JPH0428735A - Thermoplastic resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic resin composition that can be used as molded products, sheets, etc. by injection molding, blow molding, etc. More specifically, it consists of polyolefin resins, polyphenylene ether resins, polymers that have both an alkenyl aromatic compound polymer chain and an aliphatic hydrocarbon chain in the same molecule, and ester group-containing ethylene copolymers, which have a specific higher-order structure. However, it is a thermoplastic resin composition that has excellent mechanical properties, especially the strength of welded parts that often occur in injection molding.

[Conventional technology and issues]

Polyolefin resin has moldability, toughness, water resistance,
It has been widely used for various molded products, films, sheets, etc. because it has excellent organic solvent resistance and chemical resistance, low specific gravity, and low cost.

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

On the other hand, polyphenylene ether resin has excellent heat resistance,
Although it has rigidity, its range of use is limited because it has problems with moldability and solvent resistance. In order to improve the moldability, impact strength, etc. of this material, styrene resin is blended with it and used, but it still has problems with solvent resistance and its range of use is limited. It is not suitable for applications such as containers that require resistance to oily solvents.

In order to combine the advantages of these polyolefin resins and polyphenylene ether resins and compensate for their disadvantages,
Various blend compositions have been proposed, including compositions aimed at improving processability and tensile strength (Japanese Patent Publication No. 42-70
No. 69), but it cannot necessarily satisfy the relatively high mechanical strength level required in the industrial field.

In addition, for the purpose of further improving the compatibility of polyolefin resin and polyphenylene ether resin and improving mechanical strength, for example, a block copolymer of styrene and butadiene or a hydrogenated product thereof is blended. Composition (JP-A-5371158, JP-A-54-88)
No. 980, JP-A No. 59100159, etc.), compositions prepared by adding an inorganic filler to these components (JP-A No. 58-103556), etc. have been proposed.

In addition, a large amount of polyolefin resin exceeding 20% by weight is blended with the polyphenylene ether resin, and a diblock copolymer or radial teleblock copolymer consisting of an alkenyl aromatic compound and a conjugated diene, or Compositions containing these hydrogenated polymers have been proposed (JP-A-58-103557 and JP-A-60-76547), which improve melt processability, tensile properties, brittleness, etc. is shown.

On the other hand, in injection molding of thermoplastic resin, multiple injection ports (gates) are used in the mold to shorten the injection time when molding large molded products and to compensate for the lack of flowability of the molten resin. A method is often used in which molten resin is poured and merged between two gates. Also,
When molding a product with a complicated shape (for example, a product with holes), a method is used in which the molten resin is separated at the baffle plate in the mold and then re-merged.

However, in these cases, while t2, the joint part (
A weld (hereinafter referred to as a weld) occurs, and it is necessary to completely join this part. However, there are cases in which the weld strength is unsatisfactory, especially in blend systems whose main components are a combination of polyolefin resin and polyphenylene ether resin, and improvements have been desired.

In view of the current situation, the present invention aims to obtain a resin composition containing a polyolefin resin and a polyphenylene ether resin that has both good weld strength and a good balance of mechanical properties by developing a new formulation. It is.

[Means to solve the problem]

The present inventors investigated various blended compositions in order to correct and improve the unsatisfactory points of stiffness and impact strength of conventional polyolefin resin-polyphenylene ether resin blends. It has both a compound polymerization chain and an aliphatic hydrocarbon chain, and the dynamic shear modulus G' at 23°C is 3 x 10'dyn/
c) Consisting of a polymer in the range of 2 or higher and an ester group-containing ethylene copolymer, those exhibiting a specific higher-order structure have particularly good weld strength, and the part that does not form a weld (referred to as the normal part) It was discovered that a resin composition with relatively good mechanical strength could be obtained, and the present invention was completed.

That is, the resin composition according to the present invention contains the following components (A
), (B), (C) and <D), and component (A)
forms a continuous phase, component (B) forms a dispersed phase in component (A), and component (C) is at least partially present at and near the interface between component (A) and component (B), Component<D) is at least partially present in the dispersed phase of component (B);
The average ratio of the cross-sectional area of the component (D) dispersed phase to the cross-sectional area of the dispersed phase [including those containing and not containing component (D)] is in the range of 17% to 62%, and the component ( B
) and component (D), the resin composition is characterized in that it has a higher-order structure in which the average particle diameter of the dispersed phase of the component (D>) is in the range of 2 μm or less. The proportions of each component are component <A), component (B) and component (C
) is expressed in weight % by subtracting the total amount thereof to 100% by weight, and component (D) is expressed below as a weight ratio with component (B).

Component (A): Polyolefin resin: 30-78% by weight, Component (B): Polyphenylene ether resin, 20-68% by weight, Component (C): Alkenyl aromatic compound polymer chain (c,) in the same molecule.
and an alicyclic hydrocarbon group [(c-), and the dynamic shear modulus G' at 23°C is 3X 10 "dyn/
cm' or more: 2 to 50% by weight, and component (D) (d) unsaturated ester compound represented by general formula (I) 8 to 43
Ester group-containing ethylene copolymer, which is a copolymer of olefin containing ethylene as a main component and ethylene copolymer component (B)
The weight ratio [component (D)/component (B)] to
Amount in the range of 811 or more and 17/1 or less.

＼ R2H [In formula (I), R1 represents a saturated hydrocarbon group, alicyclic hydrocarbon group, or aromatic hydrocarbon group having 1 to 50 carbon atoms containing or not containing an oxygen atom, and R2 is hydrogen represents an atom or a methyl group, and X and Y represent a combination in which one of them is a direct bond and the other is an oxygen atom] According to the present invention, a resin containing a conventional polyolefin resin and a polyphenylene ether resin A resin composition can be obtained that exhibits good weld strength and relatively good mechanical properties in the normal portion compared to the other compositions.

[Detailed description of the invention]

The resin composition according to the present invention consists of the following components.

1. Component A: Polyolefin The polyolefin resins used in the present invention include propylene, butene-1, pentene-1, hexene 1,3-methylbutene-1,4-methylpentene-1, heptene-1,
Homopolymers of α-olefins such as octene-1, mutual copolymers in the form of random or block, random, block or graph I. or oxidized, halogenated, or sulfonated copolymers of these polymers, and exhibit at least partial crystallinity. These polymers can be obtained by polymerization or modification using known methods, and may be appropriately selected from commercially available polymers. Among them, propylene, butene-1,3-methylbutene-1,4-methyl A pentene-1 homopolymer or a copolymer consisting of a majority of these is preferred, and especially a crystalline propylene polymer exhibiting crystallinity based on tactical polypropylene chains, that is, a crystalline propylene homopolymer, a crystalline propylene homopolymer Propylene-ethylene block and random copolymers are preferred.

The melt flow rate (M
F R) (230℃, load 2.16kg) is 0.0
The range is preferably 1 to 150y/10 minutes, and 0.05 to 7
The range of 0 g/10 minutes is more preferable, especially 0.1 to
A range of 50 g/10 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 resin used in the present invention has a repeating structural unit represented by the general formula, in which the ether oxygen atom of one unit is connected to the benzene nucleus of the next adjacent unit. , n is at least 30, and Q is independently hydrogen, halogen, a hydrocarbon group not containing a tertiary α carbon atom, or at least 2
represents a monovalent substituent selected from the group consisting of a halohydrocarbon group having 5 carbon atoms, a hydrocarbonoxy group, and a halohydrocarbonoxy group having at least 2 carbon atoms between the halogen atom and the phenyl nucleus. .

Typical examples of polyphenylene ether resins include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-danityl-1,4-phenylene) ether, and poly(2-methyl-6-phenylene) ether. Ethyl-1,4-phenylene)ether, poly(2-methyl-6-broby-1)
, 4-phenylene) ether, poly(2,6-diprobyl-1,4-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-diphenyl-1,4-phenylene) ether, ,6-Simethoxy1.
4-phenylene) ether, poly(2,6-jethoxy-1,4 phenylene) ether, poly(2-methoxy-
6-ethoxy1,4-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-dibenzyl 1)
．． 4-phenylene)ether, poly(2-ethoxy1.
4-phenylene)ether, poly(2-chloro 1.4-
phenylene) ether, poly(25-dibromo1,4-
phenylene) ether and equivalents.

Also, a copolymer of 2,6-dimethylphenol and 2.3.6-)limethylphenol, a copolymer of 2,6-dimethylphenol and 2.3,5.6-titramethylphenol, 2. Mention may also be made of copolymers such as those of 6-dinitylphenol and 2,3,6-trimethylphenol.

Furthermore, the polyphenylene ether resin used in the present invention is a polyphenylene ether resin defined by the above general formula grafted with a styrene monomer (for example, styrene, p-methylstyrene, α-methylstyrene, etc.), a styrene-based It also includes modified polyphenylene ether resins such as blended resins.

Methods for producing polyphenylene ether resins corresponding to the above are known, for example, U.S. Pat.
No. 7358 specifications and Japanese Patent Publication No. 52-178
No. 80 and Japanese Unexamined Patent Publication No. 50-5+197.

Preferred groups of polyphenylene ether resins for the purposes of the present invention are those with alkyl substituents in the two positions ortho to the ether oxygen atom and polymers or copolymers of 26-dialkylphenol and 2.3.6-trialkylphenol. It is a combination.

Among these, a polymer of 2,6-dimethylphenol is particularly preferred. Further, the preferable molecular weight range is 0.35 to 0.7 dt' as a measure of the intrinsic viscosity measured in chloroform at 30°C.
/g, more preferably 0.44 to Q, 6d
l/g, more preferably from 0.48 to 0.1/g.
It is in the range of 56 dl/g.

In a range of values smaller than 0.35 dl/g, weld strength tends to decrease, and in a range of values greater than 0.7 dl19, moldability of the composition tends to decrease.

The alkenyl aromatic compound polymerization chain II (c1) C in the same molecule used in the present invention is hereinafter referred to as chain (c1).

], aliphatic hydrocarbon chain (e2) C and below, chain (c
2). ] (hereinafter referred to as polymer (C)). ] means that in the same polymer chain constituting the polymer, at least partially and at least one polymer chain portion of an alkenyl aromatic compound and a portion forming a polymer chain form of an aliphatic hydrocarbon are present. It is a polymer consisting of polymer chains that have two chains: chain (c1) and chain (c2).
) includes a so-called linear block structure in which at least one block is connected to each other linearly, a so-called radial teleblock structure in which a branch structure is formed, and a so-called graft-like branch structure in which one side is a trunk and the other is a branch. .

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

S Here, R1 and R2 are selected from the group consisting of hydrogen and a lower alkyl group or alkenyl group having 1 to 6 carbon atoms, and R
3 and R4 are hydrogen, a lower alkyl group having 1 to 6 carbon atoms,
selected from the group consisting of chlorine, bromine, R5, R6 and R
7 is selected from the group consisting of hydrogen, a lower alkyl group having 1 to 6 carbon atoms, and an alkenyl group, or R6 and R7
may form part of an aromatic ring, for example a naphthyl group.

Specific examples of alkenyl aromatic compounds include styrene, paramethylstyrene, alpha-methylstyrene, vinylxylene, vinyltoluene, vinylnaphthalene, divinylbenzene, bromostyrene, and chlorostyrene, or combinations thereof. Among these, styrene, α-methylstyrene, paramethylstyrene, vinyltoluene, and vinylxylene are preferred, and styrene is more preferred.

Series fII (c1) may contain a copolymer component other than the alkenyl aromatic compound in an amount not exceeding 25% by weight 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 11 (c2) may partially include a carbon-carbon unsaturated bond, a crosslinked structure, or a branched structure. Blocking components derived from monomers and alkenyl aromatic compounds containing atoms other than carbon such as oxygen, nitrogen, sulfur, silicon, phosphorus, and halogen as other copolymerization components within a range not exceeding 25% by weight; random,
It may be included in the form of a graft or the like.

Examples of monomers containing atoms other than carbon include maleic anhydride and its derivatives, acrylic acid and its derivatives,
Examples include vinyl chloride.

The proportion of chains (CI) in the polymer (C) is
10 to 80% by weight, excluding 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 25 to 80% by weight.
Polymer (C) may contain copolymer components or polymer chains other than chain (c1) and chain (C2) within the chain within the range of not exceeding 25% by weight, and the polymer chain may contain It may form a trunk or a branch of a branch-like chain, or a part of a block-like chain. Further, a branch point of a branched structure or a radial teleblock structure may contain a polyfunctional hydrocarbon group, an atom other than carbon, or a polyfunctional hydrocarbon group containing an atom other than carbon.

The polymer (C) used in the present invention has a dynamic shear modulus G' at 23°C of 3 x 10 "dyn/c
m2 or more, preferably 7 X 10'dyn/cm
”, more preferably I x 10'dyn/
It is a polymer with cwh2 or more.

The dynamic shear modulus G' can be measured using a variety of commercially available viscoelasticity measuring devices, including, for example, the Rheometrics Mechanical Spectrometer (Model No. RMS605).

The value measured using these devices at 23 DEG C. at a frequency of 1 hertz and a strain 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.
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 5°C, and is generally a thermoplastic material. This is a different substance from the elastomer component used to improve impact strength and impart flexibility to resins.

In order to obtain a polymer with a dynamic shear modulus of 3 x 10 @dyn/cm' or more, the chain (C1) and the chain (C2
) ratio, bonding method, each microstructure (stereoregularity, vinyl group when using polydiene, eis-1
4 bonds, ratio of jrans-1,4 bonds), etc., must be carefully selected.

The value of the dynamic shear modulus G' of the polymer (C3) is 3 × 10
If it is less than "dyn/Cm", the rigidity level of the resin composition containing it will be low, which is not preferable.

Specific examples of the polymer (C) include polystyrene-grafted polypropylene, polystyrene-grafted polyethylene, and ethylene-styrene, which are included in the range of graft copolymers and block copolymers of olefins and alkenyl aromatic compounds such as styrene. Block copolymer, propylene-styrene block copolymer, or 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, polybentenamer, 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, 1,3-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 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] refers to a structure having at least one chain block AJ derived from an alkenyl aromatic compound and at least one chain block rB derived from a conjugated diene. This is an alkenyl aromatic compound-conjugated diene block copolymer in which the aliphatic unsaturated groups in block B are reduced by hydrogenation.The arrangement of blocks A and B is a linear structure, Or, it includes those forming a so-called radial teleblock structure that forms a branched structure, and also contains random chains derived from a random copolymerization portion of a 5-fluorenyl aromatic compound and a conjugated diene in a part of these structures. Of these, those having a linear structure are preferred, and those selected from the ABA type and the AB type are more preferred.

The value of the dynamic shear modulus G' at 23°C of the partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymer (C) is 3 x 10 @dyn/am.
In order to control the ratio to 2 or more, it is necessary to select the ratio of the chain (c1) to the chain (C2) and the microstructure of the conjugated diene before hydrogenation in the chain (C2), especially the 1.2 bond or the 3,4 bond. Bonds and eis- and trans-1,4
The choice of binding ratio is important.

The proportion of the chain (C3), that is, the proportion occupied by the repeating unit 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 furthermore 55 to 70% 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 (C) is
This is a hydrogenated diene polymerization chain, and the microstructure of the double bond of the diene polymerization chain before hydrogenation (eis-
and trans-1,4 bond and 1°2 bond and 3.
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 (4 bonds). The ratio of the sum of 1, 2 bonds and 3, 4 bonds in the diene polymerization chain, or the ratio of 1, 2 bonds in the chain (C2) after hydrogenating this
The ratio of the sum of the bond and the portion derived from the 3.4 bond is preferably 0% by weight or more and 30% by weight or less, more preferably 4% by weight or more and 30% by weight or less, and even more preferably 8% by weight or more and 27% by weight or less. In a region 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.

Various molecular weights can be used for these hydrogenated block copolymers (c), but as a guideline for their molecular weight, the value of the number average molecular weight measured by gel permeation chromatography and converted to polystyrene. is 5,0OOIF/mo1 or more 500,000g/
-ol or less is preferable -10,0OOy/-0
More preferably 1 or more and 300,0OOy/l o1 or less, still more preferably 30,0000y/mo or more and 200,0OOy/l1o1 or less, particularly preferably 45,0OOy/mo& or more and 150,0OOy/l or less.
It is in the range below waol.

Measured by gel permeation chromatography, the number average molecular weight value according to the polystyrene conversion method is 50.
If it exceeds 0.000 iF/mol or if the number average molecular weight is less than 5,000y/+eo1, 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. 409
There is a method described in No. 0996, etc., 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 can be carried out using a hydrogenation catalyst in an inert solvent, for example, by the method described in Japanese Patent Publications No. 42-8704, No. 43-6636, or No. 46-20814. This is done by hydrogenation in the presence of. In this hydrogenation, at least 85% of the olefinic double bonds in polymer block B;
Preferably, 96% or more of the aromatic unsaturated bonds in the polymer block A are hydrogenated, and 25% or less of the aromatic unsaturated bonds in the polymer block A may be hydrogenated.

In addition, the Journal of Bolimar Science (Journal
al or PolyIler 5eience) P
art B Letters Volume 11.42
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 literature such as pages 7 to 434 (I973).

(D) Ester group-containing ethylene copolymer The ester group-containing ethylene copolymer (D
> is a copolymer consisting of an unsaturated ester compound represented by the following general formula (I) and ethylene or an olefin mainly consisting of ethylene.

＼ R2H [In formula (I), R1 represents a saturated hydrocarbon group, alicyclic hydrocarbon group, or aromatic hydrocarbon group having 1 to 50 carbon atoms containing or not containing an oxygen atom, and R2 is hydrogen It represents an atom or a methyl group, and represents a combination in which one of X and Y is a direct bond and the other is an oxygen atom. ] Regarding RI, the more preferable carbon number range is 1 to 30,
More preferably, it is in the range of 1 to 20.

Specific examples of RI include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, 2-ethylhexyl group, octyl group, lauryl group, and valmityl group. , stearyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, menthyl group, 2-norbornyl group, 3-norbornyl group, phenyl group, p-)lyl group, xylyl group, 2-naphthyl group, benzyl group, 2- Phenylethyl group, 2-hydroxyethyl group, 4-hydroxybutyl group, methoxymethyl group, 2-methoxyethyl group, 2-
Examples include butoxyethyl group, 4-methoxyphenyl group, 2-acetoxyethyl group, glycidyl group, 2,3-epoxybutyl group, 2,3-epoxy-2-methylpropyl group, and the like.

Note that the portion bonded to X in R1 does not contain anything that becomes an oxygen atom, and therefore does not form a peracid ester.

Specific examples of the unsaturated ester compounds used in the present invention include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate,
Lauryl acrylate, stearyl acrylate, cyclohexyl acrylate, benzyl acrylate, acrylic acid-
Acrylic acid esters such as 2-phenylethyl, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, glycidyl acrylate, and 2,3-epoxy-2-methylpropyl acrylate, and acid components of these esters. is methacrylic acid instead of acrylic acid, vinyl esters such as vinyl acetate, vinyl propionate, vinyl acetate, vinyl hexanoate, vinyl octoate, vinyl laurate, vinyl stearate, vinyl phenylacetate, etc.; Examples include 2-propenyl esters in which the unsaturated hydrocarbon moiety of the ester is not a vinyl group but a 2-propenyl group.

Among these unsaturated ester compounds, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl acetate, vinyl propionate, glycidyl acrylate, and glycidyl methacrylate are more preferred, and even more preferred is acetic acid. vinyl, glycidyl acrylate.

The above unsaturated ester compounds may be used alone or in combination.

Polyethylene that does not contain the above-mentioned unsaturated ester compound as a copolymerization component, or polyethylene that has been copolymerized with a copolymerization component that does not have an ester group, such as acrylic acid or methacrylic acid, may have an unsatisfactory weld strength level of the resin composition. Become.

As monomer components for refining the ester group-containing ethylene copolymer (D>), in addition to the above-mentioned ethylene and unsaturated ester compounds, propylene, 1- It may contain olefins such as butene, ]-hexene, etc.

The proportion of the unsaturated ester compound (I) in the ester group-containing ethylene copolymer (D) is preferably 8 to 43% by weight, preferably 12 to 33% by weight, more preferably 15% by weight.
~30% by weight. In a range of less than 8% by weight and more than 43% by weight, the weld strength level of the resulting resin composition tends to be low.

The unsaturated ester compound, ethylene and other olefins, or vinyl compounds constituting the copolymer (D>) may be bonded in a block type, random type, graft type, etc.
Various types can be mentioned and used, but a random type is easy to use.

Regarding the molecular weight (or degree of polymerization) of these ester group-containing ethylene copolymers (D), various ranges of molecular weight (or degree of polymerization) can be used, but among them, a more preferable range is determined by melting, which is one of the guidelines for molecular weight. Flow rate (MF
R) (JIS K 7210-1975), 0
．． 001-1000g/10 minutes, more preferably 0
．． 01-100g/10min, particularly preferably 0.1
~50y/10min, especially preferably 1~20
g/10 minutes. If it exceeds 1000 y/10 minutes or less than 0.001 g/10 minutes, the mechanical strength and weld strength of the composition tend to be low.

The ester group-containing ethylene copolymer (D) can be produced by various methods. ~400
A method in which polyethylene is brought into contact at 40 to 300 degrees Celsius, a method in which polyethylene is mixed with an unsaturated ester compound and irradiated with gamma rays under high vacuum to form a polymer, or a method in which polyethylene and an unsaturated ester compound are mixed in an organic solvent such as xylene. Examples include a method of making a polymer in the presence of a radical generator.

2. Composition ratio of constituent components The proportion of each polymer component in the resin composition according to the present invention is the weight of component (A), component (B), and component (C) based on the total amount of these components as 100% by weight. It is expressed in %, and component (D) is shown below as a weight ratio with component (B).

Component (A): Polyolefin resin 30-78% by weight, Preferably 35 to 70% by weight, More preferably 38 to 66% by weight, More specifically, the content is in the range of 39 to 60% by weight.

If it is less than 30% by weight, unsatisfactory solvent resistance tends to occur;
If it exceeds 78% by weight, problems tend to occur in heat resistance and rigidity.

Component (B) Polyphenylene ether resin゛20-68
% by weight, preferably 25-60% by weight, more preferably 27-55% by weight, still more preferably 31-52% by weight.

If it is less than 20% by weight, the heat resistance rigidity level tends to be unsatisfactory, and if it exceeds 68% by weight, problems tend to occur in solvent resistance and moldability.

Component (C) - A polymer having both an argenyl aromatic compound polymer chain g (e,) and an aliphatic hydrocarbon chain [(c2) in the same molecule - 2 to 50% by weight, preferably 5 to 40% by weight , more preferably from 7 to 35% by weight, still more preferably from 9 to 30% by weight.

If it is less than 2% by weight, the weld strength and impact resistance of the composition tend to be poor, and if it exceeds 50% by weight, it tends to be poor in solvent resistance.

Component (D): Ester group-containing ethylene copolymer component (D
), the ratio to the amount of component (B) is important, and the weight ratio of component (D) to component (B) [component (D)/component (B)] is 0.08. /1 or more and 1.7/1 or less, preferably 0.08/1 or more and 1/1 or less, more preferably 0.16/1 or more and 07 or less, and even more preferably 0.1
The range is 6/1 or more and 05/1 or less.

If it is less than 0.08/1, the weld strength of the composition tends to be at an unsatisfactory level, and if it exceeds 1.7/1, the rigidity and heat resistance of the composition tend to be low.

3. Higher-order structure formed by the components In the resin composition according to the present invention, the higher-order structure formed by the components is important. Component (A) forms a continuous phase, component (B
) must form an independent dispersed phase. Ingredients (A
) forms a continuous phase, good solvent resistance can be obtained. Component (, C) is at least partially present near the interface between component (A) and component (B) and acts as a compatibilizer, and component (D) is at least partially present in the dispersed phase of component (B). exists inside.

If component (C) is not present at or near the interface, the mechanical strength of the resin composition tends to be insufficient.

In the present invention, the proportion of the component (D) dispersed phase in the component (B) dispersed phase is important from the viewpoint of bringing out the effect of component <D> more efficiently and obtaining a higher level of weld strength. be. This is component (B) each dispersed phase [
The cross-sectional area of the component (D) dispersed in the component (B) that component (B) occupies in the cross-sectional area of the component (including those with and without D> as a dispersed phase) The percentage of the ratio is measured for at least 200 or more component (B) dispersed phases, and the average value (S) is used to determine the degree of the difference.

The range for (S) is 17% or more and 62% or less, more preferably 17% or more and 53% or less, and even more preferably 25% or more.
% or more and 47% or less, particularly preferably 25% or more 41
% or less. When (S) is less than 17%, the weld strength of the composition tends to be low, and when it exceeds 62%, the stiffness of the composition tends to be low.

These higher-order structures are obtained by cutting out a part of the resin composition or molded product, staining it with osmium tetroxide, ruthenium tetroxide, etc., and then creating ultrathin sections. It can be observed using a transmission electron microscope such as JEM-100CX manufactured by Co., Ltd. By the above-described staining, each polymer component in the resin composition is selectively and identifiably dyed, and the state of existence of the copolymer can be confirmed. Furthermore, the above-mentioned electron micrograph can be taken, and the area, ratio, size, etc. of the dispersed phase of each observed component can be measured using an image analysis device such as Subica ■ manufactured by Nippon Avionics Co., Ltd., for example.

In the present invention, the component (B) in the dispersed phase (
D) The morphology of the dispersed phase is also important. From the viewpoint of obtaining a higher level of weld strength, the range of the dispersed particle size of component (D>) in the component (B) dispersed phase is 2 μm or less, more preferably 1 μI or less, and even more preferably 0.5 μm.
The range is as follows. When the dispersed particle size of component (D> exceeds 2 μm), the weld strength of the composition tends to decrease.

The dispersed particle size of the component (D) dispersed phase in the component (B) dispersed phase was determined by using the above-mentioned electron micrograph using an image analysis device,
The equivalent circle diameter (R) of at least 200 or more dispersed phases of component (D) is determined and averaged as ().

The dispersed phase (component (B)) can take on various forms depending on the shearing that it receives during melt mixing and molding. Examples include a spherical shape, a spheroid shape in which the sphere is stretched in one direction, and a spheroid shape in which the sphere is stretched in two directions. An example of this is the success of a disc. For example, the size of these dispersed phases is preferably 0.01μ or more and 15μ or less on average at the longest part;
More preferably 0.05 μ- or more and 10 μ- or less, 0.1
It is particularly preferable that the ring diameter is greater than or equal to μ and less than or equal to 7 μ. In a range larger than these, the impact strength level of the resin composition tends to be low, and in a range smaller than these, it tends to become a stress concentration point.
, it tends to be difficult to contribute to improving impact strength.

In addition, various ratios of the length of the longest part and the length of the shortest part of the dispersed component (B) phase are possible;
More preferably 50/1 or less, even more preferably 20/1
It is in the range of 1 or less, particularly preferably 10/1 or less. The smaller this ratio is, the higher the weld strength level tends to be.

The form of the dispersed phase of these components (B) can be determined by their structure, which can be determined by, for example, a scanning electron micrograph of the skin layer portion of an injection molded product, the aforementioned transmission electron micrograph, and image analysis. The method for achieving this can be determined by comprehensively considering, for example, the chemical structure of each component, molecular weight, blending method, blending conditions, melt mixing method, melt mixing conditions, etc. The blending method and conditions and the crosstalk method and conditions described below are for illustrative purposes only and are not intended to be limiting.

The resin composition according to the present invention may include (5) a thermoplastic or thermosetting resin other than the above polymer components, rubber, an antioxidant, a weather resistance improver, if necessary, within a range that does not impair the object of the present invention;
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.

4. Blending and cross-mixing method The blending method for obtaining the resin composition according to the present invention generally involves blending resins together or with a stabilizer, colorant,
Furthermore, various methods of blending resin and filler can be applied.1 For example, each component in powder or granule form is made into a uniformly dispersed mixture using a Henschel mixer, a super mixer, a ribbon blender, ■ a blender, etc. Then, the mixture can be melt-kneaded using a twin-screw kneading extruder, a -screw kneading extruder, a roll, a Banbury mixer, a plastomill, a Brabender blastograph, etc.
Among these, a twin-screw kneading extruder (L/D=20 to 60) is preferred. The melt-kneading temperature is usually in the range of 200°C to 350°C.

In addition, component (A), component (B) constituting the present invention, and the components (A), (B), and
A method in which at least one of component (C) and component (D) or a part thereof is supplied from different positions and kneaded sequentially to form a composition, and at least one component of each polymer component is supplied using a plurality of mixing machines. Various mixing and mixing methods, such as mixing and kneading with other components in a molten state while melting and kneading, and mixing at least two of each polymer component in a solution or slurry state using a common solvent. The method is applicable.

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

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

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

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

〔Example〕

1. Details of each component
/10 minutes) was used.

B: BoI Phenylene Ale Mitsubishi Yuka Co., Ltd. prototype poly(2,6-dimethyl-1゜4-)unisine) ether (intrinsic viscosity value measured using chloroform at 30°C is 0.52 dl) /g> was used.

C)・Hydrogenated styrene synthesized by the method shown below.
A butadiene block copolymer was used.

In an autoclave that was sufficiently purged with nitrogen, cyclohexane from which water had been removed was used as a solvent, and in the presence of n-butyllithium containing a small amount of tetrahydrofuran.
Polymerization of styrene is carried out at a temperature of about 60-80°C, then a butadiene solution is added to polymerize the polybutadiene block chains bonded to the polystyrene chains, and then a styrene solution is added to polymerize the polystyrene block chains bonded to the polybutadiene chains. Polymerization was carried out to obtain a styrene-butadiene block copolymer containing 60% by weight of styrene block chains.

This block copolymer was thoroughly dried, dissolved in dehydrated cyclohexane in an autoclave sufficiently purged with nitrogen, and dissolved in the presence of a nickel naphthenate catalyst.
A poor solvent (methanol) was added to the 8 reaction solution which was subjected to hydrogenation treatment for 9 hours under a hydrogen pressure of 10 to 13 kg/clI2 at 0°C, and the melt cuttings and polymer were separated by filtration, and then dried under reduced pressure. , a partially hydrogenated styrene-butadiene block copolymer [abbreviation (C-1): 1] was obtained.

No carbon-carbon double bonds originating from the polybutadiene chain were detected by nuclear magnetic resonance spectroscopy. By gel permeation chromatography, the number average molecular weight in terms of polystyrene was 7.9 x 10'g/-〇! The weight average molecular weight was determined to be 9.7xlO'g/-01.

A 2-thick sheet was made by press molding, and the dynamic shear modulus was measured using a Rheometrics mechanical spectrometer (model number RMS605).
It was 3.8 x 10''dyn/Cm2 under the conditions of 3°C, frequency of 1 Hz, and strain amount of 0.1 to 1.5%.

In addition, for comparison with (C-1), a commercially available hydrogenated styrene-butadiene block copolymer, Kraton G1650 manufactured by Shell Chemical Co., Ltd. [abbreviation (C-2),
Styrene component copolymerization amount = 28% by weight] was used. By gel permeation chromatography, the number average molecular weight in terms of polystyrene was 8. I X 10'g/sol
was measured. The dynamic shear modulus was determined to be 1.5 x 10” dyn/ by the same method and conditions as in (C-1) above.
cm” was measured.

D: A commercially available ethylene-glycidyl methacrylate-vinyl acetate copolymer (trade name: BOND FAST 2B, manufactured by TAIHIKAGAKU KOGYO Co., Ltd.) was used. MFR of this item (I90℃)
is 3 g/10 minutes, the amount of glycidyl methacrylate copolymerized is about 10% by weight, and the amount of vinyl acetate copolymerized is about 7% by weight.

2. Mixing and kneading of the resin composition A predetermined amount of each component shown in Table 1 below was thoroughly mixed and stirred with a small amount of the stabilizer shown below in a super mixer, and then mixed with a TEX44 twin-screw machine manufactured by Japan Steel Works, Ltd. Using a mold extruder, the mixture was melt-kneaded at a set temperature of 280°C to form a composition, which was then extruded into a strand shape and made into a pellet using a cutter.

The extruder used was L/D = 30, and in addition to the normal hopper (first hopper), the cylinder was equipped with an intermediate hopper in the middle of the cylinder, and the structure was such that raw materials could be supplied from there as well. It has become.

The screw used for mixing has two kneading parts that apply strong shear to the resin to melt and mix it, one of which is located between the first hopper and the intermediate hopper, and the other is located between the intermediate hopper and the tip of the cylinder. It has a structure located in between.

The two screws were rotated in different directions, and the screw rotation speed was 300 revolutions per minute.

The discharge amount, that is, the total supply rate of each component supplied to the mixer was set to 33 to 38 kg per hour.

In addition, when mixing each component, use the product name Irganox 1010 (manufactured by Ciba Geigy) as a phenolic stabilizer.
, and 0.3 parts by weight of Cyanox 1790 (trade name: manufactured by American Cyanamid Company), respectively, and 0.3 parts by weight of P-EPQ (manufactured by Sandoz Co., Ltd.) as a phosphorus stabilizer (total polymer components). (based on the total amount of 100 parts by weight).

3 Creation of test pieces for physical property measurement and evaluation For each Example and each Comparative Example except Comparative Example 6, an in-line screw injection molding machine, Model IS-90B manufactured by Toshiba Machinery Co., Ltd., was used, the cylinder temperature was set at 280 ° C. Mold cooling temperature 60
Test pieces were prepared by injection molding at ℃. Regarding Comparative Example 6, a test piece was created by press molding.

A test piece for weld strength measurement was prepared using the mold shown in Figure 1, measuring 641 mm in length x 12.5 mm in width x 4 cm in thickness, with a weld in the center. In , the resin is injected from the injection hole 1 in the center of the mold, split and flows in the direction of the arrow through the runner 2.3, and flows into the specimen mold parts 4.5.6 and 7 in opposite directions, respectively. , converge in the center.

4. Measurement and Evaluation Method Weld strength and Izot impact strength were measured and evaluated under the following conditions.

1) Weld strength Using the sample for measuring weld strength described above, an Izot impact test was carried out and measured without making a notch. The measurement atmosphere temperature was 23°C.

2) Izot impact strength Measured using an Izot impact tester manufactured by Toyo Seiki Seisakusho in accordance with TSOR18O-1969 (JIS J7110) (notched Izot impact strength). The measurement atmosphere temperature was 23°C and -30°C.

3) Flexural modulus ISOR178-1974 Procedure 12 (
It was measured using an Instron testing machine according to JIS K 7203).

4) Observation and measurement of higher-order structure A part of the resin composition molded product (sheet, thickness approximately 2 ms + length approximately 174 mm x width approximately 59 @ II) was cut out from the center, dyed with ruthenium tetroxide, and then An ultrathin section was prepared using a microtome, and an electron microscope image obtained using a transmission electron microscope (JEM-100CX, manufactured by JEOL Ltd.) was photographed. The obtained photographs were analyzed using an image analysis device [Subika manufactured by Nippon Avionics Co., Ltd.]
The area ratio (I00 fraction) of component (B) dispersed phase and component (D) dispersed in component (B) dispersed phase and the area ratio (I00 fraction) of component (B) dispersed in the dispersed phase Ingredient (D)
The equivalent circular diameter of the dispersed phase was measured.

These analytical operations were performed for each of 200 dispersed phases of component (B) and 200 dispersed phases of component (D) dispersed in component (B), and their averages were determined.

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 Table 1.

In addition, regarding Comparative Example 6 in Table 1, the state of the strand extruded from the die was not stable during melt-kneading.

In addition, since the specimen obtained by press molding was bent by its own weight when measuring the bending modulus of elasticity, it was not possible to measure this, and the rigidity was judged to be extremely low, so no other physical properties were measured. .

〔Effect of the invention〕

As can be seen from Table 1, Example 1, Example 2 and Comparative Example 1,
In comparison with Comparative Example 2, in a resin composition whose main components are component (A) polyolefin resin, exemplified by polypropylene, and component (B) polyphenylene ether resin,
The value of dynamic shear modulus G' at 23°C is 3.8
Component (C), which is within the scope of the present invention, is exemplified by a hydrogenated styrene-butadiene triblock copolymer with a 10 'dyn/am' D) A resin composition comprising a combination of ester group-containing ethylene copolymers has significantly higher Izot impact strength at the weld portion than a resin composition lacking either component (C) or component (D).

In addition, from the comparison between Examples 1 and 2 and Comparative Example 3, it was found that instead of component (C), dynamic shear modulus G′ at 23°C
A resin composition containing a polymer having a value outside the range shown in the present invention has a significantly low level of stiffness, as exemplified by flexural modulus.

From the comparison between Examples 1 and 2 and Comparative Example 4, component (B)
Those in which the weight ratio of component (D) to The level of rigidity is significantly higher than that of

From the comparison between Examples 1 and 2 and Comparative Example 5, in the higher-order structure of the resin composition, the component (B) that occupies the cross-sectional area (
D) Those whose cross-sectional area ratio falls within the range of the present invention have significantly higher weld strength than those whose cross-sectional area ratio falls outside of this range.

From the comparison between Examples 1 and 2 and Comparative Example 7, component (B)
Component (D) in the dispersed phase When the average particle diameter of the dispersed phase is within the range of the present invention, the weld strength is significantly higher than that when the average particle diameter is outside the range.

In addition, from transmission electron micrographs, each Example and Comparative Example 2
It was confirmed that at least a part of component (C) existed near the interface between the component (A) continuous phase and the component (B) dispersed phase in each of the comparative examples except for Component (C). From this, it can be inferred that component (C) contributes to improving the physical property balance.

As described above, the effects of the present invention are clear.

[Brief explanation of drawings]

FIG. 1 is a diagram of a mold for manufacturing a test piece for weld strength measurement. FIG. 2 is a transmission electron micrograph showing the particle structure of the resin composition of Example 2. The magnification is 30,000 times,
61 on the photograph corresponds to 0.2 μm in the actual resin composition. FIG. 3 is a transmission electron micrograph showing the particle structure of the resin composition of Comparative Example 7. The zero magnification is the same as FIG. 2. In FIG. 1, 1... Resin injection port, 2.3... Runners 4 to 7... Test piece mold part.

Claims (1)

[Claims] 1. Consists of the following components (A), (B), (C) and (D), where component (A) forms the continuous phase and component (B) forms the component (A).
), component (C) is at least partially present at and near the interface between component (A) and component (B), and component (D) is at least partially present in component (B). Existing in the dispersed phase, the average proportion of the cross-sectional area of the component (D) dispersed phase to the cross-sectional area of the component (B) dispersed phase [including those containing and not containing component (D)] is 17%. A thermoplastic resin composition in which the average particle size of the dispersed phase of component (D) in the dispersed phase consisting of component (B) and component (D) is in the range of 2 μm or less; (A): Polyolefin resin: 30 to 78% by weight, Component (B): Polyphenylene ether resin: 20 to 68% by weight, Component (C): Alkenyl aromatic compound polymerization chain in the same molecule (c_1
) and an aliphatic hydrocarbon chain (c_2), 23
The dynamic shear modulus G' at °C is 3 x 10^8 dyn/
Polymer in the range of cm^2 or more: 2 to 50% by weight, and component (D): unsaturated ester compound represented by general formula (I) 8 to 4
Component (B
) weight ratio [component (D)/component (B)] is 0.0
Amount in the range of 8/1 or more and 1.7/1 or less. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In formula (I), R^1 is a saturated hydrocarbon group with a carbon number of 1 to 50, which may or may not contain an oxygen atom, or an alicyclic hydrocarbon group. group or aromatic hydrocarbon group, R^2 represents a hydrogen atom or a methyl group, and X and Y represent a combination in which one of them is a direct bond and the other is an oxygen atom. ]