JPH03185059A - 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 polar group and having high strength of 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 is composed of (A) 20-70wt.% 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 polar group and produced by polymerizing (i) 5-43wt.% of a conjugated unsaturated carbonyl compound 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 O, S or =N-R<5> (R<5> is O, 1-50C saturated aliphatic group, etc.)] and (ii) olefins composed mainly of ethylene.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to thermoplastic resin compositions, and more specifically, polyolefins, polyphenylene ethers, and polyphenylene ethers containing polymeric chains of alkenyl aromatic compounds in the same molecular chain. The present invention relates to a thermoplastic resin composition comprising a polymer having both an aliphatic hydrocarbon chain and a polar group-containing ethylene copolymer, and which has particularly excellent strength in a welded portion formed 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 tit fats 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 for the purpose of combining the advantages of these polyolefins and polyphenylene ethers and compensating for their disadvantages.

For example, there are compositions (Japanese Patent Publication No. 7069/1983) aimed at improving processability and tensile strength, but they do 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, a large amount of polyolefin exceeding 20% by weight is blended with polyphenylene ether, 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, is also added. Compositions containing agglomerates have been proposed in JP-A-58-103557 and JP-A-60-76547, suggesting 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 Φ 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, thereby creating a resin composition containing polyolefin and polyphenylene ether that has both good weld strength and a good balance of mechanical properties. It's trying to get something.

[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 having both an alkenyl aromatic compound polymer chain and an aliphatic hydrocarbon chain with a polar group-containing ethylene copolymer, the weld strength is good and the weld-free part (hereinafter referred to as The present invention was completed based on the discovery that a resin composition with relatively good mechanical strength in the normal portion (referred to as the normal portion) can be obtained.

That is, the present invention is a thermoplastic resin composition comprising the following acid 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 cl) and an aliphatic hydrocarbon chain (c2) and (d) general formula: % formula % [wherein R1 is a saturated aliphatic or aliphatic represents a cyclic hydrocarbon group or an aromatic hydrocarbon group, R2,
R3 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, X is an oxygen atom, a sulfur atom, =NR' (where R1' is a hydrogen atom, (represents a saturated aliphatic or alicyclic hydrocarbon group or aromatic hydrocarbon group having 1 to 50 carbon atoms) or a direct bond] 5 to 43% by weight of a conjugated unsaturated carbonyl compound represented by
The resin composition of the present invention has a polar group-containing ethylene copolymer of 1 to 25% by weight obtained by polymerizing an olefin mainly composed of A resin composition with relatively good mechanical properties in the normal part was obtained.

[Detailed description of the invention] <Structural component> The resin composition of the present invention consists of the following components.

(a) Polyolefin The polyolefin used in the present invention is composed of propylene, butene-1, pentene-1,3-methylbutene-1, hexene-1, heptene-1,4-methylpentene-1 and octene-1. It is a copolymer consisting of a majority of these materials 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. Crystalline propylene obtained by polymerizing at least 62 monomers selected from the group consisting of 1.
Ethylene or/and butene-1 block copolymers are preferred.

Furthermore, among these, the present invention uses propylene-ethylene block or random copolymers and propylene-ethylene-butene-1 block or random copolymers that exhibit crystallinity based on isotactic polypropylene chains. In the composition, the weld strength tends to be high, and in particular, a propylene-ethylene block copolymer (2 to 15% by weight of ethylene, preferably 4 to 12% by weight) or a propylene block copolymer that exhibits crystallinity based on a rigid polypropylene chain. - Compositions using ethylene-butene-1 block copolymer (ethylene 1-13, preferably 3-10% by weight nibutene 0.5-10, preferably 2-7% by weight) have higher weld strength. It shows a tendency to

Furthermore, a mixture of a majority of these crystalline propylene polymers with a rubbery copolymer containing multiple α-olefins containing ethylene and, in some cases, a small amount of non-conjugated diene, can improve the balance of mechanical properties. Can be used on surfaces.

Specific examples of these α-olefin rubbers include ethylene-propylene copolymer rubber, ethylene-phthene-1 copolymer rubber, ethylene-propylene-butene-1 copolymer rubber, and 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°C, load 2.16kg) is 0.01 to 1
The range of 50g/710 minutes is preferable, and 0.05 to 70g/
The range of lo is more preferable, especially O, 1 to 50 g.
The range of 710 minutes is preferable, and further 0.5 to 30g710
A range of minutes is preferred. If the MFH value is higher than this range, the level of mechanical property balance will be low, and if it is lower than this range, moldability will be difficult, which is not preferable.

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

(b) Polyphenylene ether The polyphenylene ether used in the present invention has a structural unit represented by the general formula, where n is at least 30
and Q is each independently a hydrogen atom, a halogen atom, a hydrocarbon group not containing a tertiary alpha carbon atom, a hydrocarbon group in which a halogen atom is substituted through at least 62 carbon atoms, a hydrocarbon group containing at least 62 carbon atoms, and It represents a monovalent substituent selected from the group consisting of a hydrogenoxy group and a halohydrocarbonoxy group substituted via at least two carbon atoms with a halogen atom.

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-
1゜4-phenylene)ether, poly(2-ethyl 6-
Broby-1,4-phenylene)ether, poly(2,
6-Cyptyl-1,4-phenylene)ether, poly(
2,6-dipropenyl-1,4-phenylene) ether, poly(2,6-dilauryl-1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether -Simethoxy1,4-phenylene)ether, poly(2,6-jethoxy-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-14)
-phenylene) ether, poly(2,6-dipendylene-1,4-phenylene) ether, poly(2-ethoxy-
1,4-phenylene) ether, BoIJ (2-10-1,4-phenylene) ether, poly(2,5-dibromo-1,4-phenylene) ether, and the like.

Also, a copolymer of 2,6-dimethylphenol and 2.3.6-dolimethylphenol, a copolymer of 2,6-dimethylphenol and 2.3.5.6-titramethylphenol, 2.6 Copolymers such as a copolymer of -ethylphenol and 2.3.6-1-limethylphenol can also 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 (for example, styrene, p-methylstyrene, a-methylstyrene, etc.), or 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 Publications No. 52-17880 and Japanese Patent Application Laid-Open No. 50-51197.

Preferred groups of polyphenylene ethers for the purposes of the present invention are those with alkyl substituents in the two positions ortho to the ether oxygen atom and polymers of 2,6-dialkylphenols and 2,3,6-1-realkylphenols. Or a copolymer.

Among these, a polymer of 2,6-dimethylphenol is particularly preferred. In addition, the preferable molecular weight range is 0.35 to 0.70 dl/g, more preferably 0.44 to 0.70 dl/g, as a measure of the intrinsic viscosity measured in chloroform at 30°C. 60dl/g
more preferably 0.48 to 0.56 dI
/g range. o, in the range of values smaller than 35d1/g, the weld strength tends to decrease;
．． In a range of values greater than 70 dI/g, the moldability of the composition tends to decrease.

(c) A copolymer having both an alkenyl aromatic compound polymerization chain (c,) and an aliphatic hydrocarbon chain (c2) in the same molecular chain Alkenyl aromatic compound polymerization in the same molecule used in the present invention A copolymer (c) (hereinafter referred to as a copolymer (c)) having both a chain (c1) (hereinafter referred to as a chain (cl)) and an aliphatic hydrocarbon chain (c2) (hereinafter referred to as a chain (c2)).
(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 (c7) and the chain (c2) are
This 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' Here, R' and R2 are hydrogen atoms, lower alkyl groups having 1 to 6 carbon atoms, or alkenyl groups, and R3 and R4 are hydrogen atoms, lower alkyl groups having 1 to 6 carbon atoms, chlorine or bromine atoms. Yes, R8, R6 and R7 are hydrogen atoms, carbon number 1-
6 lower alkyl or alkenyl group, or R6 and R7 together with the carbon atom to which they are attached form a naphthyl group.

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

The chain (c3) may contain a copolymer component other than the alkenyl aromatic compound in an amount not exceeding 25% by weight, expressed 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. This chain (c2), which is saturated by a hydrogenation treatment method and includes structures similar to or similar to the polymer chain of olefins, partially has carbon-carbon unsaturated bonds, crosslinked structures, and branched structures. The chain (c2) may contain 100% of the total weight of the polymer (c).
Monomers and alkenyl aromatics containing atoms other than carbon such as oxygen, nitrogen, sulfur, silicon, phosphorus, halogen, etc. as other copolymerization components, within a range not exceeding 25% by weight as the number of strokes expressed as weight%. Blocks components derived from group compounds,
Examples of monomers containing atoms other than carbon, which may be included in random, grafted, etc. forms, include maleic anhydride and its derivatives, acrylic acid and its derivatives, vinyl chloride, and the like.

The proportion of the chain (c1) in the polymer (c) is
10 to 80% by weight, assuming the total weight of c) as 100% by weight
The proportion of chain (c2) is preferably in the range of 20 to 90% by weight, more preferably 30 to 75% by weight.
Polymer (c) may contain copolymer components or polymer chains other than chain (c5) and chain (c2) within the chain within a range not exceeding 25% by weight, and the polymer chain may contain It may form a trunk or branch of a branched chain, or a part of a block chain, or at a branch point of a branched structure or radial teleblock structure, a polyfunctional hydrocarbon group or an atom other than carbon, carbon may contain polyfunctional hydrocarbon groups containing atoms other than .

The polymer (c) used in the present invention preferably has a dynamic shear modulus G' at 23°C of 3 x 108
dyn/cm” or more, more preferably 7 x 108
dyn/Cm2 or more, more preferably I x 10
' It is a polymer with dyn/Cm2 or more.

The dynamic shear modulus G' can be measured using various commercially available viscoelasticity measurement devices. For example, the Rheometrics mechanical spectrometer (model number R
MS605) etc. Using these devices, 23℃
The value measured at a frequency of 1 Hz and a strain amount in the range of 0.1 to 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, polyisobutylene, 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').

In order to obtain a polymer with a dynamic shear modulus of 3 x 108 dyn/Cm2 or more, the chain (c3) and the chain (c2
), 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, 13-butadiene, 2-methyl-
Those selected from 1,3-butadiene are preferred, and 1,3-butadiene is more preferred. In addition to these conjugated dienes, a small amount of lower olefinic hydrocarbons such as ethylene, propylene, and l-butene, cyclopentadiene, and non-conjugated dienes may also 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 an alkenyl aromatic compound having a structure having at least one chain block rAJ derived from an alkenyl aromatic compound and at least one chain block rBJ derived from a conjugated diene. This is an aromatic compound-conjugated diene block copolymer in which the aliphatic unsaturated groups in block B are reduced by hydrogenation. Block A
The sequences of and B include those that form a linear structure or those that form a so-called radial teleblock structure that forms a branched structure, and some of these structures include a combination of an alkenyl aromatic compound and a conjugated diene. It may contain random chains derived from random copolymerization moieties. Among these, those having a powdery structure are preferred, and those selected from A-B-A type or A-B type are more preferred.

In the partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymer (c), the dynamic shear modulus at 23°C is 3 X I O' dyn/
In order to control it so that it is more than
) and chain (c2) and the microstructure of the conjugated diene before hydrogenation in chain (c2), especially 1.2
bond or 3.4 bond and cis- and trans-1,4
- The choice of the ratio of binding is important.

The proportion of the chain (cl), that is, the proportion occupied by the repeating units derived from the alkenyl aromatic compound, is preferably in the range of 55 to 80% by weight, more preferably in the range of 55 to 75% by weight, and even more preferably in the range of 55 to 70% by weight. Preferably, in a range of 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 rigidity level of the resin composition tends to be low.
If the amount is more than 0% 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 bond and 1.2 bond and 3,4
The molecular structure of the chain (c2) after hydrogenation and the physical properties of the copolymer (c) are greatly influenced by the proportion of the sum of 1, 2 bonds and 3.4 bonds in the total number of bonds (bonds). The proportion of the sum of 1, 2 bonds and 3.4 bonds in the diene polymerization chain, or the proportion of the sum of the parts derived from 1, 2 bonds and 3.4 bonds in the chain (c2) after hydrogenating this is preferably 0 to 30% by weight, more preferably 4 to 30% by weight, and 8 to 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. Further, about 25% or less of the aromatic unsaturated bonds derived from the alkenyl aromatic compound may be hydrogenated.

Regarding the molecular weight of these hydrogenated block copolymers,
Various types of 6 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, and 10. ，
000 to 300.000 is more preferable. More preferably 30,000 to 200,000, and h 4M
I4112-4=l/IJA r l"1
It is in the range of 8I"l -I e 8I"11"11"1. If the number average molecular weight exceeds 500,000 or is less than 5,000, the mechanical strength of the composition tends to 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. 3,595,942 and US Pat. No. 4,090
There is a method described in each specification of No. 996, in which block copolymerization is carried out in an inert solvent using a lithium catalyst or a Ziegler type catalyst.

Hydrogenation treatment of these block copolymers is described, for example, in Japanese Patent Publications Nos. 42-8704, 43-6636, and 4B.
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% of the olefinic type double bonds in polymer block B, preferably / J + OQ IMML-A < ML-118:%
+n Jr h fir AH-in1,.

25% or less of the aromatic unsaturated bonds in Ri A may be hydrogenated.

In addition, the Journal of Polymer Science (Jou
rnal of Polymer 5science
Part B Letters Volume 11.4
Hydrogenation can also be carried out using p-1 luenesulfonyl hydrazide or the like in an inert solvent according to the method shown in literature such as P. 27-434 (1973).

(d) Polar group-containing ethylene copolymer The polar group-containing ethylene copolymer (d) used in the present invention is mainly composed of a conjugated unsaturated carbonyl compound represented by the following general formula (I) and ethylene or ethylene. It is a copolymer with an olefin component.

R''R' [wherein R' represents a saturated aliphatic or alicyclic hydrocarbon group or an aromatic hydrocarbon group having 1 to 50 carbon atoms, R2,
R8 and R4 each represent a hydrogen atom, a methyl group, or an ethyl group, at least six of R3 and R4 are hydrogen atoms, X is an oxygen atom, a sulfur atom, and =N-R' (here, R5 is hydrogen (represents an atom, a saturated aliphatic or alicyclic hydrocarbon group or an aromatic hydrocarbon group having 1 to 50 carbon atoms) or a direct bond] The preferred range of the number of carbon atoms for R' is 1 to 24, still more preferably 1 to 10, particularly preferably 1 to 6, particularly preferably 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 still more preferably a hydrogen atom.

More preferably, the combination of R3 and R4 is a case where both are hydrogen atoms.

A more preferable selection for X is a direct bond or a bond through an oxygen atom, and even more preferably an oxygen atom bond.

-M Specific examples of the conjugated unsaturated carbonyl compound represented by formula (I) include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, and acrylic acid. 2-ethylhexyl, pentyl acrylate, octyl acrylate, lauryl acrylate, palmityl acrylate, stearyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, 2-methylcyclopentyl acrylate, 2-methylcyclohexyl acrylate, 4-acrylate methylcyclohexyl,
Acrylic esters such as phenyl acrylate, paratolyl acrylate, and naphthyl acrylate: Regarding the above acrylic ester compounds, methacrylic ester compounds in which the unsaturated carboxylic acid component constituting the ester is methacrylic acid instead of acrylic acid: Ester The unsaturated carboxylic acids constituting the acrylic acid are cis-2-butenoic acid and trans-2-butene instead of acrylic acid.
ノ drunk a ・ノ 〃+1 + 丙8勺工 ncom
4-convex F; Conjugated unsaturated acid esters that are carboxylic acids; methyl thioacrylate, ethyl thioacrylate, cyclohexyl thioacrylate, phenyl thioacrylate,
paratolyl thioacrylate, methyl thiomethacrylate,
Ethyl thiomethacrylate, octyl thiomethacrylate,
Conjugated unsaturated thiocarboxylic acid esters such as cyclohexyl thiomethacrylate and phenyl thiomethacrylate: acrylic acid amide, methacrylic acid amide, N-methylacrylic acid amide, N-ethylacrylic acid amide, N-octylacrylic acid amide, N-cyclohexyl Acrylic acid amide, N-phenylacrylic acid amide, N,N-dimethylacrylic acid amide, N,N-diethylacrylic acid amide, N-methyl-N-ethylacrylic acid amide, N-methyl-N-phenylacrylic acid amide , N-methyl-N-
Acrylic acid amide compounds such as cyclohexyl acryl amide: The conjugated unsaturated carboxylic acid component constituting these acryl amide is substituted for acrylic acid by methacrylic acid,
Conjugated unsaturated carboxylic acid amides, which are conjugated unsaturated carboxylic acids such as cyamyl-2-butenoic acid, trans-2-butenoic acid, tiglic acid, and angelic acid; methyl vinyl ketone, ethyl vinyl ketone, phenyl vinyl ketone, etc. Examples include conjugated unsaturated ketones.

Among these conjugated unsaturated carbonyl compounds, it is more preferable that R1 in the general formula (I) is an alkyl group having 1 to 50 carbon atoms, R2 is a hydrogen atom or a methyl group, and both R3 and R4 are A hydrogen atom, and X is an oxygen atom, specifically an alkyl ester of acrylic acid or methacrylic acid with an alkyl group having 1 to 5 carbon atoms.
It is in the range of 0, more preferably in the range of 1 to 25, particularly preferably in the range of 1 to 10, particularly preferably methyl, ethyl or acrylic acid or methacrylate. It is a propyl ester.

In addition to the above-mentioned ethylene and conjugated unsaturated carbonyl compounds, the monomer components constituting the polar group-containing ethylene copolymer (d) include propylene and l-butene, within a range not exceeding about one-tenth of ethylene. , 1-hexene, and the like.

Further, a carboxylic acid unsaturated ester compound such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl phenylacetate, allyl acetate, etc. may be contained in an amount less than the equivalent of the conjugated unsaturated carbonyl compound (d).

The proportion of the conjugated unsaturated carbonyl compound (I) in the polar group-containing ethylene copolymer (d) is preferably 5 to 43% by weight, preferably 8 to 35% by weight, more preferably 11% by weight.
~35% by weight, more preferably 15-30% by weight. In a range of less than 5% by weight and more than 43% by weight, the weld strength level of the resulting resin composition becomes low.

The molecular weight of the polar group-containing ethylene copolymer (d) is determined by the melt flow rate value (MFR; temperature: 190°C).
, load 2.16kg) is 0.001~500g/lo
The range of minutes is more preferable, and even more preferably 0.01 to 5 minutes.
0 g/10 min, particularly preferably 0.05 to log710
min, particularly preferably 0.1 to 5 g/10 min.

If the melt flow rate value exceeds 500g710 minutes,
Weld strength level is lowered to 0.001g/10
If it is less than 1 minute, the flowability of the composition will be difficult.

The polar group-containing ethylene copolymer (d) can be produced by various methods. For example, a conjugated unsaturated carbonyl compound, an olefin, and in some cases a vinyl compound are added and the mixture is heated at 50 to 4000 atm and 40 to
A method of reacting at 300°C, a method of mixing polyethylene with a conjugated unsaturated carbonyl compound, and in some cases, an additional carboxylic acid unsaturated ester compound, etc., and irradiating it with gamma rays under high vacuum to create a polymer, or Botethylene, a polyethylene copolymer, etc., a conjugated unsaturated carbonyl compound, and optionally a carboxylic acid unsaturated ester compound are mixed, and a radical generator is present in an organic solvent such as xylene. Nano)e? −
4-:, J-1xlr xRl! k IJ'% b
9. There are various bonding methods between the conjugated unsaturated carbonyl compound and the olefin constituting the copolymer (d), such as block type, random type, and graft type, all of which can be used, but the random type is Easy to use.

Composition ratio of constituent components> The proportion of each polymer component in the resin composition of the present invention is determined by polyolefin (a), polyphenylene ether (b), polyphenylene ether (b),
Alkenyl aromatic hydrocarbon polymerization chain (c
The total amount of the copolymer (c) having both 1) and an aliphatic hydrocarbon chain (c2) and the polar group-containing ethylene copolymer (d) 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, the solvent resistance is unsatisfactory +1-
Me no ri ri meeting u hi eta ni pu I tofu 4 bh yuan
Piece ← l-e zero green yo righteousness (this tends to occur easily).

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 to 25% by weight, even more preferably 10 to 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 polar group-containing ethylene copolymer (d) is 1 to 25% by weight
, preferably 2 to 20% by weight, more preferably 3 to 18% by weight
% 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.) may also be added.

<Blending method> As a blending method for obtaining the resin composition of the present invention, various methods of blending -89 with resins or resins with stabilizers and colorants, and furthermore with resins and fillers can be applied. I can do it. For example, powdered or granular components are first made into a uniformly dispersed mixture using a Henschel mixer super mixer, a ribbon blender, a blender, etc.
Next, melt-kneading can be carried out using a twin-screw kneading extruder, a -screw kneading extruder, a roll, a Banbury mixer, a blast mill, a Brabender plastograph, or the like. The melt crosstalk 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;
Using multiple mixing machines, at least one component of each polymer component is melt-kneaded and mixed with the other components in a molten state to form a mixture. Various mixing/intermixing methods can be applied, such as mixing two components in a solution or slurry state using a common solvent.

The resin composition obtained as described above can be melted and mixed and then extruded to form pellets.

<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 can be easily performed by molding methods generally applied to thermoplastic resins, such as injection molding, extrusion molding, or blow molding, among which injection molding is most preferred.

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

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

The components used are as follows.

(a) Polyolefin A propylene-ethylene block copolymer manufactured by Mitsubishi Yuka ■ was used. Table 2 shows the melt flow rate (MFR) and ethylene component content.

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

(b) Polyphenylene ether Mitsubishi Yuka ■ A prototype poly(2,6-dimethyl 1,4-phenylene) ether (intrinsic viscosity value measured using chloroform at 30° C.: 0.52 df/g) was used.

(c) A copolymer having both an alkenyl aromatic compound polymer chain (cl) and an aliphatic hydrocarbon chain (c2) in the same molecule A hydrogenated styrene-butadiene block copolymer synthesized by the method shown below. used.

A commercially available styrene-butadiene block copolymer [styrene copolymerization amount 60% by weight, trade name TR2400, manufactured by Nihon Gosei Rubber ■] was thoroughly dried.

In an autoclave purged with nitrogen, dissolved in cyclohexane from which moisture had been removed, in the presence of a nickel naphthenate catalyst,
Hydrogenation treatment was performed for 9 hours at 60-70°C under hydrogen pressure of 10-13 kg/cm. A poor solvent (methanol) was added to the reaction solution, and the solvent and polymer were separated by filtration.
Drying under reduced pressure was performed to obtain a hydrogenated styrene-butadiene block copolymer. In analysis by nuclear magnetic resonance absorption, no carbon-carbon double bond originating from the polybutadiene chain was detected. As measured by gel permeation chromatography, the number average molecular weight in terms of polystyrene was 8.1 x 104, and the weight average molecular weight was 10XIO'. The dynamic shear modulus according to the above measurement method is 4 × 10
'dyn/cm'.

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 1.2 bonds and 3.4 bonds was 14.3% by weight, and the portion derived from 1,4-bonds was 85.7% by weight.

(d) Polar group-containing ethylene copolymer The polar group-containing ethylene copolymer (d6) and (
d7) was prepared by the following method.

In normal autoclave type polyethylene manufacturing equipment, 20
Ethylene compressed to 00 kg/cm2 and (d6
), methyl methacrylate or (d7), ethyl acrylate is added together with the initiator ni-t-butyl peroxide, and the temperature is maintained at 150 to 300°C with stirring for several minutes to carry out bulk polymerization. The copolymer (d) was separated and taken out through a filter, extruded into a strand, and cut into pellets with a cutter.

In addition, ethylene-methyl acrylate copolymer (trade name: Yucalon HMA) (di) manufactured by Mitsubishi Yuka ■ shown in Table 1,
(d2) and (d4), and ethylene-ethyl acrylate copolymer (trade name: Yucalon EEA) (d3) and (d5) were used. Table 1 shows the characteristic values of each copolymer (d).
and shown in Table 2. The content of conjugated unsaturated carbonyl compounds in each sample was measured by elemental analysis and infrared spectroscopy.

For comparison purposes, commercially available low-density polyethylene [LDPE, MFR+ 4g710min, density: 0] shown in Table 2 was used.
．． 920g/cm3. Trade name: Mitsubishi Polyethylene YK-30
, Mitsubishi Yuka (unmanufactured) and ethylene-acrylic acid copolymer [EAA, MFR: 7g/10 min, acrylic acid copolymerization amount = 8.5% by weight, trade name: Yucalon EAA A22
0M, manufactured by Mitsubishi Yuka ■] was used. The amount of acrylic acid copolymerized was measured by a neutralization method.

Examples 1 to 6 and Comparative Examples 1 to 5 After thoroughly mixing and stirring the amounts of each component shown in Table 2 in a super mixer, the temperature was set at 280 using a TEX twin-screw extruder made by Japan Steel Works (Kibu). The mixture was melt-kneaded at °C to form a composition, extruded into strands, and pelletized using a cutter.

In addition, when mixing and purifying 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 a phenolic 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.

Using an in-line screw type injection molding machine, model 1S-90B manufactured by Toshiba Machinery Co., Ltd., the setting temperature was 280°C.
Test pieces were prepared by injection molding using each of the above pellets at a mold cooling temperature of 60°C.

The test piece for weld strength measurement was 64 mm long x 12.5 mm wide x 4 mm thick using the mold shown in Figure 1.
A test piece with a weld in the center was prepared. Figure 1
, the resin is injected from the injection hole (1) in the center of the mold, split into two parts, and flowed in the direction of the arrow through the runners (2) and (3), and then into the test piece mold parts (4) and (5). , (6), (7
) from opposite directions and merge in the center.

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

(2) Weld strength Weld strength was measured using the above-mentioned specimen for measuring weld strength, without making a notch, according to the Izot impact test method described below. The measurement atmosphere temperature was 23°C.

2) Izot test method Measurement was carried out using an Izot impact tester manufactured by Toyo Seiki Seisakusho in accordance with ISOR18O-1969 (JIS 7110) (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 1 and 2.

[Effect of the invention] As can be seen from Table 2, the resin composition according to the present invention, namely polyolefin (a) and polyphenylene ether (b)
In the resin composition containing hydrogenated styrene-
A polymer (c) having both an alkenyl aromatic polymer chain and an aliphatic hydrocarbon chain in the same molecular chain, exemplified by a butadiene block copolymer; Compared to a composition that does not contain either polar group-containing ethylene copolymer (d), exemplified by a polyethylene copolymer containing a conjugated unsaturated carbonyl compound such as ethyl acid or methyl methacrylate as a copolymerization component. The weld strength was extremely high, and at the same time, the impact strength of the normal part was 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, X is an oxygen atom, a sulfur atom, =N-R
^5 (here, R^5 represents a hydrogen atom, a saturated aliphatic or alicyclic hydrocarbon group having 1 to 50 carbon atoms, or an aromatic hydrocarbon group) or a direct bond] Conjugated unsaturated carbonyl represented by Compound 5-43% by weight
1 to 25% by weight of a polar group-containing ethylene copolymer obtained by polymerizing an olefin mainly composed of and ethylene.