JPH0198647A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition excellent in mechanical properties, solvent resistance and moldability, by mixing a specified PP resin with a polyphenylene ether resin and a specified hydrogenated alkenylaromatic compound/conjugated diene block copolymer. CONSTITUTION:A resin composition comprises 20-80wt.% polypropylene resin (a) which is an alpha-olefin polymer based on propylene, possesses crystallinity ascribable to isotactic polypropylene, has a content of polymer units derived from alpha-olefins other than propylene in the range of 1-30wt.%, 20-80wt.% polyphenylene ether resin (b), and 4-50wt.% hydrogenated alkenyl-aromatic compound/conjugated diene block copolymer (c) containing 45-80wt.% polymer units derived from an alkenyl-aromatic compound. The content of alpha-olefins as comonomer components, other than propylene, in said resin (c) is preferably 1-30wt.%. From the viewpoint of attaining a high impact resistance, it is preferably above 1wt.%, and from the viewpoint of mechanical properties, it is preferably in the range of below 30wt.%.

Description

Detailed Description of the Invention (I) Background of the Invention 1. Technical Field The present invention exhibits a particularly excellent balance of mechanical properties, centering on impact strength, and has excellent bottom formability, solvent resistance, and chemical resistance. Concerning good resin M acid.

For details, see polypropylene resins with specific properties, polyphenylene ether resins, and hydrogenated alkenyl aromatic compounds.
Made of a conjugated diene block copolymer, it has an excellent balance of mechanical properties centered on impact strength, and has good moldability, organic solvent resistance, and chemical resistance, making it suitable for injection molding, extrusion molding, or blow molding. Concerning suitable resin compositions.

2. Prior art Polyolefins have been widely used for various molded products and sheets because they have excellent moldability, toughness, water resistance, organic solvent resistance, chemical resistance, etc., low specific gravity, and low cost. It has heat resistance that needs improvement, which is an obstacle to developing new uses.

On the other hand, polyphenylene ether resin has excellent heat resistance.
-i, but since there are hot spots in moldability and solvent resistance,
Its range of use is limited. For example, it is blended with styrene resin for the purpose of improving molding processability and impact strength, etc., but it has problems with solvent resistance, so there is a limit to its range of use. It is not suitable for fields where durability is required. Various blend compositions have been proposed to combine the advantages of these polyolefins and polyphenylene ethers and compensate for their disadvantages.For example, various blend compositions have been proposed to improve processability and tensile strength. There is a composition (Japanese Patent Publication No. 42-7069), 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 and polyphenylene ether resin and improving mechanical strength, for example, block copolymers of styrene and butadiene are made by blending these hydrogenated substances. Composition (Unexamined Japanese Patent Publication No. 1983)
No.-71158, JP-A No. 54-88960, Jikai Wd
59-10 (responses to various publications in No. 1159), f111 bottoms made by adding inorganic fillers to these components (Japanese Patent Application Laid-open No. 103556/1983), etc. have been proposed, which improve moldability and mechanical properties. Strength can be improved, but the amount of polyolefin blended is small or the matrix (continuous phase)
Since it is made of a polyphenylene ether resin or a combination of this and a styrene resin, the organic solvent resistance of the polyolefin is not fully exhibited. In addition, a large amount of polyolefin exceeding 20 couls of 4 tons 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 and these hydrogen are added as compatibilizers. Compositions containing added polymers have been proposed (Japanese Patent Application Laid-open Nos. 58-103557 and 60-76547), and as shown in the publications, low-density polyethylene is used as an example of polyolefin. and a blend of this and a polyphenylene ether resin, the compatibility is improved by the distribution of hydrogenation of the alkenyl aromatic compound-conjugated diene diblock co-Ji adduct.
It is believed that issues such as timeliness and vulnerability can be improved. but,
Improving compatibility alone is not sufficient to satisfy the properties required of resins in general. For example, time opening 1j560-7
No. 6547 discloses a 9m base material, i.e., polyphenylene ether, low-density polyethylene as a large amount of polyolefin, and a hydrogenated alkenyl aromatic-conjugated diene diblock copolymer as a compatibilizing component for both components. Three-component resin compositions have a significantly inferior level of rigidity, which limits their use. Among the above combinations, resin compositions using polypropylene as the polyolefin have slightly improved rigidity and heat resistance, but there are cases where they are insufficient for practical use, and there is room for improvement.

[Summary of the Old Invention The present invention further improves the above-mentioned points, and is applicable to various application fields, such as relatively high mechanical strength required for heat distribution of industrial parts, etc. The object of the present invention is to provide a resin composition that exhibits good solvent resistance and moldability.

For this purpose, we conducted a study on polyphenylene ether resin, polyolefin, and compounding agents for each building.
In the combination of a polyphenylene ether resin and a polyolefin resin with a hydrogenated alkenyl aromatic compound-conjugated diene block copolymer having a specific property, a polypropylene resin having a specific range of properties is used as the main component as the polyolefin resin. The present invention has been completed based on the discovery that a resin composition with an excellent balance of mechanical properties, excellent solvent resistance and molding processability can be obtained by obtaining a particularly excellent impact strength level.

Therefore, the resin composition according to the present invention is an α-olefin polymer having propylene as a main component, an a-olefin polymer based on tactical polypropylene, which exhibits crystallinity, and has a content of polymerized units derived from an α-olefin other than propylene of 1. ~
Polyolefin resin (a) 2O in the range of 30% by weight
~80% by weight, polyphenylene ether resin Φ)20~
80 fifi%, heavy unit derived from alkenyl aromatization adduct t-45 weight thttII excess 80] l [hydrogenated alkenyl aromatic compound-conjugated diene block copolymer (C) containing below weight ratio 4 to 50 weight ratio It is a resin composition consisting of.

According to the present invention, a resin composition can be obtained that exhibits a higher level of mechanical strength balance, better solvent resistance, and moldability than conventional resin compositions containing polyolefin and polyphenylene ether resin.

(G) Detailed Description of the Invention 1, Constituent Component (1) Polypropylene Resin (a) The polypropylene resin used in the present invention consists of the following first group or second group polymers. In other words, the first group consists of propylene as the main component, and propylene and α- other than propylene.
It is a polymer selected from co-structured polymers with at least one kind of olefin selected from olefins, such as block, random, and graft forms. The second group consists of copolymers or propylene homopolymers of the first group and other α-olefin polymers: i.e., ■ homopolymers of α-olefins other than propylene,
- a copolymer obtained by total polymerization of a plurality of olefins selected from olefins, more preferably a co-If type that exhibits rubbery properties at room temperature (more preferably the above-mentioned copolymer); copolymer of @]: is an olefin polymer selected from the mixture with copolymer of
The olefin polymers of the first group and the second group are both based on tactical polypropylene and exhibit crystallinity.

In the present invention, α-olefins other than propylene refer to linear or branched monoolefins having a double bond at the end, or monoolefins substituted with alicyclic groups, examples of which include: , ethylene, butene
1, pentene-1, hexene-1,3-methylbutene-
1,4-Methylpentene-1, heptene-1, octene-1, vinylcyclohexane, vinylcyclopentane, etc. can all be used in co-VX with propylene, but they are easily available and easy to co-form. From the point of view of
More preferably, it is selected from ethylene and butene-1, and still more preferably ethylene.

Tactical polypropylene, which exhibits crystallinity, is made of not only propylene homopolymer, but also propylene and other copolymer components, mainly the above-mentioned α-olefins, randomly (including those showing various randomness indexes) and blocks. , grafts, etc., may be present in the form of a co-N@ body, exhibiting various densities and degrees of crystallinity, a tactical index determined by solvent extraction, and NMR.
They may have various degrees of toughness as determined by the tactical pentad fraction determined by the method.

Crystallinity based on isotactic polyglopyrene chains can be determined by specifically measuring melting and crystallization behavior using a differential taxis Mf meter, and measuring viscoelastic temperature change behavior using a mechanical spectrometer, etc. . From the viewpoint of increasing the rigidity of the resin composition, the above-mentioned toughness and melting point are preferably higher.

Examples of N, di α-olefins that exhibit rubbery properties at room temperature include ethylene-propylene rubber (EPR), ethylene-butene-1 copolymer rubber (EBR), and ethylene-propylene-butene-1 copolymer rubber. So-called EPDM containing A, t7'j, and a small amount of non-conjugated diene as a copolymerization component can also be used. Among these, EPR, EBR, and EPBR are more preferred, and EPR is even more preferred. These α-olefin polymers that exhibit rubber-like properties at room temperature should be mixed with propylene homopolymers. A method of supersweetening the α-olefin heavy sweetener exhibiting rubbery properties at room temperature in at least one stage before or after the polymerization step, and
Examples include a method of separately sweetening each component and then mixing them in a melt-kneaded or solution state, and a method of mixing and kneading them at the same time when mixing with the Φ) component and the (C) component. Applicable.

These polypropylene resins include non-conjugated dienes such as 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, dicyclopentadiene, 4-ethylidene-2-norbornene, vinylcyclohexene, and vinylcyclopentene. It may also be included as a copolymerization component of kaama vlJwoshofila. Among these polypropylene resins, olefin polymers other than graft copolymers are preferred, and from the viewpoint of ease of availability and balance with physical properties, olefin polymers are more preferred even if they contain a small amount of polyethylene. It is selected from a bilene-ethylene block copolymer backbone, a mixture of a propylene-ethylene block copolymer and EPR, a mixture of a polypropylene homopolymer and EPR, and more preferably a 4-propylene-ethylene block copolymer. It is the body.

The proportion of α-olefin as a copolymerization component other than propylene in the polypropylene resin is preferably 1 to 30% by weight, more preferably 3 to 25% by weight, more preferably 5 to 20% by weight. lis~1
It is in the range of 6 weights.

From the viewpoint of obtaining high impact strength, it is preferable that the weight ratio is 1 or more, and a! From the viewpoint of general physical properties, a range of 301i and below is preferable.

Other than propylene in polypropylene resin (7)a
- The copolymerization ratio of olefins can be determined by ordinary NMR method or infrared spectroscopy.

Various ratios of room temperature xylene soluble content (hereinafter referred to as CXS) in the polypropylene resin can be used, but preferably 3 to 40% by weight, more preferably FiS to 30% by weight, and Preferably it ranges from 11 to 25% by weight, particularly preferably from 13 to 22% by weight. 401ii The rigidity level decreases in the range where there is a lot of impact strength.From the viewpoint of obtaining high impact strength, 33ii4
The above is preferable. The method for measuring CXS content is shown below. The basic procedure is to immerse the sample of No. 22 in boiling xylene 300 for 20 minutes to dissolve it, then cool it to room temperature, then filter it with an appropriate solid-liquid separation means such as a G4 type glass filter, and then dry it. Obtain the value by calculating backwards from the solid phase weight determined by

The properties of CXS contained in the above polypropylene resin are characterized by various factors determining the molecular structure, such as its copolymerization ratio with propylene 2 and other α-olefins, molecular weight, molecular weight distribution, and randomness index. , various types of these can be used, but in particular, CXS
The preferable range h for the copolymerization ratio of α-olefin other than propylene in the copolymer is 10% by weight or more, as the content of α-olefin other than propylene in the copolymer.
The viscosity in solution, which is a guideline for the molecular weight of CXS, is within the range of 30 to 70% by weight, more preferably 30 to 70% by weight, for example, 1% in orthodichlorobenzene.
The value of intrinsic viscosity at 40℃ is 0.2dll? More than 7d
t/f or less, more preferably 0.5 dllf or more 5 d
i/f or less, more preferably 0.5 di/ or more and 4 dl/f or less, particularly preferably 141
/ 1 or more and 4 dt/f or less, particularly preferably 2 dt/f
j/t m 4dll? The range is as follows.

One of the preferred conditions in the present invention is the ratio between the amount of α-olefin as a copolymerization component in the polypropylene resin and the amount of CXS listed above. The amount of α-olefin as a Kyodo @ component (unit: 1. The value divided by the amount of CXS (unit: 1 double) is 0.1 or more and 3 or less, more preferably 15 or more and 2 or less. , more preferably 0.
Fio is particularly preferably 2 or more and 1.25 or less, and 3 or more and 1.1 or more. When this value exceeds 3t-, the impact strength level tends to decrease despite the large amount of copolymerized components, and when this value is smaller than 0.1 in the b range, the impact strength level especially at low temperatures tends to decrease.

Melt flow rate MFR of polypropylene resin (23
0°C, load 2.16 kp) is preferably in the range of 0.01 to 400, more preferably in the range of 0.15 to 60, and 9
The range of O, S to 40 is preferable.

MFR+7) value is smaller than 0.01, W, ti
Difficulties tend to occur in workability, and in a range greater than 400, the mechanical strength level tends to be low.

As the polypropylene resin, one having a smaller MFR value, that is, one having a high molecular weight, is prepared by a known method, for example, in the presence of a radical generator (organic and inorganic peroxides, organotin compounds, organic azo adducts, etc.). It also includes molecules that have undergone molecular changes that fall within this MFH range due to heat treatment in the absence of the compound, or heating and mechanical shearing during melt-kneading.

The above-mentioned polypropylene resin can be produced by various known methods, and commercially available products can be used.

+21 HolJ phenylene ether at JIW (
b) The polyphenylene ether resin used in the present invention is connected to the general formula nucleus, where n is at least 30 and Q is so n
Each independently hydrogen, halogen, M-free hydrocarbon group containing tertiary α-carbon atom, halohydrocarbon group having at least 2 carbon atoms 'f: between halogen atom and phenyl nucleus, hydrocarbon oxy Represents a monovalent substituent selected from the group consisting of groups and heterohydrocarbonoxy groups having at least two carbon atoms between the halogen atom and the phenyl nucleus.

A typical example of polyphenylene ether is poly(
2,6-dimethyl-1,4-7-dinilene) ether, HoIJ (2,6-diethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether , poly(2-methyl-6-furopyru)
, 4-)unisine) ether, poly(2,6-ciglopyru-1,4-)unisine) ether, poly(2-ethyl-6-broby-1,4-phenylene) ether, poly
J (2,6-dif-thyl-1°4-phenylene) ether, BoIJ (2,6-difurobenyl-1,4-)unisine) ether, poly(2°6-zyl+71 flu 1.
4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether, poly(2,6-simethoxy 1,4-)unisine) ether, poly(2,
6-jethoxy-1,4-phenylene) ether, poly(2-methoxy-6-nitoxy-1,4-phenylene)
Ether, poly(2-ethyl-6-methylallylic acid)
1,4-phenylene) ether, holJ (2,6-dichloro-1,4-phenylene) ether, poly(2-methyl-6-phenyl-1,4-phenylene) ether,
HoI7 (2,6-cybenzyl-1,4-phenylene)
Ether, poly(2-ethoxy-1,4-phenylene)
Ether, Bo1J (z-/Colo-1,4-phenylene)
ethers, poly(2,5-dibromo-1,4-phenylene) ethers and the like.

Also, copolymers of 2,6-dimethylphenol and 2.3.6-)limethylphenol, copolymers 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 used in the present invention is
It also includes polyphenylene ether gold obtained by grafting a styrene monomer (eg, styrene, p-methylstyrene, α-methylstyrene, etc.) onto the polyphenylene ether defined by the above general formula.

Methods for producing polyphenylene ethers corresponding to the above are known, for example, U.S. Pat.
No. 06875, No. 3257357 and No. 32573
58 Report Specification and Japanese Patent Publication No. 52-17880
No. and Japanese Patent Application Laid-Open No. 50-51197.

A group of polyphenylene ethers which are preferred for the purposes of the present invention are those with alkyl substitution A' in the two oron positions relative to the ether oxygen atom and those with alkyl substitution A' in the two oron positions relative to the ether oxygen atom and those with both 2,6-dialkylphenol and 2.3.6-trialkylphenol. It is the body.

Among these, 2,6-dimethylphenol polymers are particularly preferred. Further, the preferable molecular weight range is 0.2 to 0, rdt7t, more preferably 0.25 to 0.6 dllf, as a measure of the intrinsic viscosity in chloroform at 30°C. more preferably 0.25 to 0.55 d
ll t, particularly preferably 0.3 to 0.52 dl
l f range. 0.2dll? In the range of smaller rlA values, the mechanical strength of the composite sole is low;
In a range of values larger than dllt, the molding processability of the composition tends to decrease.

(3) Hydrogenated alkenyl aromatic compound - Conjugated diene block copolymer (C) Hydrogenated alkenyl aromatic metal compound used in the present invention -
Conjugated diene block copolymer (hereinafter sometimes referred to as hydrogenated block copolymer) (C) is a chain block "A" derived from an alkenyl aromatization product and a chain block rBJ derived from a conjugated diene. This is a block copolymer in which the aliphatic unsaturated groups in block B of an alkenyl aromatic compound-conjugated diene block copolymer having at least one structural gold are reduced by hydrogenation. The arrangement of blocks A and B includes gold having a linear structure or a branched structure, ie, a so-called radical teleblock structure. Moreover, a part of these structures may contain random chains derived from a random copolymerization portion of an alkenyl aromatization product and a conjugated diene.

The distribution of the monomer components is not particularly limited, and may be uniform, non-uniform, or tapered such that the amount of the monomer components increases or decreases along the molecular chain. Therefore, even if the molecular weights of multiple A blocks and B blocks are the same, they are different.
You can. Among these, diblocks (A-B blocks), triblocks (A-B-A blocks, B-A-B blocks), and tetrablocks (8-B-
A-8 block), pentablock (A-B-A-B-
A block, B-A-B-A-13 block) or a linear structure in which the total number of blocks of block A and block B is 6 or more is more preferable, and among these, di-block, tri-block , a tetrablock structure is more preferable, and one having an A-B-A) rib block structure is particularly preferable.

The alkenyl aromatization adduct forming block A't has a chemical structure represented by the following general formula.

CR"=CHR"s In the formula, R1 and R"#i are selected from the group consisting of hydrogen and a lower alkyl group or alkenyl group having 1 to 6 carbon atoms, and R1
and R4 is selected from the group consisting of hydrogen, a lower alkyl group having 1 to 6 carbon atoms, chlorine, and bromine, and asXna and R7 are 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 be linked together with a hydrocarbyl group to form a 7-tyl group.

Specific examples of alkenyl aromatic compounds include styrene, halamethylstyrene, -monomethylstyrene, vinylxylene, vinyltoluene, vinylnaphthalene, divinylbenzene, bromostyrene, and hychlorostyrene, which can also be used in combination. Among these, styrene, a-methyl δ-styrene, para-methylstyrene, vinyltoluene, and vinylxylene are preferred, and styrene is more preferred. Specific examples of the b0 conjugated diene include 1,3-butadiene, 2-methyl -1
, 3-butadiene, 2,3-dimethyl-1,3-2-tadiene, 1,3-pentadiene, etc. Among these, 1,3-butadiene, II-methyl-1,3-2-tadiene,
Examples include butadiene. 4q 1,3-butadiene is particularly preferred. In addition to these conjugated dienes, a small amount of lower olefinic hydrocarbons such as ethylene, propylene, and 1-butene, dicyclopentadiene, and nonconjugated dienes may be included.

The hydrogenated alkenyl aromatic adduct-conjugate is preferably in the range of more than 45% by weight and less than 80% by weight, more preferably in the range of 47% by weight and more than 75% by weight, and more than 50% by weight and less than 70ifi%. Particularly preferred is a range of 55 qbw and 70 qbw or less. If the proportion of repeating units derived from alkenyl aromatization adducts in the polymer (C) exceeds 80% by weight, the impact strength of the resin composition will be at an unsatisfactory level;
If the ratio is less than 5, the rigidity level and heat resistance of the resin paraboloid will be unsatisfactory, which is not preferable.

Among the aliphatic chain moieties in these block copolymers (C), the proportion of unsaturated bonds derived from conjugated dienes and remaining without being hydrogenated is preferably 50 or less, and 20
% or less is more preferable, and 10% or less is particularly preferable.

Further, about 25 or less of the aromatic unsaturated bonds derived from the alkenyl aromatization compound may be hydrogenated.

Various types of these hydrogenated block copolymers (C) can be used, but as a guide for their molecular weight, the value of the number average molecular weight measured by Kel permeation chromatography and the polystyrene conversion method is 5, 000
f/mol or more and 500,000 t/mol or less, preferably 10,000 f/mol or more and 300
,000 f/mol or less is more preferable. More preferably 30,000? /mo1 or more 200
．． 000 t/mol or less, particularly preferably 45
．． 000 f/m04 or more 150,000 t7m
It is within the range of o1 or less. Measured by gel permeation chromatography, the number average molecular weight value according to polystyrene conversion method is 500,000 f/mo
Those with a number average molecular weight of more than J and a number average molecular weight of 5 according to the same method.
,000 f/mol f: Anything below this tends to be expensive in terms of manufacturing costs.

In measuring the molecular weight and molecular weight distribution curve by gel permeation chromatography (4), monodisperse polystyrene was used as a standard substance when determining the relationship between elution time and molecular weight. Each average molecular weight was a polystyrene equivalent molecular weight.

The molecular weight distribution of these hydrogenated block copolymers (C) can be measured by the gel permeation chromatography described above, but those with various molecular weight distributions can be used. Furthermore, the so-called Q value, which is obtained by dividing the weight average molecular weight value by the total number average molecular weight value, may be within any range. In addition, the molecular weight distribution may have not only one but multiple mountain-like dispersions, or it may contain a small amount of components with a higher or lower molecular weight than the main dispersion in addition to the mountain-like main dispersion, and the shape of the molecular weight distribution is In addition to a mountain-shaped main dispersion, it is also possible to use a shape that shows a trailing shape. However, among these, from the viewpoint of mechanical properties,
It preferably has a Yamabushi dispersion of 1 or 2, more preferably 1, and has a Q value of preferably 1.05 or more and 3 or less, more preferably 1.1 or more and 2 or less.

The molecular weights of the alkenyl aromatic chain block (block A) and the conjugated diene chain block to which water X has been added (block B) in the hydrogenated block copolymer (C) are as follows:
Various types and combinations of sweeteners can be used as long as they satisfy the above number average molecular weight.

Some of these hydrogenated block copolymers (C) have a hydrogenated conjugated diene M chain moiety and exhibit crystallinity derived from this chain. This is presumed to be due to a hydrogenated conjugated diene polymer chain or a molecular structure similar to polyolefin. The hydrogenated block copolymer (C) can be measured using a differential scanning calorimeter (hereinafter abbreviated as DSC) manufactured by Crystal Seimei. Examples of this device include PERKIN-ELMER or 1) up
On is available from Company N and can be used. By the way, the above crystallinity can also be determined by measuring viscoelasticity using a mechanical spectrometer or the like. As a specific example of melting point measurement, in an atmosphere of an inert gas such as nitrogen or the like for use with these DSC devices, for example, the
The melting behavior can be measured at a heating rate of 0°C. The sample is heated to a temperature above the predicted melting point, then cooled at a rate of 10°C per minute, left to stand for about 1 minute, and then heated at a rate of 10°C per minute. be able to. Regarding the crystallinity of the hydrogenated conjugated diene weighted block portion in the molecule of the hydrogenated block copolymer (C) in the present invention, various types can be used, including those that exhibit crystallinity and those that do not. So 61. From the viewpoint of obtaining high mechanical properties, it is more preferable to exhibit a clear melting point, with a melting point of 140°C or more and 160°C or less,
Preferably -20°C or more and 130°C or less, particularly preferably 0°C or more and 110°C or less, and preferably 2
0°C or more and 100°C or less, particularly preferably #i
The temperature is in the range of 40°C or higher and 100°C or lower.

Various types of glass transition temperature based on the hydrogenated conjugated diene polymerization chain portion of the hydrogenated block copolymer (C) can be used.

The glass transition temperature can be measured by the above-mentioned DSC method or by measuring the temperature change behavior of viscoelasticity using a mechanical spectrometer or the like.

A number of methods have been proposed for producing alkenyl aromatic compound-conjugated diene block co-polymer. A typical method is, for example, Japanese Patent Publication No. 40-2379.
There is a method described in U.S. Pat. No. 8, U.S. Pat. As one such block copolymer, rTR24 is available from Japan Synthetic Rubber Co., Ltd.
Some are commercially available under trade names such as 00J.

Hydrogenation treatment of these block copolymers can be carried out using methods described in Japanese Patent Publications No. 42-8704, No. 43-6636, or No. 46-20814, using an inert compound such as cyclohexane. It is carried out by hydrogenation in a solvent in the presence of a hydrogenation catalyst. In this hydrogenation, at least 50%, preferably 80% or more, preferably 90% or more of the olefin type double bonds in the heavy body block B are hydrogenated, and the aromatic content in the n1 heavy body block A is hydrogenated. When less than 25 mos of unsaturated polyester is hydrogenated, Journal of Polymer
er 5science part 33 polyme
r letters volume 11, 427-4
It is also possible to carry out hydrogenation using para-toluenesulfonyl hydrazide or the like in an inert solvent according to the method shown on page 34 (1973).

λ Composition ratio of constituent fraction Polypropylene resin (
The ratio of a) is the total amount of polypropylene resin (a), polyphenylene ether resin (b), and hydrogenated alkenyl aromatic compound-conjugated diene block copolymer (C) '1
As a loO weight scratch, a range of 20 to 80 weight is recommended, among which a range of 25 to 67 weight is preferable, and a range of 25 to 5
A range of 8 weights or less is particularly preferred, and a range of 33 to 55 weights is particularly preferred. If it is less than 20% by weight, the organic solvent resistance will not be sufficient, and if it exceeds 80% by weight, the heat resistance will be at an unsatisfactory level, making it impossible to achieve the object of the present invention, which is not preferred. Similarly, polyphenylene ether resin (
The proportion of b) is the proportion of resin components (a), (b) and (
C) Accounting amount t-100 heavy eating damage is recommended to be in the range of 20 to 80 weight, and among these, the range of 23 to 65 weight is preferable, and the range of 30 to 65 weight is more preferable.
] A range of 335 to 53 weight is preferable. zo! m
If it is less than s, the rigidity level will be unsatisfactory, and 80 weight III
If it exceeds 20%, the organic solvent resistance will be insufficient, which is not preferable. The amount of the hydrogenated alkenyl aromatic compound-conjugated diene block copolymer (C) is the amount of the above (a), (b),
The total amount of the proportion of (C) as Zoo weight is preferably in the range of 4 to 50 weight units, more preferably 4 to 30 weight units, particularly preferably 7 to 25 weight units, especially lO to 20 weight units. A weight range is preferred. If the weight is less than 4, the impact strength level will be insufficient, and if it exceeds 50 weight, the rigidity level will be unsatisfactory and the object of the present invention cannot be achieved, which is not preferable.

In the present invention, in addition to the above-mentioned essential components,
- From the viewpoint of further enhancing the effect and obtaining a higher level of mechanical properties, the following diamide compound (d) can be added.

The diamide compound (d) optionally used in the present invention is represented by the following general formulas CD-1), CD-2), and CD-3).

Here, R" is a saturated or unsaturated chain hydrocarbon residue having a linear or side chain having 1 to 10 carbon atoms, an alicyclic hydrocarbon residue, or an aromatic hydrocarbon residue, or The derivative group R11 and R1! are each n
A may be the same or different; A is a saturated or unsaturated chain hydrocarbon residue having 1 to 10 carbon atoms or a side chain, an alicyclic hydrocarbon residue, or an aromatic hydrocarbon residue; Alternatively, these derivative residues.

Examples of R'' include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, an imbutylene group, a pentamethylene group, a cyclopentyl group, a hexamethylene group, a cyclohexylene group, an octamethylene group,
decamethylene group, phenylene group.

R" and R11 include, for example, a methyl group, an ethyl group, a globyl group, an isopropyl group, a butyl group, an isobutyl group,
Examples include t-butyl group, pentyl group, isopentyl group, cyclopentyl group, hexyl group, isohexyl group, cyclohexyl group, heptyl group, octyl group, decyl group, and phenyl group.

RIO1R" and 1c12 can have one or more substituents, and the following can be used as the substituents, for example.

-R"(R": Ct to C8 hydrocarbon group) -X
(X: (halogen such as j%Br, F)-OR” (
R": H or C0-C1 hydrocarbon group)-NR"
R''(R',R''B: Hlftuc, ~C,) hydrocarbon group) -〇〇OR'(R': Ht 7'eu
C, ~C, (7) Hydrocarbon i) -COOH and its metal salts are acid anhydride groups, -8o, f(, -No2, -
such as NOl and -CN.

Among these diamide compounds, more preferably general formula C
This is the monster group shown in D-1). Specific examples of these compounds include adipic acid dianilide, itaconic acid dianilide, and the like.

The amount of the diamide compound added is 0 as an extra number for 100 parts by weight of polymer components (a) to (C).
~50 parts by weight, preferably 0.05~
The amount is 30 parts by weight, more preferably 1 to 20 parts by weight, especially 2 to 15 parts by weight. From the viewpoint of the effect of addition of the diamide compound (d), it is preferable to add a larger amount of the diamide compound (d).
A range beyond the overlapped portion is not preferable because the level of mechanical strength is not sufficient and there is a concern that appearance may deteriorate due to exposure on the surface of the molded product.

Note that when the molding temperature changes due to the addition of a stabilizer or plasticizer, diamide compounds with different melting points can be used accordingly.

Further, the diamide compound is intended to be melted and flowable in a fluid state during molding, but to be solidified or crystallized during use.

Therefore, the melting point of the diamide compound of the present invention is usually 100
℃ to 350℃, but it is desirable that the temperature is lower than the daily working temperature and higher than the operating temperature. The lower limit is the melting point, glass transition point, etc.), and the upper limit is the decomposition start temperature of the system.

The polypropylene resin (a) and the hydrogenated block copolymer (C), which are the constituent components of the resin composition according to the present invention, are usually molded in a temperature range higher than 100°C. The lower limit of the molding temperature of the polyphenylene ether resin (b) is, for example, the lower limit of the glass transition point when mixed with a styrene resin, and the upper limit is about 100°C, and the upper limit is the temperature of the polyphenylene ether in air. The temperature at which decomposition begins is generally around 350°C.

In the present invention, in addition to the above-mentioned components, other additional components may be added as necessary to the extent that the effects of the present invention are not impaired, such as antioxidants, weather resistance improvers, nucleating agents for polyolefins, slip agents, Inorganic or organic optical fillers, reinforcing agents, flame retardants, each a
It is possible to add a coloring agent, an antistatic agent, a mold release agent, a small amount of a radical generator (organic peroxide, etc.) for controlling the molecular weight of the polyolefin, and the like.

9. Plasticizers such as triphenyl phosphate used in polyphenylene ether resins, polystyrene, rubber-reinforced high-impact polystyrene, ABSm resin, and various styrenic polymers such as styrene-maleic anhydride copolymer are added. Furthermore, the addition of fillers such as glass fiber, wollastonite, potassium titanate, whiskers, mica, talc, and calcium carbonate can improve the balance of physical properties such as rigidity, formability, dimensional accuracy,
Dimensional stability is equally effective.

3. Phase structure formed by the M4 component The resin composition according to the present invention can achieve the object of the present invention within the above composition ratio range, and the phase structure formed by each component is not particularly limited. , interpenetrating network structure (Japanese Patent Publication No. 6G-57463), etc. are not particularly required, but for the purpose of obtaining high solvent resistance, it is more preferable to use polypropylene resin as the continuous phase.

- (Blending method) As a blending method for obtaining the resin composition according to the present invention, generally, resins are mixed together or resins are mixed with stabilizers, colorants,
Furthermore, various methods of blending the resin and filler can be applied. For example, powdered or granular components are uniformly dispersed in a Henschel mixer, a super mixer, a ribbon blender, a blender, etc., and then a twin-screw mixed extruder, a -screw mixed extruder, roll, banbury mixer, plastomill,
A Prabender Plastograph melt mixer may be used. The melting crosstalk temperature is usually in the range of 200°C to 350°C. The resin composition obtained as described above can be extruded into pellets after being melted and mixed.

4. Hanging of the resin composition according to the present invention The resin composition according to the present invention can be easily formed into a KE shape by molding methods generally applied to thermoplastic resins, such as injection molding, extrusion bottom shape, hollow bottom shape, etc. Of these, injection molding is the most preferred. Due to its good mechanical properties, it can be used for automobile parts, exterior parts such as concrete 11felKa bumpers, door panels, fenders, moldings, emblems, wheel covers, engine hoods, roofs, spoilers, instrument panels, console boxes, etc. It is suitable for interior parts such as trims, and also for exterior parts of electrical equipment, specifically for parts such as televisions, refrigerators, roads, and so-called office automation equipment.

(5) Experimental Example 1, Measurement and Evaluation Method The physical property values and properties in the Examples and Comparative Examples shown below were measured and evaluated under the following conditions.

1) MFR (Measure of flowability) Measure MFR of polypropylene resin according to JIS K7210-1975. The MFR of the composition was measured by the method described above with some modifications.

The items to be changed were the measurement temperature and load, and the conditions were 280° C. and load skf.

2) Flexural modulus (rigidity guideline) 180 R178-1974 Procedure 1
2 (JIS K7203) using an Instron testing machine. The value of the flexural modulus at 80°C was determined by setting up a constant temperature bath so that the test piece, the support stand used for measurement, and the pressurizing wedge part were placed in a hot air constant temperature bath.
Measurement shall be carried out after adjusting the condition in an atmosphere of ±1℃ for 20 minutes or more.9.

3) Izot impact value 180 R18O-1969 (JIS K7110
) (notched Izot impact strength) using a Toyo Seiki Urasakusho Enki Izot impact tester.

4) Drop weight impact strength: Create a sheet (120 x 80 m, 2 sheets thick) by injection molding, set it on a support stand (hole diameter 50 m +), and drop a dart, which is a load sensor. (2x7k
The deformation and fracture behavior of the lf)% test piece under impact load was measured, and the nine-impact energy absorbed up to the point of crack initiation in the resulting impact pattern was calculated, which was taken as the impact strength of the material.

5) Heat deformation resistance (measure of heat resistance) ISOR75-1958MethodA (JIS 72
07-1974 Method A).

Incidentally, annealing treatment was performed at 100° C. for 30 minutes and a mental injection molding sample was used.

2. Mixing and mixing of resin composition After thoroughly mixing and stirring the specified jjk of each component shown in the table below using a super mixer, PCM2 manufactured by Ikegai Iron Works.
Using a shaft type extruder, the mixture was melt-kneaded at 280° C. to form a composition, which was then extruded into a strand shape and made into pellets using a cutter.

3. Creation of test pieces for physical property measurement and evaluation In-line screw injection molding machine, IS-90B manufactured by Toshiba Kitanura Seisakusho
B1 cylinder @ 280℃, mold cooling temperature 60℃
A test piece was prepared by performing X-shaped injection at ℃.

4. Details of each fraction 1) Polypropylene resin (a) Mitsubishi Yuka four-layer polypropylene homopolymer and propylene-ethylene block copolymer were used.

The MFR and ethylene component content are shown in the table.

Ethylene fraction content was determined by conventional NMR methods. The CXS content was measured by the method shown in the section "1. Component (1) Polypropylene resin (a)".

2) Polyphenylene ether (b) Poly(2,6-dimethyl-1,4-)unilene) ether manufactured by Mitsubishi Yuka ■ was used. The values of intrinsic viscosity (in chloroform at 30° C.), which is a guideline for molecular weight, are shown in the table.

3) Hydrogenated alkenyl aromatic compound-conjugated diene block copolymer (C) The hydrogenated alkenyl aromatic compound-conjugated diene block copolymer (C) used in the examples was a commercially available styrene-conjugated diene block copolymer (C).
A butadiene block copolymer or a styrene-butadiene block copolymer synthesized according to the method described below was obtained by hydrogenation treatment according to the method shown below.

Sweet acid of styrene-butadiene block copolymer: Put it in an autoclave sufficiently purged with nitrogen, use cyclohexane from which water has been removed as a solvent, and add a small amount of tetrahydrocarbon
Polymerization of styrene is carried out at a temperature of about 60 to 80°C in the presence of n-butyllithium containing 17 runs, and then a butadiene solution is added to complete the polymerization of the polybutadiene block chain bound to the polystyrene chain. A styrene solution was added thereto to polymerize the polystyrene block chains attached to the polybutadiene chains, thereby obtaining a styrene-butatadiene block copolymer containing 60 styrene block chains. Table 2 shows the analytical values for each sample.

Hydrogenation treatment of styrene-butadiene block copolymer: Next, each of the above-mentioned block copolymers and the commercially available Nippon Siki Rubber Co., Ltd. and the styrene-butadiene block copolymer synthesized by the above method were Thoroughly dried, dissolved in cyclohexane from which water was removed in an autoclave that had been purged with nitrogen, and hydrogenated at 60 to 70 tl::, 10 to 13 kg/ad in the presence of a nickel naphthenate catalyst. Hydrogenation treatment was carried out under pressure for 9 hours. A poor solvent (methanol) is added to the reaction solution, the solvent and the superimposed body are separated by filtration, and dried under reduced pressure to obtain hydrogenated styrene.
A butadiene block copolymer (C) was obtained. Table IK'! shows the analysis values for each sample. I stopped it.

(hereinafter referred to as "Kinpaku") In addition, in the above hydrogenated samples (abbreviations 5B-1, 5B-2 and 5B-4 shown in Table 1), aliphatic carbon-carbon dioxide remaining without being hydrogenated. Juunokai is NMR
It was not detected by method and infrared spectroscopy.

For the purpose of comparison, a commercially available hydrogenated styrene-butadiene block copolymer (containing styrene component, Vt 29 weight ring, trade name Kraton G1652, manufactured by Shell Chemical Co., Ltd.) was used.

4) Diamide compound (d) Commercially available adipic acid dianilide was used as a representative example of the diamide compound (d).

In addition, when kneading each component, a phenolic antioxidant: pentaerythrityl-tetrakis (3-(
3,5-di-tert-butyl-4-hydroxyphenylglobionate] (Product name: Irganox 1010.
(manufactured by Ciba Geigy) t, (a), 佽), (C) and (
d) Accounting amount of component: 0.3 g per 100 iL portion
Volume, 710, t&.

5. Explanation of Examples and Comparative Examples In Table 2, from the comparison between Example 1 and Comparative Example 2, which used the component (a) t- whose MFR is close to The impact strength level of the composition using the laminated body is much higher than that of the composition using only the polypropylene laminated body as the component (a), and the effect of the present invention is clear.

Similarly, Examples 1 to 6 show that various glopyrene-ethylene block copolymers within the scope of the invention have good impact strength levels, and the effect of the invention is clear.

In addition, from the comparison between Example 1 and Example 9, Example 2 and Example 8, and Example 1O1 and Example 11, diamide compound 0) was added to the combination of ingredients within the scope of the present invention. The mR material exhibits even higher physical properties, and the effects of the present invention are further enhanced.

Claims (1)

[Claims] (1) It is an α-olefin polymer whose main component is propylene, exhibits crystallinity based on isotactic polypropylene, and has a content of polymerized units derived from α-olefins other than propylene in the range of 1 to 30% by weight. A certain polypropylene resin (a) 20 to 80% by weight, a polyphenylene ether resin (b) 20 to 80% by weight, a hydrogenated alkenyl aromatic compound containing more than 45% by weight and not more than 80% by weight of polymerized units derived from an alkenyl aromatic compound. - A resin composition comprising 4 to 50% by weight of a conjugated diene block copolymer (C).