical polymerization initiator
．． 15 parts, as a radical (co)polymerizable organic peroxide,
0.6 parts of t-butylberoxymethacryloyloxyethyl carbonate, 21 parts of styrene, and 9 parts of acrylonitrile
% and added to the solution.

By raising the temperature to 60 to 65°C and carrying out a polymerization reaction for 2 hours, the vinyl monomer containing a radical polymerization initiator and a radical (co)polymerizable organic peroxide was impregnated. Next, the temperature was raised to 80 to 85°C, and a polymerization reaction was carried out for 7 hours. A grafted precursor was obtained by washing with water and drying.

This grafted precursor was extruded using an extruder (200° C.) to carry out a grafting reaction, thereby obtaining a multiphase thermally assembled resin B-1. The dispersed particle size of the styrene-acrylonitrile copolymer observed in B-1 using a scanning electron microscope is 0.3 to 0.4 μm, and the grafting rate of the styrene polymer to the ethylene-glycidyl methacrylate copolymer is was 32%.

(2) Polymers C-2 to C-4 Under the production conditions of C-1, C-2 to C-6 were produced by changing the type of functional group-containing olefin polymer or vinyl monomer.

Below under The rest White 4. (d) component (1) Polymers D-1 to D-4 The following ethylene-propylene copolymer rubber was used.

The components (a), (b), (c), and (d) described above were mixed in the composition ratios shown in Table 1, and mixed into pellets using a twin-screw extruder. At this time, sodium dihydrogen phosphate (
a) + (b) + (c) + (d) 0.0 per 100 parts. Two parts were mixed.

After sufficiently drying the obtained pellets, test pieces for evaluation were obtained using an injection molding machine set at 260°C.

Impact resistance (Izod impact strength). The thickness was 1/8', with a notch, and measured at 23°C in accordance with ASTM D256.

Mechanical strength (tensile strength) was measured according to ASTM D638.

Heat resistance (heat distortion temperature): Measured at a thickness of 1/4' and a load of 18.6 kg/cj according to ASTM D648.

Molded product surface appearance: The appearance of the flat molded plate was visually evaluated according to the following criteria.

0: Good x: Failure phenomenon occurred near the gate In Comparative Example-1, the amount of component (a) used was large outside the range of the present invention, and the heat resistance was poor.

In Comparative Example 2, the amount of component (a) used was small and outside the scope of the present invention, and the surface appearance of the molded product was poor.

Comparative Example 3 is an example in which component (c) of the present invention was not used, and the impact resistance and surface appearance of the molded product were poor.

In Comparative Example 4, the amount of components (c) + (d) used was small and outside the scope of the present invention, and the impact resistance was poor.

Margin below f. Effects of the Invention The composition of the present invention has excellent impact resistance, mechanical strength, heat resistance, and surface appearance of molded products, and is suitable for automobile exteriors, interior parts, and electrical/electronic products that require high quality. It provides molded products such as various parts and housings, and has great industrial value.

Claims (1)

[Claims] (1) (a) 90 to 20% by weight of thermoplastic polyester resin and/or thermoplastic polyester elastomer, (b) 10 to 80% by weight of polycarbonate, (a) + (
b) A copolymer mainly consisting of an olefin unit and an unsaturated compound unit having at least one functional group selected from a carboxyl group, an acid anhydride group, an oxazoline group, and an epoxy group based on 100 parts by weight of the total amount of components. A total amount of 1 to 600 parts by weight of a polymer (c) grafted with a vinyl (co)polymer consisting of at least one vinyl monomer and an ethylene-α-olefin copolymer (d) A thermoplastic resin composition characterized in that the weight ratio of components (c)/(d) is 1 to 90/99 to 10.