JPH03185061A - 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 epoxy group and having high strength at the weld mark part formed by molding as well as excellent mechanical properties. CONSTITUTION:The objective thermoplastic resin composition is composed of (A) 20-77wt.% of a polyolefin such as crystalline propylene polymer, (B) 20-77wt.% of a polyphenylene ether such as 2,6-dimethylphenyl polymer, (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 having a kinetic shear modulus of >=3X10<8>dyn/cm<2> at 23 deg.C and (D) 1-25wt.% of an ethylene copolymer containing epoxy group and produced by copolymerizing an unsaturated epoxy compound, ethylene or olefins composed mainly of ethylene and, as necessary, a vinyl compound.

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, it relates to a thermoplastic resin composition containing a polyolefin, a polyphenylene ether, and an alkenyl aromatic compound polymer chain and a fatty acid in the same molecular chain. It is made of a combination of a polymer having a group hydrocarbon chain and a dynamic shear modulus in the range of 3 x 10' dyn/c- or more at 23°C and an epoxy group-containing ethylene copolymer, and is a weld that can be used for molding processing. The present invention relates to a thermoplastic resin composition that has particularly excellent partial strength.

[Conventional technical issues] 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 are blended and used to improve the moldability, impact strength, etc. of resins, but problems remain in solvent resistance, which limits the scope of their 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, they do not always 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, etc.), compositions in which an inorganic filler is added to these components (Special Publication No. 103556/1983), etc. 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 coalescence have been proposed (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 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 improve the unsatisfactory weld strength of conventional polyolefin-polyphenylene ether compositions, the present inventors investigated various blended components and found that
Block copolymers and epoxy that have both an alkenyl aromatic compound polymer chain and an aliphatic hydrocarbon chain in the same molecular chain and have a dynamic shear modulus of 3 x 10 'dyn/cm'' or more at 23°C. By blending the group-containing ethylene copolymer (d), a resin composition can be obtained that has good weld strength and relatively good mechanical strength in the non-welded part (hereinafter referred to as the normal part). They discovered this and completed the present invention.

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

(a) 20 to 77% by weight of polyolefin, (b) 20 to 77% by weight of polyphenylene ether, (c) combination of alkenyl aromatic compound polymer chain (C3) and aliphatic hydrocarbon chain (c2) in the same molecular chain. hold it,
The dynamic shear modulus (G') at 23°C is 3
Copolymers 2 to 5 in the range of O'dyn/cm2 or more
0% by weight and (d) 1 to 25% by weight of epoxy group-containing ethylene copolymer.The resin composition of the present invention exhibits better weld strength than conventional resin compositions containing polyolefin and polyphenylene ether. A resin composition with relatively good mechanical properties was obtained.

[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 is α such as propylene; butene-1: bentene-1; hexene-1; 3-methylbutene-1: 4-methylpentene-1, heptene-1; octene-1, etc. - Homopolymers of olefins, mutual copolymers in the form of random or block, these α
- A copolymer, such as a random, block or graft copolymer, mainly composed of olefins and with not more than 20% by weight of ethylene, which is at least partially crystalline.

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

Among these, a homopolymer of 6, propylene; butene-1; 3-methylbutene-1: 4-methylpentene-1, or a copolymer consisting of a majority weight of these is preferable, and especially a crystalline propylene-based polymer, That is, crystalline propylene homopolymers, crystalline propylene-ethylene block and random copolymers are 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. As a material, propylene-ethylene block copolymers (2 to 15% by weight of ethylene, preferably 4 to 12% by weight) or propylene-ethylene block copolymers, which tend to have high weld strength and exhibit crystallinity based on tactical polypropylene chains, particularly Compositions using butene-1 block copolymers (ethylene 1-13, preferably 3-IO wt% nibutene 0.5-10, preferably 2-7 wt%) tend to have higher weld strength. show.

Further examples include a mixture of a majority of these crystalline propylene polymers and a rubbery copolymer containing a plurality of α-olefins containing ethylene and, in some cases, a small amount of non-conjugated diene.

Specific examples of these α-olefin rubbers include ethylene-propylene copolymer rubber, ethylene-butene-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~
A range of 150g and 710 minutes is preferable, and 0.05 to 70g
The range of 710 minutes is more preferable, especially 0.1 to 50 minutes.
The range of g710 minutes is preferable, and more preferably 0.5 to 30 g71
A range of 0 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.

(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 hydrogen, a halogen, or a hydrocarbon group not containing a tertiary α carbon atom, a halohydrocarbon group substituted with a halogen atom via at least two carbon atoms, a hydrocarbonoxy group, and a halogen At least 2 atoms
represents a monovalent substituent selected from the group consisting of halohydrocarbonoxy groups substituted through 5 carbon atoms.

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-dipropenyl-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-styaryloxy-1,4-)unisine) 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, PoJ (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-drimethylphenol 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 styrenic monomer (for example, styrene, p-methylstyrene, α-methylstyrene, etc.),
It also includes modified polyphenylene ethers such as those blended with styrene resins.

Methods for producing polyphenylene ethers corresponding to the above are known, for example, U.S. Pat.
No. 06875, No. 3257357 and No. 325735
8 This Winter Specification 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-dialkylphenols. Or a copolymer.

Among these, a polymer of 2,6-dimethylphenol is particularly preferred. Moreover, the preferable molecular weight range is 0.35 to 0.70 dI when expressed as a measure of the intrinsic viscosity measured in chloroform at 30°C! /g, more preferably L< is 0.44 to 0.60al/g.
g(7) range, more preferably 0.48 to 0.5
It is in the range of 6 J/g. In a range of values smaller than 0.35 Iii/g, weld strength tends to decrease, and in a range of values greater than 0.70 dI/g, moldability of the composition tends to decrease.

(c) has both an alkenyl aromatic compound polymerization chain (cl) and an aliphatic hydrocarbon chain (C2) in the same molecular chain,
The dynamic shear modulus G' at 23°C is 3 x 10
The copolymer used in the present invention has an alkenyl aromatic compound polymer chain (hereinafter referred to as chain (C9)) and an aliphatic hydrocarbon chain within the same molecular chain. (C2) (hereinafter referred to as chain (C2)) (hereinafter referred to as copolymer (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
This includes a so-called linear block structure in which at least 6 blocks are connected linearly to each other, 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 having a chain (C,) 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, R6, R6 and R7 are hydrogen atoms, carbon number 1-
6 lower alkyl group or alkenyl group, or R6 and R? 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 (c,) accounts for 100% by weight of the total weight of the polymer (c)
The copolymerization component other than the alkenyl aromatic compound may be contained within a range not exceeding 25% by weight as the number of strokes.

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 includes those that are saturated by hydrogenation treatment and 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, and the chain (C2) may have a total weight of 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,
It may be included in a random, grafted, etc. format. 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 the chain (C1) in the polymer (c) is
c) 10 to 80% by weight, assuming the total weight of 100% by weight
The proportion of chain (C2) is preferably in the range of 20 to 75% by weight, more preferably in the range of 20 to 90% by weight, and more preferably in the range of 25 to 80% by weight.

The polymer (c) may contain copolymer components or polymer chains other than the chain (cl) and the chain (C2) within a range not exceeding 25% by weight, and the polymer chain is It may form a trunk or a branch of a branched chain, or a part of a block chain. Furthermore, a polyfunctional hydrocarbon group, an atom other than carbon, or a polyfunctional hydrocarbon group containing an atom other than carbon may be included at the branch point of the branched structure or radial teleblock structure.

The polymer (C) used in the present invention preferably has a dynamic shear modulus G' at 23°C of 3 x 10
'dyn/cm' or more, more preferably 7 x 10
'dyn/cm'' or more, more preferably I
It is a polymer of 10"dyn/cm" 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
MS 605) etc. Using these devices, 23
℃, frequency 1 Hz, strain amount 0.1-1.5%
The value measured in the range of is defined as the value of dynamic shear modulus G'.

Therefore, -JQ is known as rubber, room temperature e.g.
It is a substance that exhibits properties completely different from natural rubber, polybutadiene rubber, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, polyisobutylene, thiocol rubber, etc., which exhibit elasticity at 0 to 25°C, and is generally This is a different substance from the elastomer component used to improve impact strength and impart flexibility to thermoplastic resins.

Differences between the polymer (C) and substances generally known as rubber 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 I O8dyn/cm”
In order to obtain the above polymer, chain (cl) 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 value of the dynamic shear modulus of the polymer (c) at 23° C. is in a range of less than 3×10′ dyn/cm 2 , the rigidity level of the resin composition tends to be low.

Specific examples of the polymer (C) include polystyrene-grafted polypropylene, polystyrene-grafted polyethylene, ethylene-styrene block copolymers, propylene included in the range of graft copolymers and block copolymers of olefin and styrene, etc. - Styrene block copolymer; or a block copolymer consisting of an alkenyl aromatic compound and the conjugated diene shown below, or a partially hydrogenated product of 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 copolymer is 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 1-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 J has a structure having at least one chain block “A” derived from an alkenyl aromatic compound and at least one chain block rBJ derived from a conjugated diene. This block copolymer is a six-alkenyl aromatic compound-conjugated diene block copolymer in which the aliphatic unsaturated groups in block B are reduced by hydrogenation. Block A
The arrangement of and B includes a linear structure or a so-called radial teleblock structure which is 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, 6 having a linear structure is preferable, and one selected from ABA type or AB type is more preferable.

In order to control the shear modulus G' at 23°C of the partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymer to be 3 x 108 dyn/cm2 or more, the chain (C3) and Chain (c2)
and the microstructure of the conjugated diene before hydrogenation in chain (c2), especially the ratio of 1.2 or 3.4 bonds to cis- and trans-1,4-bonds, are 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 65% by weight. preferable. In a range 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, and
If the amount is greater than % 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 is a hydrogenated diene polymerization chain, and the double bond of the diene polymerization chain before hydrogenation is Structure (cis- and t
rans-1, 4 bonds, 1.2 bonds and 3.4 bonds)
The molecular structure of the chain 9M (c, l) and the copolymer (c
) are greatly affected. The proportion of the sum of 1, 2 bonds and 3.4 bonds in the diene polymerization chain, or the proportion of 1, 2 bonds and 3 in the chain (c2) after hydrogenating this
．． The proportion of the sum of the parts derived from 4 bonds is 0 to 30% by weight
is preferable, 4 to 30% by weight is more preferable, and 8 to 27% by weight is more preferable.
% by weight is more preferred. In a range exceeding 30% by weight, the dynamic shear modulus of the polymer (C) at 23° C. tends to show a low value, 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 can be used, but as a guideline for their molecular weight, those with a number average molecular weight value of 5.000 to 500.000 as measured by gel permeation chromatography and converted to polystyrene are preferred; 10.
000 to 300,000 is more preferable. More preferably, it is in the range of 30,000 to 200,000, particularly preferably 45,000 to 150,000. If the number average molecular weight exceeds 500,000 or falls below 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 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.

Additionally, the Journal of Polymer Science (Jo
urnal of Polymer 5science
Part B Letters Volume 11.
It is also possible to carry out hydrogenation using p-)-luenesulfonyl hydrazide or the like in an inert solvent according to the method shown in the literature such as (pp. 427-434 + 1973).

(d) Epoxy group-containing ethylene copolymer The epoxy group-containing ethylene copolymer used in the present invention is a copolymer consisting of an unsaturated epoxy compound and ethylene or an ethylene-based olefin, or these and a vinyl compound. (hereinafter referred to as copolymer (d)).

An unsaturated epoxy compound is a compound that has both an unsaturated group that can be copolymerized with ethylene or a vinyl compound and an epoxy group in the same molecule.

For example, unsaturated epoxy compounds such as unsaturated glycidyl esters, unsaturated glycidyl ethers, epoxy alkenes, and p-glycidyl styrenes represented by the following general formulas (I), (II), and (Ill). Yes, and these can also be used together.

Formula (wherein, R has 2 to 2 carbon atoms and has an ethylenically unsaturated bond)
18 hydrocarbon groups. ) Formula (wherein, R has 2 to 2 carbon atoms and has an ethylenically unsaturated bond)
18 hydrocarbon group; are glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butene carboxylic acid glycidyl esters, allyl glycidyl ether, 2-methylallyl glycidyl ether, p-styryl-glycidyl ether, 3,4-epoxybutene,
3.4-Epoxy-3-methyl-1-butene, 3.4-
Epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene,
Examples include vinylcyclohexene monoxide and p-glycidyloxystyrene. Among these, more preferred are allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and p-glycidyloxystyrene, still more preferred are glycidyl methacrylate and allyl glycidyl ether, and particularly preferred are glycidyl methacrylate.

In addition to ethylene, the copolymer (d) may contain other olefins in an amount not exceeding one-tenth of the olefin, such as propylene, butene-1,3-methylbutene-1,4- Examples include methylpentene-1.

Furthermore, in the present invention, vinyl compounds are used in a broad sense, and vinyl compounds include vinyl esters containing a saturated carboxylic acid component having 2 to 6 carbon atoms, and vinyl esters containing saturated carboxylic acid components having 1 to 1 carbon atoms.
Acrylic esters, methacrylic esters and maleic esters, vinyl halides, vinyl ethers, N-vinyl lactams, N-vinylcarboxylic acid amides, etc. containing saturated alcohol components in the range of 0. A combination of these is also possible. Among these, vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether are more preferred. more preferably vinyl acetate, methyl acrylate,
They are ethyl acrylate, methyl methacrylate, and ethyl methacrylate.

The proportion of the unsaturated epoxy compound in the copolymer (d) is preferably 5 to 43% by weight, preferably 8 to 43% by weight,
More preferably 8 to 33% by weight, still more preferably 12 to 33% by weight
It is in the range of 33% by weight.

In a range of less than 5% by weight and more than 43% by weight, the weld strength of the resulting resin composition tends to be low.

The proportion of the vinyl compound in the copolymer (d) is 38
The range is preferably 28% by weight or less, more preferably 25% by weight or less. Copolymer (d)
By adding a vinyl compound as a copolymerization component,
The impact strength of the resulting resin composition tends to be high, but in the region of more than 38% by weight, the impact strength tends to be low.

The bonding method of the unsaturated epoxy compound, ethylene, other olefin, or vinyl compound constituting the copolymer (d) may include block type, random type, graft type, etc.
Various types are available, and any of them can be used, but a random type is easier to use.

The molecular weight (or degree of polymerization) of the copolymer (d) can be used within various ranges;
) whose main component is ethylene, the more preferable range is 0.001-1000 g/10 min, more preferably 0.001-1000 g/10 min, expressed in terms of melt fluorate value (JIS K7210-1975), which is one of the guidelines for molecular weight. is 0.01 to 100 g/10 min, particularly preferably 0
．． 1 to 50 g/10 min, especially preferably 1 to 50 g/10 min.
It is in the range of 20g/10 minutes. If it exceeds 1000 g/10 minutes or less than 0.001 g/10 minutes, the mechanical strength and weld strength of the composition tend to be unsatisfactory.

The copolymer (d) can be produced by various methods. For example, an unsaturated epoxy compound and ethylene or an olefin mainly composed of ethylene, and in some cases, a vinyl compound is added in the presence of a radical generator. A method of reacting at ~4000 atmospheres and 40 to 300°C, a method of mixing polyethylene with an unsaturated epoxy compound, and in some cases, an additional vinyl compound, and irradiating it with gamma rays under high vacuum to create a polymer, or Examples include a method in which polyethylene and an unsaturated epoxy compound, and optionally a vinyl compound are mixed together, and a radical generator is present in an organic solvent such as xylene to prepare a polymer.

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),
The total amount of block copolymer (C) and 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, solvent resistance tends to be unsatisfactory, and if it exceeds 77% by weight, problems tend to occur 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 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 copolymer (d) contains 1 to 25% by weight, preferably 2 to 2% by weight.
The range is 0% by weight, more preferably 3-18% by weight, even more preferably 4-15% 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 a thermoplastic or thermosetting resin other than the above-mentioned polymer component, a rubber component, an antioxidant, a weather resistance improver, Nucleating agents, slip agents, inorganic or organic fillers and reinforcing agents, flame retardants.

Each f! Colorants, antistatic agents, mold release agents, small amounts of radical generators (organic peroxides,
Components such as azo compounds, organic tin compounds, etc.) can also be added.

Blending method> As a blending method for obtaining the resin composition of the present invention, various methods can be generally applied to blend resins together, resins and stabilizers or colorants, or even resins and fillers. . 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., and then a twin-screw kneading extruder, a -screw kneading extruder, a roll , a Banbury mixer, a plastomill, 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 mixing 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 mixed with other components in a molten state, and at least two of each polymer component are mixed in a common solvent. Various mixing and cross-mixing methods can be applied, such as mixing in a solution or slurry state.

The resin composition obtained as described above can be melt-kneaded 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 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 Mitsubishi Yuka ■ polypropylene homopolymer, propylene-
An ethylene block copolymer was used. Melt flow rate (MFR) and ethylene component content are shown in Table 3, Table 4,
It is shown in Tables 5 and 6.

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

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

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

(Synthesis of HSB-1) A commercially available styrene-butadiene block copolymer [styrene copolymerization amount 60% by weight, trade name TR2400, manufactured by Nihon Gosei Rubber ■] was thoroughly dried, and moisture was removed in an autoclave purged with nitrogen. Dissolved in the removed cyclohexane and heated at 60-70°C for 10-13k in the presence of nickel naphthenate catalyst.
A poor solvent (methanol) was added to the reaction solution that had been subjected to hydrogenation treatment for 9 hours under a hydrogen pressure of "g/cm", and the solvent and polymer were separated by filtration, dried under reduced pressure, and partially hydrogenated. A styrene-butadiene block copolymer was obtained.

(Synthesis of HS B-2) In a nitrogen-substituted autoclave, using cyclohexane from which water has been removed as a solvent, in the presence of n-butyllithium containing a small amount of tetrahydrofuran, about 60 to 80%
℃ temperature, then add butadiene liquid to polymerize the polybutadiene block chains bonded to the polystyrene chains, then add styrene liquid to polymerize the polystyrene block chains bonded to the polybutadiene chains, and then add the styrene liquid to polymerize the polystyrene block chains bonded to the polybutadiene chains, A styrene-butadiene block copolymer containing 60% by weight was obtained.

This styrene-butadiene block copolymer was
Hydrogenation was performed in the same manner as the hydrogenation treatment used in the synthesis of SB-1 to obtain a partially hydrogenated styrene-butadiene block copolymer.

Dynamic shear elasticity of HSB-1, HSB-2 and commercially available partially hydrogenated styrene-bucc diene block copolymers (trade names: Kraton G1652 and Kraton G1650, manufactured by Shell Chemical Co., Ltd., manufactured by Kiki) used for comparison. The measured values of the ratio and other analytical values are shown in Table 1. In addition, in analysis by ordinary nuclear magnetic resonance absorption method, no carbon-carbon double bond originating from the polybutadiene chain was detected.

In Table 1, the amount of styrene copolymerized and the ratio of the portion derived from the 1.2-bond and the portion derived from the 1.4-bond of butadiene in the hydrogenated polybutadiene block are C''-N
It was measured by MR (nuclear magnetic resonance absorption method using a carbon isotope with a mass number of 13).

The number average molecular weight was measured as a polystyrene equivalent value using gel vermini-diene chromatography.

The dynamic shear modulus (G') was measured using a Rheometrics mechanical spectrometer (model number RMS 605).
) at 23° C., 5 frequencies, 1 Hz, and a strain amount in the range of 0.1 to 1.5%.

(d) Copolymer In a normal autoclave type polyethylene manufacturing equipment, 20
Ethylene compressed to 0.00 kg/cm'', a predetermined amount of glycidyl methacrylate or glycidyl methacrylate and ethyl acrylate were added together with an initiator (di-t-butyl peroxide), and heated to 150-300°C with stirring.
The copolymer (d) was separated and taken out through a separator, extruded into a strand, and cut with a cutter to form pellets.

In addition, commercially available ethylene-glycidyl methacrylate-vinyl acetate copolymers and ethylene-glycidyl methacrylate copolymers (trade names: Bond First-2B and Bond First-2E, manufactured by Sumitomo Chemical ■) were used. The contents of each sample are shown in Table 2. In Table 2, the amounts of copolymerization of glycidyl methacrylate, vinyl acetate, and ethyl acrylate are values measured by infrared spectroscopy.

For comparison purposes, commercially available low density polyethylene (LDPE, MFR: 4.0 g/l 0 min, density:
0.920 g/cm”, product name: 2Mitsubishi Polyethylene Y
K-30 manufactured by Mitsubishi Yuka ■) and ethylene-acrylic acid copolymer (EAA, MFR+ 7g/10 min, acrylic acid copolymerization amount 28.5% by weight, product name: Yucalon-EAA
A-220M, manufactured by Mitsubishi Yuka Corporation) was used. The amount of acrylic acid copolymerized in the ethylene-acrylic acid copolymer is a value measured by a neutralization method.

Examples 1 to 8 and Comparative Examples 1 to 14 After sufficiently mixing and stirring the predetermined amounts of each component shown in Tables 2 and 3 in a super mixer, TEX manufactured by Japan Steel Works
Using a twin-screw extruder, the mixture was melted and mixed at a set temperature of 280°C to obtain a composition, which was then extruded into a strand shape and made into a pellet 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.

Using an in-line screw injection molding machine, model IS-90B manufactured by Toshiba Machinery Works, the cylinder temperature was set at 280°C.
A test piece was prepared by injection molding using each of the pellets described above 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.
Figure 1: A test piece with a weld in the center was prepared.
, 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.

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 was 23°C.

2) Izot test method Measurement was performed 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.

3) Flexural modulus ISOR17B-1974 Procedure 12 (
It was measured using an Instron testing machine according to JIS K7203).

Regarding the composition of the present invention and the comparative composition, the types and amounts of various components and the physical properties of the various compositions obtained using these are summarized in Table 3, Table 4, Table 5, and Table 6.

[Effect of the invention] In Table 3, from the comparison between Example 1, Comparative Example 1, and Comparative Example 2, polyolefin (a) and polyphenylene ether (b
), the block copolymer (c)
A resin composition containing both block copolymer (c) and copolymer (d) has significantly higher weld strength than one containing only either block copolymer (c) or copolymer (d), and the effect of the present invention is is clear. This is true for the comparison between Example 2 and Comparative Example 1 and Comparative Example 3 in Table 5, the comparison between Example 3 and Comparative Example 1 and Comparative Example 4, and the comparison between Example 5 and Example 6 in Table 4. The same applies to the comparison between Comparative Example 5 and Comparative Example 6, the comparison between Example 7 and Comparative Example 7 and Comparative Example 8, and the comparison between Example 8 and Comparative Example 11 and Comparative Example 12 in Table 6. Among the components constituting the present invention, the effects of the present invention are evident for various polyolefins.

In Table 5, Example 8, Example 9, Comparative Example 9, and Comparative Example 1
In comparison with 0, 1 block copolymer constituting the present invention (
Regarding C), the value of the dynamic shear modulus G' is within the range of the present invention, whereas the value of the flexural modulus, which is a measure of the stiffness of the composition, is at a high level. The flexural modulus values of the compositions, including those whose values were outside the range of the present invention, were extremely low, and the effect of the present invention was clearly demonstrated.

As shown in each example in Table 3, the copolymer (d) constituting the present invention can be used within the various ranges shown in the present invention, and the effects of the present invention are clear.

In addition, from the comparison between Example 8 and Comparative Examples 13 and 14 in Table 6, a composition containing a polymer (d) in which the unsaturated monomer copolymerized with ethylene is an unsaturated epoxy compound Instead of copolymer (d), low-density polyethylene containing no unsaturated monomer is copolymerized with ethylene, or unsaturated carboxylic acid is used as the unsaturated monomer copolymerized with ethylene. The weld strength is significantly higher than that of a composition containing an ethylene-acrylic acid copolymer, which clearly demonstrates the effects of the present invention.

[Brief explanation of drawings]

FIG. 1 is a plan view of a mold for producing a test piece for measuring the bend strength. 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) has both an alkenyl aromatic compound polymerization chain and an aliphatic hydrocarbon chain in the same molecular chain, and has a dynamic behavior at 23°C. 2 to 50% by weight of a copolymer having a target shear modulus of 3 x 10^8 dyn/cm^2 or more and (d) 1 to 25% by weight of an epoxy group-containing ethylene copolymer.