JPH03185060A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition composed of a polyolefin, a polyphenylene ether, a specific polymer and an ethylene copolymer containing ester group and having high strength at the weld mark part formed by molding as well as high impact strength at the other normal part. CONSTITUTION:The objective thermoplastic resin composition having high mechanical strength is composed of (A) 20-77wt.% of a polyolefin, (B) 20-77wt.% of a polyphenylene ether, (C) 2-50wt.% of a copolymer containing a polymer chain of an alkenyl aromatic compound and a chain of an aliphatic hydrocarbon in the same molecule and (D) 1-25wt.% of an ethylene copolymer containing ester group and produced by copolymerizing (i) 8-43wt.% of an unsaturated ester of formula (R<1> is 1-50C saturated aliphatic or alicyclic hydrocarbon group or aromatic hydrocarbon group; R<2> to R<4> are H, CH3 or C2H5; X is direct bond or methylene) and (ii) olefins composed mainly of ethylene.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a thermoplastic resin composition, and more specifically, the present invention relates to a thermoplastic resin composition, and more specifically, the present invention relates to a thermoplastic resin composition, and more specifically, it relates to a thermoplastic resin composition containing a polyolefin, a polyphenylene ether, an alkenyl aromatic compound polymer chain and a fatty acid in the same molecular chain. The present invention relates to a thermoplastic resin composition which is made of a polymer having both group hydrocarbon chains and an ester group-containing ethylene copolymer, and which has particularly excellent strength in the weld portion that occurs during molding.

[Conventional technology] Polyolefins have excellent moldability, toughness, water resistance, organic solvent resistance, chemical resistance, etc., and are low in specific gravity and inexpensive, so they have traditionally been used for various molded products, films, sheets, etc. Widely used.

However, polyolefins generally do not have very high heat resistance or rigidity, and in order to develop new uses, it is necessary to further improve these properties.

On the other hand, polyphenylene ether has excellent heat resistance and rigidity, but has drawbacks in moldability and solvent resistance, so its range of use is limited. Styrenic resins have been blended and used to improve the moldability, impact strength, etc. of this resin, but the problem remains in solvent resistance, which limits the scope of its use. For example, it is not suitable for fields that require oil resistance, such as gasoline containers.

Various blend compositions have been proposed to combine the advantages and compensate for the disadvantages of these polyolefins and polyphenylene ethers. However, it does not necessarily meet the relatively high mechanical strength level required in the industrial field.

In addition, for the purpose of improving the compatibility of polyolefin and polyphenylene ether and improving mechanical strength, for example, compositions containing block copolymers of styrene and butadiene or hydrogenated products thereof (Japanese Patent Application Laid-open No. 53-
No. 71158, JP-A-54-88960, JP-A-59
100159), compositions in which inorganic fillers are added to these components (Japanese Patent Laid-Open No. 103556/1983), and the like have been proposed. In addition, polyphenylene ether is blended with a large amount of polyolefin exceeding 20% by weight, and a diblock copolymer or radial teleblock copolymer consisting of an alkenyl aromatic compound and a conjugated diene having a compatibilizing effect, or a hydrogenated polymer thereof Compositions containing coalescence have been proposed (Japanese Patent Application Laid-open Nos. 58-103557 and 60-76547), and it is disclosed that melt processability, tensile properties, brittleness, etc. are improved. .

On the other hand, in injection molding of large thermoplastic resin products, in order to shorten the injection time and compensate for the lack of flowability of the molten resin, molten resin is poured into the mold through multiple injection ports (gates). A method of merging between multiple gates is often used. Furthermore, in the molding of products with complex shapes (for example, products with holes), a method is used in which the molten resin is separated at baffle plates in the mold and then remerged. However, in these cases, a joint (hereinafter referred to as a weld) inevitably occurs, and in blend systems whose main components are a combination of polyolefin and polyphenylene ether, there are cases where the strength of the weld is unsatisfactory, and improvement is desired. It was rare.

[Problems to be Solved by the Invention] In view of the above-mentioned current situation, the present invention develops a new composition to create a resin containing polyolefin and polyphenylene ether resin that has both good weld strength and a good balance of mechanical properties. The aim is to obtain a composition.

[Means for Solving the Problems] In order to compensate for and improve the unsatisfactory weld strength of conventional polyolefin-polyphenylene ether compositions, the present inventors investigated various compounding components, and found that By blending a block copolymer that has both an alkenyl aromatic compound polymer chain and an aliphatic hydrocarbon chain with an ester group-containing ethylene copolymer,
Areas with good weld strength and no welds (
The present invention was completed based on the discovery that a resin composition with relatively good mechanical strength of the normal portion (hereinafter referred to as the normal portion) can be obtained.

That is, the present invention is a thermoplastic resin composition comprising the following components and composition.

(a) 20-77% by weight of polyolefin, (b) 20-77% by weight of polyphenylene ether, (c) Polymerization chain of alkenyl aromatic compound within the same molecule (
2 to 50% by weight of a copolymer having both c1) and an aliphatic hydrocarbon chain (c2) and (d) general formula: [wherein R1 is a saturated aliphatic or alicyclic carbonized carbon atom having 1 to 50 carbon atoms] Represents a hydrogen group or an aromatic hydrocarbon group, R2,
Rs and R4 each represent a hydrogen atom, a methyl group, or an ethyl group, at least one of R3 and R4 is a hydrogen atom, and X represents a direct bond or a methylene group] 8 to 43% by weight of an unsaturated ester represented by The resin composition of the present invention has an ester group-containing ethylene copolymer of 1 to 25% by weight, which is a copolymer with an olefin mainly composed of ethylene. A resin composition was obtained that exhibited weld strength and had relatively good mechanical properties in the normal portion.

[Detailed description of the invention] Constituent ingredients The resin composition of the present invention consists of the following components.

(a) Polyolefin The polyolefin used in the present invention includes propylene, butene-1, pentene-1, hexene-1,3-methylbutene-1,4-methylpentene-1, heptene-1, octene-1, etc. It is a polymer or a copolymer consisting of a majority of these polymers by weight. In particular, during the polymerization of crystalline propylene-based polymers, that is, crystalline propylene homopolymer, crystalline propylene-ethylene or butene-1 random copolymer, and polypropylene, propylene, ethylene or butene-1 is continuously added before and after the polymerization. A crystalline propylene-ethylene or/and butene-1 block copolymer obtained by polymerizing at least two monomers selected from the group consisting of 1 is preferred.

Furthermore, among these, the composition of the present invention using a propylene-ethylene block or random copolymer and a propylene-ethylene-butene-1 block or random copolymer exhibiting crystallinity based on tactical polypropylene chains. The weld strength of products tends to increase, especially propylene-ethylene block copolymers (ethylene 2 to 15% by weight, preferably 4 to 12% by weight) that exhibit the same crystallinity.
) or propylene-ethylene-butene-1 block copolymer (ethylene 1-13, preferably 3-10% by weight nibutene 0.5-10, preferably 2-7% by weight), weld strength shows a tendency to become higher.

Furthermore, a mixture of a majority of these crystalline propylene polymers with a rubbery copolymer containing multiple α-olefins containing ethylene or a small amount of non-conjugated diene in some cases improves the balance of mechanical properties. Available in Specific examples of these α-olefin rubbers include ethylene-propylene copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene rubber, -1+
+Shinjin-4I, (-~--mono-pyrene-butene-1 copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber, etc.).

The melt flow rate (MF) of these crystalline propylene polymers and their mixtures with α-olefin rubber
R; 230℃, load 2, 16kg) C, 0.01~
150g/l 0 minutes is preferable, 0.05-70g71
More preferably 0 minutes, particularly preferably 0.1 to 50 g/lo min, and even more preferably 0.5 to 30 g/lo min.

If the MFH value is higher than this range, the level of mechanical property balance will be low, and if the MFH value is lower than this range, there will be difficulties in molding processability, which is not preferred).

These polymers can be obtained by polymerization or modification using known methods, and may be appropriately selected from commercially available polymers.

(b) Polyphenylene ether resin having a structural unit represented by the polyphenylene ether used in the present invention, where n is at least 630, and Q
are each independently a hydrogen atom, a halogen atom, a tertiary α
Hydrocarbon radicals containing no carbon atoms, halohydrocarbon radicals in which halogen atoms are substituted through at least 62 carbon atoms, hydrocarbonoxy radicals and halocarbon radicals in which halogen atoms are substituted through at least 2 carbon atoms Represents a monovalent substituent selected from the group consisting of hydrogenoxy groups.

A typical example of polyphenylene ether is poly(
2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, -Methyl-6-broby-1.4
-phenylene)ether, poly(2,6-dipropyl-
l.

4-phenylene) ether, poly(2-ethyl-6-broby-1,4-phenylene) ether, poly(2,6
-Cyptyl-1,4-phenylene) ether, poly(2
, 6-diprobenyl-1,4-phenylene) ether,
Poly(2,6-dilauryl-1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether, poly(2,6-simethoxy 1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether, ,6-jetoxy-1,4
-phenylene) ether, poly(2-methoxy-6-nitoxy-1,4-phenylene) ether, poly(2-ethyl-6-stearyloxy-1,4-phenylene) ether, poly(2,6-dichloro-1 ,4-phenylene)ether, poly(2-methyl-6-phenyl-1,4
-phenylene) ether, poly(2,6-dipendylene-1,4-phenylene) ether, poly(2-ethoxy-
1,4-phenylene)ether, bo(2-chloro-1
, 4-phenylene) ether, poly(2,5-dibromo-1,4-phenylene) ether and the like.

Also, a copolymer of 2,6-dimethylphenol and 2.3.6-dimethylphenol, a copolymer of 2,6-dimethylphenol and 2.3,5,6-titramethylphenol, 2.6 -Copolymers such as a copolymer of dinitylphenol and 2,3,6-dimethylphenol can be mentioned.

Furthermore, the polyphenylene ether used in the present invention is a polyphenylene ether defined by the above general formula grafted with a styrene monomer (e.g., styrene, p-methylstyrene, α-methylstyrene, etc.), or a polyphenylene ether with a styrene resin. Also included are modified polyphenylene ethers such as blended polyphenylene ethers.

Methods for producing polyphenylene ethers corresponding to the above are known, for example, U.S. Pat.
No. 06875, No. 3257357 and No. 325735
89 specifications and Japanese Patent Publication No. 52-17880 and Japanese Patent Publication No. 50-11q7EL Missing 01 Shizukuma Senshichih A11)
A group of polyphenylene ethers preferred for the purposes of the present invention are polymers of 2,6-dialkylphenols and 2,3,6-trialkylphenols having alkyl substituents in the two positions ortho to the ether oxygen atom or It is a copolymer.

Among these, a polymer of 2,6-dimethylphenol is particularly preferred. Further, the preferred molecular weight range is 0.35-0.70 dl/g, more preferably 0.44-0. 6C1/g, more preferably 0.48 to 0.56 dl/
g range. In the range of values smaller than 0.35 dl/g, the weld strength tends to decrease;
In a value range larger than 0 dI/g, the molding processability of the composition tends to decrease.

(c) Alkenyl aromatic compound in the same molecular chain A: *
Food r. Copolymer with copolymer with copolymer with r”-1 used in the present invention Polymer chain of alkenyl aromatic compound (cl) (hereinafter referred to as chain) in the same molecule used in the present invention (c1)) and a copolymer (c) (hereinafter referred to as copolymer (c)) having both an aliphatic hydrocarbon chain (c, ) (hereinafter referred to as chain (c,))
(referred to as c)) means that a polymer chain portion of an alkenyl aromatic compound and a portion forming a polymer chain form of an aliphatic hydrocarbon are at least partially contained in the same polymer chain constituting the polymer. It is a polymer consisting of at least one polymer chain, and the chain (cl) and chain (c2) are
It includes a so-called linear block structure in which at least one block is connected to each other in a linear manner, a so-called radial teleblock structure in which a branched structure is formed, and a so-called graft-like branched structure in which one side is a trunk and the other is a branch.

The alkenyl aromatic compound forming a chain (cl) has a chemical structure represented by the following general formula.

R'' In the formula, R' and R2 are hydrogen and a lower alkyl group or alkenyl group having 1 to 6 carbon atoms, and R3 and R4 are a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, a chlorine or a bromine atom, , R6R6 and R7 are selected from the group consisting of a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, and an alkenyl group, or R8 and R7 form a part of an aromatic ring, for example, a naphthyl group, etc. Good too.

Specific examples of alkenyl aromatic compounds include styrene, α-
Methylstyrene, methylstyrene, vinylxylene, vinylnaphthalene, divinylbenzene, bromostyrene and chlorostyrene, and may be combinations thereof; among these, styrene, α-methylstyrene, methylstyrene, vinylxylene are preferred. , styrene is more preferred.

The chain (cl) may contain a copolymer component other than the alkenyl aromatic compound in an amount not exceeding 25% by weight as a stroke number when the total weight is 100% by weight.

The chain (c2) is a hydrocarbon chain mainly composed of aliphatic saturated hydrocarbons, and specifically, it is a polymer chain of olefins or a carbon-carbon unsaturated bond of a polymer of conjugated dienes. It also includes those saturated by hydrogenation treatment to have a structure similar to or similar to the polymer chain of olefins. This chain (c2) may partially include a carbon-carbon unsaturated bond, a crosslinked structure, or a branched structure. Oxygen, nitrogen,
Components derived from monomers containing atoms other than carbon, such as sulfur, silicon, phosphorus, and halogen, and alkenyl aromatic compounds may be included in a block, random, graft, or other form. Examples of monomers containing atoms other than carbon include maleic anhydride and its derivatives, acrylic acid and its derivatives, vinyl chloride, and the like.

The proportion of chains (c,) in the polymer (c) is
10 to 80% by weight, assuming the total weight of c) as 100% by weight
The range is preferably from 20 to 75% by weight, and more preferably from 20 to 75% by weight. The proportion of chains (c2) is preferably in the range of 20 to 90% by weight, more preferably in the range of 25 to 80% by weight.

Polymer (c) may contain copolymer components or polymer chains other than chains (c, l and chain (c2)) within the chain, within a range not exceeding 25% by weight, and the polymer chain may form a trunk, a branch, or a part of a block chain of a branched chain.Also, at the branch point of a branched structure or radial teleblock structure, a polyfunctional hydrocarbon group or an atom other than carbon, It may contain polyfunctional hydrocarbon groups containing atoms other than carbon.

The polymer (c) used in the present invention preferably has a dynamic shear modulus G' at 23°C of 3
'dyn/cm' or more, more preferably 7 x 10
8 dyn/cm” or more, more preferably 1 x l O
9 dyn/cm" or more.

The dynamic shear modulus G' can be measured using various commercially available viscoelasticity measurement devices. - Examples include the Rheometrics Mechanical Spectrometer (model number RMS605). Using these devices, the frequency El l hertz and the strain amount 0.1 at 23°C.
The value measured in the range of ~1.5% is defined as the value of the dynamic shear modulus G'.

Therefore, it is commonly known as rubber, and at room temperature e.g.
Natural rubber that exhibits elasticity at ~25°C, polybutadiene rubber,
It is a substance that exhibits properties completely different from butadiene-styrene copolymers, butadiene-acrylonitrile copolymers, boisisobutylene, thiocol rubber, etc., and is generally used for the purpose of improving impact strength and imparting flexibility to thermoplastic resins. It is a different substance from the elastomer component.

Differences between the polymer (c) and substances generally known as rubbers or elastomers can be determined by measuring and comparing numerical values such as tensile strength, tensile modulus, tensile elongation, and torsional rigidity. , in the present invention, is determined based on the dynamic shear modulus (G').

Dynamic shear modulus is 3 x 10'dyn/cm2
In order to obtain the above polymer, chain (c, l and chain (c
2), the bonding method, each microstructure (stereoregularity, vinyl group when using polydiene, cis
-1,4 bond, trans -1,4 bond ratio) etc. must be carefully selected.

When the physical properties of the polymer (c) are in the range of rubber or elastomer, the rigidity level of the resin composition tends to be low.

Specific examples of the polymer (c) include polystyrene-grafted polypropylene, polystyrene-grafted polyethylene, and ethylene-styrene, which are included in the scope of graft copolymers and block copolymers of olefins and alkenyl aromatic compounds such as styrene. Block copolymer, propylene-styrene block copolymer: Alternatively, a block copolymer consisting of an alkenyl aromatic compound and the conjugated diene shown below, or a graft copolymer of an alkenyl aromatic compound to a conjugated diene polymer rubber, polypentenamer, etc. Among these, partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymers are more preferred.

Specific examples of the above conjugated dienes include 1,3-butadiene,
2-methyl-1,3-butadiene, 2゜3-dimethyl-
Examples include 1,3-butadiene, 1,3-pentadiene, etc. Among these, those selected from 1゜3-butadiene and 2-methyl-1,3-butadiene are preferred, and 1,3-butadiene is more preferred. It is. In addition to these conjugated dienes, a small amount of lower olefinic hydrocarbons such as ethylene, propylene, and l-butene, cyclopentadiene, and nonconjugated dienes may be included.

Hereinafter, the partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymer will be explained in more detail. "Partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymer" refers to a structure having at least one chain block rAJ derived from an alkenyl aromatic compound and at least one chain block "B" derived from a conjugated diene. This is a block copolymer in which the aliphatic unsaturated groups in block B of the alkenyl aromatic compound-conjugated diene block copolymer are reduced by hydrogenation. Block A
The arrangement of and B includes a linear structure or a so-called radial teleblock structure having a branched structure. Moreover, a part of these structures may include a random chain derived from a random copolymerization portion of an alkenyl aromatic compound and a conjugated diene. Among these, those having a linear structure are preferred, and those selected from the A-B-A type or the A-B type are more preferred.

In the partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymer (c), the value of the dynamic shear modulus at 23°C is 3 × 10 'dyn/c
In order to control m2, chain (cl) and chain (c
The selection of the ratio of 2) and the microstructure of the conjugated diene before hydrogenation in chain (c2), in particular the 1.2 bonds or the 3.
The selection of the ratio of 4-bonds to cis- and trans-1,4-bonds is important.

The proportion of chains (c, l, that is, the proportion of repeating units derived from alkenyl aromatic compounds) is preferably in the range of 55 to 80% by weight, and 55 to 80% by weight.
The range of 75% by weight is more preferable, and the range of 55 to 70% by weight is even more preferable. If the range is less than 55% by weight, the dynamic shear modulus of the polymer (c) at 23°C tends to be a low value, and at the same time the resin The stiffness level of the composition tends to be low, and in the range of more than 80% by weight, the impact strength level of the composition tends to be low.

The chain (c2) constituting the partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymer (c) is
This is a hydrogenated diene polymerization chain, and the microstructure of the double bond (cis-
and trans -1, 4 bonds and 1.2 bonds and 3.4
The molecular structure of the chain (c, l) and the physical properties of the copolymer (c) after hydrogenation are greatly influenced by the proportion of the sum of 1, 2 bonds and 3.4 bonds in the diene polymerization chain (bonds). The proportion of the sum of the 1, 2 bonds and the 3.4 bonds, or the proportion of the sum of the parts derived from the 1, 2 bonds and the 3.4 bonds in the chain (c2) after hydrogenation is 0 to 3. 30% by weight is preferred, 4-30% by weight is more preferred, 8-30% by weight
27% by weight is more preferred. In a range exceeding 30% by weight, the shear modulus of the polymer (c) at 23° C. tends to be low, and the resulting resin composition tends to have a low rigidity level.

Among the aliphatic chain moieties in these block copolymers, the proportion of unsaturated bonds remaining without hydrogenation is 10
% or less, more preferably 4% or less, and about 2% of the aromatic unsaturated bonds derived from the alkenyl aromatic compound.
5% or less may be hydrogenated.

Regarding the molecular weight of these hydrogenated block copolymers,
Various types can be used, but as a guideline for their molecular weight, it is preferable that the number average molecular weight by the polystyrene conversion method measured by gel permeation chromatography is 5.000 to 500.000, 6. ，
000 to 300.000 is more preferable. More preferably, it is in the range of 30,000 to 200,000, particularly preferably in the range of 45,000 to 150,000. If the number average molecular weight is more than 500,000 or less than 5,000, the mechanical strength of the composition will be unsatisfactory.

Many methods have been proposed for producing alkenyl aromatic compound-conjugated diene block copolymers.

As a typical method, for example, Japanese Patent Publication No. 40-23798
No. Publication, US Patent IE7(!';QR942@71)r
There is a method described in FII No. 4090996, each of which uses a lithium catalyst or a Ziegler type catalyst.
Block copolymerization is carried out in an inert solvent.

Hydrogenation treatment of these block copolymers is described, for example, in Japanese Patent Publications No. 42-8704, No. 43-6636, and No. 46
Hydrogenation is carried out in an inert solvent in the presence of a hydrogenation catalyst according to methods described in various publications such as No. 20814. In this hydrogenation, at least 90%, preferably 96% or more of the olefinic double bonds in polymer block B are hydrogenated, and 25% or less of the aromatic unsaturated bonds in polymer block A are hydrogenated. May be added.

In addition, the journal Jou Polymer Science (Jou
rnal of Polymer 5science)
Part B Letters Volume 11.4
Hydrogenation can also be carried out using p-toluenesulfonyl hydrazide or the like in an inert solvent according to the method shown in literature such as P. 27-434 (1973).

(d) Ester group-containing ethylene copolymer used in the present invention (
d) is a copolymer of an unsaturated ester compound represented by the following general formula (I) and ethylene or an olefin containing ethylene as a main component.

\4 [Wherein, R1 represents an aliphatic (including alicyclic) saturated hydrocarbon group or an aromatic hydrocarbon group having 1 to 50 carbon atoms, and R2
, R3 and R4 each independently represent a hydrogen atom, a methyl group or an ethyl group, at least one of R3 and R4 is a hydrogen atom, and X represents a direct bond or a methylene group. 1R1 is a more preferable carbon number range. is from 1 to 24, more preferably from 1 to 10, particularly preferably from 1 to 6, particularly preferably from 1 to 3. Preferred molecular forms are linear or branched, with linear saturated hydrocarbon groups being more preferred.

Each of R2, R3 and R4 is more preferably a methyl group or a hydrogen atom, and even more preferably a hydrogen atom.

More preferably, X is a direct bond.

-JR Specific examples of the unsaturated ester represented by formula (1) include vinyl acetate, vinyl propionate, vinyl butyrate,
Vinyl isobutyrate, vinyl valerate, vinyl isovalerate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl cyclohexanoate, cyclohexyl vinyl acetate, phenyl vinyl acetate, vinyl benzoate; acetic acid Allyl, allyl propionate, allyl butyrate, allyl isobutyrate, allyl valerate, allyl isovalerate, allyl caproate, allyl caprylate, furyl laurate, allyl palmitate, allyl stearate, allyl cyclohexanoate, allyl cyclohexyl acetate, Allyl phenylacetate, allyl benzoate:
Examples of moieties corresponding to acids constituting unsaturated esters include acetyl group, propanoyl group, butanoyl group, 2-methylpropanoyl group, pentanoyl group, 2-methylpentanoyl group, hexanoyl group, octanoyl group, lauroyl group, and balmitoyl group. 2-propenyl group, 2-methyl-2- Propenyl group, cis-1-propenyl group, trans-1-propenyl group, cis-1-butenyl group, trans-1-butenyl group, cis-2-buten-1-yl group, trans-2-buten-l- yl group, 1
Examples include unsaturated ester compounds selected from -buten-2-yl group, 2-methylene-butyl group, cis-2-penten-1-yl group, trans-2-penten-1-yl group, etc. It will be done.

These unsaturated ester compounds can be used in combination with each other.

Among these unsaturated ester compounds, vinyl acetate and vinyl propionate are more preferred.

In addition to the above-mentioned ethylene and unsaturated ester compounds, the monomer components constituting the ester group-containing ethylene copolymer (d) include, in an amount not exceeding about one-tenth of ethylene,
Olefins such as propylene, 1-butene, 1-hexene, etc. may be included. Further, an alkyl ester of acrylic acid or methacrylic acid such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate may be contained in an amount less than the equivalent of the unsaturated ester compound (d).

The proportion of the unsaturated ester compound (I) in the ester group-containing ethylene copolymer (d) is preferably 8 to 43% by weight, preferably 10 to 38% by weight, more preferably 15% by weight.
~35% by weight.

In a range of less than 5% by weight and more than 50% by weight, the weld strength level of the resulting resin composition tends to be low.

The molecular weight of the ester group-containing ethylene copolymer (d) is determined by the melt flow rate value (MFR; 190°C
, load 2.16kg) is more preferably in the range of 0.01 to 100g710 minutes, even more preferably 0.1 to 50g
710 minutes, particularly preferably 0.5 to 25 g/10 minutes, particularly preferably 0.5 to 20 g/10 minutes. 0.
In the range of less than 01 g/lo min and exceeding 100 g/lo min, the level of weld strength of the resulting composition becomes low.

The ester group-containing ethylene copolymer (d) can be produced by various methods. For example, in the presence of a radical generator, an unsaturated ester compound and an olefin are mixed at 50 to 4000
A method of reacting at atmospheric pressure and 40 to 300'C, a method of mixing polyethylene with an unsaturated ester compound and irradiating it with gamma rays under high vacuum to make a polymer, or a method of reacting polyethylene and an unsaturated ester compound in an organic solvent such as xylene. Examples include a method of making a copolymer in the presence of a radical generator.

There are various bonding methods between the unsaturated ester compound and the olefin constituting the copolymer (d), such as block type, random type, and graft type, all of which can be used, but random type is used. Easy to do.

<Composition ratio of constituent components> The proportion of each polymer component in the resin composition of the present invention is determined by adjusting the proportion of each polymer component in the resin composition of the present invention.
), a copolymer (c) having both an alkenyl aromatic hydrocarbon polymerization chain (c3) and an aliphatic hydrocarbon chain (c2) in the same molecular chain, and an ester group-containing ethylene copolymer (d)
The total amount is shown below as 100% by weight.

Polyolefin (a) is 20 to 77% by weight, preferably 25 to 60% by weight, more preferably 30 to 55% by weight.
, more preferably in the range of 30 to 50% by weight.

If it is less than 20% by weight, it tends to have unsatisfactory solvent resistance, and if it exceeds 77% by weight, it tends to have problems in heat-resistant rigidity.

Note that it is desirable that the polyolefin (a) forms a matrix, and it is preferable that the polyolefin (a) is added in an amount sufficient to form a continuous phase.

Polyphenylene ether (b) is 20 to 77% by weight,
Preferably 25 to 60 weight, more preferably 30 to 55
% by weight, more preferably in the range of 30 to 50% by weight.

If it is less than 20% by weight, the heat resistance rigidity level tends to be unsatisfactory, and if it exceeds 77% by weight, problems tend to occur in solvent resistance and moldability.

The copolymer (c) contains 2 to 50% by weight, preferably 6 to 3% by weight.
It is in the range of 0% by weight, more preferably 8-25% by weight, even more preferably 10-20% by weight.

If it is less than 2% by weight, problems tend to occur in the weld strength and impact resistance of the ordinary part of the composition, and if it exceeds 50% by weight, problems tend to occur in solvent resistance.

The ester group-containing ethylene copolymer (d) is 1 to 25% by weight, preferably 2 to 20% by weight, more preferably 3 to 25% by weight.
18% by weight, more preferably in the range of 4 to 15% by weight.

If it is less than 1% by weight, the weld strength of the composition tends to be at an unsatisfactory level, and if it exceeds 25% by weight, the rigidity of the composition tends to be low.

The resin composition according to the present invention may optionally include thermoplastic or thermosetting resins other than the above-mentioned polymer components, rubber components, antioxidants, weather resistance improvers, Nucleating agents, slip agents, inorganic or organic fillers and reinforcing agents, flame retardants, various colorants, antistatic agents, mold release agents, small amounts of radical generators for controlling the molecular weight of polyolefins (organic peroxides, azo compounds) , organic tin compounds, etc.).

<Blending method> As a blending method for obtaining the resin composition of the present invention, various methods of blending resins together, resins and stabilizers or colorants, or even resins and fillers can be applied. . For example, each component in powder or granule form,
First, make a uniformly dispersed mixture using a Henschel mixer, super mixer, ribbon blender, ■blengue, etc., then use a twin-screw kneading extruder, -screw kneading extruder, roll, Banbury mixer, blast mill, Brabender Plast. Melt-kneading can be performed using a graph or the like. The melt mixing temperature is usually in the range of 200°C to 350°C.

In addition, a -shaft or twin-shaft type kneading extruder with multiple raw material supply devices attached to different positions of the barrel part is used to feed the resin,
A method of supplying at least one or a part of the polymer components (a), (b), (c) and (d) constituting the present invention from different positions and sequentially kneading them to form a composition;
A method in which at least one component of each polymer component is melt-kneaded using a plurality of mixing machines and mixed and kneaded with other components in a molten state, and a common solvent is used for at least 62 components of each polymer component. Various mixing and kneading methods can be applied, such as mixing in a solution or slurry state.

The resin composition obtained as described above can be melted and mixed and then extruded into a pellet shape.

<Application of the resin composition according to the present invention> Since the resin composition of the present invention has good mechanical properties, it can be used for parts such as interior and exterior parts of automobiles, exterior parts of electrical equipment, and so-called office automation equipment. Shitsuru. As a molding method, molding methods generally applied to thermoplastic resins, ie, injection molding, extrusion acid forming, etc. can be easily molded by blow molding, etc., among which injection molding is the most preferred.

In particular, it is suitable for use in molded products that produce welds in injection molding.

[Example] Below, the present invention will be explained in more detail with reference to Examples.

The components used are as follows.

(a) Polyolefin A polypropylene homopolymer and a pyrene-ethylene block copolymer manufactured by Mitsubishi Yuka were used.

The melt flow rate (MFR) and ethylene component content are shown in Tables 2 and 3.

The ethylene component content in the polyolefin was determined by infrared spectroscopy.

(b) Polyphenylene ether resin Mitsubishi Yuka ■Prototype poly(2,6-cymethyl-1.4-
Phenylene) ether (having an intrinsic viscosity of 0.52 d!!/g measured using chloroform at 30° C.) was used.

(c) Copolymer A hydrogenated styrene-butadiene block copolymer synthesized by the method shown below was used.

A commercially available styrene-butadiene block copolymer [styrene copolymerization amount 60% by weight, trade name TR2400, manufactured by Japan Synthetic Rubber ■] was thoroughly dried and dissolved in cyclohexane from which water had been removed in an autoclave purged with nitrogen. , in the presence of nickel naphthenate catalyst, 60-70°C, lO-13
Hydrogenation treatment was carried out for 9 hours under a hydrogen pressure of 1.5 kg/cm. A poor solvent (methanol) was added to the reaction solution, the solvent and polymer were separated by filtration, and the polymer was dried under reduced pressure to obtain hydrogenated styrene. -Butadiene block copolymer was obtained. Analysis by nuclear magnetic resonance absorption spectrometry did not detect any carbon-carbon double bonds originating from the polybutadiene chain. Measurement by gel permeation chromatography showed that the The number average molecular weight was 8.1X10' and the weight average molecular weight was 10XIO'.The dynamic shear modulus was 4X10'dyn/cm'' by the above-mentioned measurement method.

Analysis by C''-NMR (nuclear magnetic resonance absorption spectrometry for carbon isotopes with a mass number of 13) shows that the amount of styrene copolymerized in polymer (c) is 60% by weight, and that the amount of butadiene in the hydrogenated polybutadiene block is 60% by weight. The portion derived from the 1.2-bond and 3.4-bond was 14.3% by weight, and the portion derived from the 1.4-bond was 85.7% by weight.

(d) Ester group-containing ethylene copolymer The ester group-containing ethylene copolymer (d5) shown in Table 1 was prepared by the following method.

In normal autoclave type polyethylene manufacturing equipment, 20
Ethylene and vinyl propionate compressed to 0.00 kg/cm2 were added together with the initiator di-t-butyl peroxide, and the temperature was maintained at 150-300"C with stirring for several minutes, and the copolymer ( d5) is separated and taken out and extruded into a strand,
It was cut into pellets using a cutter.

In addition, commercially available ethylene-vinyl acetate copolymers shown in Table 1 [trade name: Mitsubishi Polyethylene EVA V6O13, Mitsubishi Polyethylene 505, V213K, manufactured by Mitsubishi Yuka Co., Ltd., and trade name 22 Vaflex EV-170, EV-40LX,E
V45-LX, EV-150, and EV-40X, manufactured by Mitsui Polychemicals (manufactured by Kiki), were used.The amount of copolymerization of the unsaturated ester compound was measured by a saponification method.

For comparison purposes, commercially available low-density polyethylene [LPDE, trade name: Mitsubishi Polyethylene YK-30, M] shown in Table 3 was used.
FR: 4g/lO min, density: 0. 920g/cm
', manufactured by Mitsubishi Yuka ■], ethylene-acrylic acid copolymer [EAA, MFR near g/10 min, acrylic acid copolymerization amount 28.5% by weight, trade name: Yucalon-EAA A 2
20 M, manufactured by Mitsubishi Yuka ■] was used. The amount of acrylic acid copolymerized was measured by a neutralization method.

Examples 1 to 7 and Comparative Examples 1 to 10 After thoroughly mixing and stirring the amounts of each component shown in Tables 2 and 3 in a super mixer, using a TEX twin-screw extruder manufactured by Japan Steel Works, Melt and knead at a set temperature of 280°C,
After preparing the composition, it was extruded into strands and made into pellets using a cutter.

In addition, when mixing each component, 0.3 parts by weight each of Irganox 1010 (trade name, manufactured by Ciba Geigy) and Cyanox 1790 (trade name, manufactured by American Cyanamid Company) as phenolic stabilizers, and phosphorus stabilizer. Sandstarb P-EPQ (trade name,
0.3 parts by weight (manufactured by Sando ■) (synthesized amount of all polymer components 1
00 parts by weight) was added.

For evaluation testing, an in-line screw injection molding machine, model IS-90B manufactured by Toshiba Machinery Works, was used, and the cylinder temperature was set at 280°C.
Test pieces were prepared by injection molding using each of the above pellets at a mold cooling temperature of 60°C.

A test piece for weld strength measurement was prepared using the mold shown in FIG. 1 with a length of 64 mm, a width of 12.5 H, and a thickness of 4 mm, with a weld formed in the center. In Figure 1, resin is injected from the injection hole (1) in the center of the mold.
The flow is divided and flows in the direction of the arrow through the runners (2) and (3), and the specimen mold parts (4), (5), (6), (7)
They flow in from opposite directions and meet in the center.

Weld strength and Izot impact strength were measured under the following conditions.

1) Weld strength Using the above-mentioned sample for measuring weld strength, it was measured according to the following Izot impact test method without inserting a notch. The measurement atmosphere temperature is 23°C.

2) Izot impact test method Measurements were made using an Izot impact tester manufactured by Toyo Seiki Seisakusho in accordance with ISOR18O-1969 (JIS K7110) (notched Izot impact test method). The measurement atmosphere temperature is 23°C and -30°C.

Regarding the composition of the present invention and the comparative composition, the types and amounts of various components and the physical properties of various compositions obtained from these are summarized in Tables 2, 3, and 4.

[Effects of the Invention] As can be seen from Tables 2, 3, and 4, in the resin composition according to the present invention, that is, the resin composition containing polyolefin (a) and polyphenylene ether resin (b), hydrogenated styrene-butyl A polymer (c) having both an alkenyl aromatic polymer chain and an aliphatic hydrocarbon chain in the same molecular chain, exemplified by Genblock copolymer, and vinyl acetate or propionic acid in an amount within the range shown in the present invention. A composition containing an ester group-containing ethylene copolymer (d), exemplified by a polyethylene copolymer containing vinyl as a copolymer component, contains either the polymer (c) or the copolymer (d). The weld strength is significantly higher than that of a composition without the laminate, and at the same time, the impact strength of the normal part is also good, and the effects of the present invention are clear.

[Brief explanation of drawings]

FIG. 1 is a plan view of a mold for producing a test piece for weld strength measurement. l・・・・・・・・・・・・Resin injection holes 2 and 3
······runner

Claims (1)

[Claims] A thermoplastic resin composition comprising the following components and composition. (a) 20-77% by weight of polyolefin, (b) 20-77% by weight of polyphenylene ether, (c) Polymerization chain of alkenyl aromatic compound within the same molecule (
c_1) and aliphatic hydrocarbon chain (c_2) 2 to 50% by weight and (d) General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 represents a saturated aliphatic or alicyclic hydrocarbon group or an aromatic hydrocarbon group having 1 to 50 carbon atoms, and R^
2, R^3 and R^4 each represent a hydrogen atom, a methyl group or an ethyl group, at least one of R^3 and R^4 is a hydrogen atom, and X represents a direct bond or a methylene group] Contains 1-25% by weight of an ester group ethylene copolymer, which is a copolymer of 8-43% by weight of an unsaturated ester and an olefin mainly composed of ethylene.