JPH10219074A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition, good in compatibility among different kinds of resins and excellent in impact resistance. SOLUTION: This resin composition comprises (A) 90-10 pts.wt. aromatic vinylic resin consisting essentially of a rubber-modified aromatic vinylic resin, (B) 10-90 pts.wt. thermoplastic resin incompatible with the component A and 0.03-10 pts.wt. copolymeric resin modifier composed of (C) 95-70wt.% vinylic resin part having the compatibility with the component A and (E) 5-30wt.% polyester resign part having the reactivity with the component B. The rubber- modified aromatic resin in the component A respectively satisfies specific conditions of (i) a rubber-like polymer dispersed particle diameter, (ii) the number of particles having a salami structure in the particles and (iii) the ratio of the fraction insoluble in toluene and the rubber content.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition widely used as a molding material.

[0002]

2. Description of the Related Art It has been known that a resin composition generally called a polymer alloy is obtained by modifying a thermoplastic resin by blending a resin having a property different from that of the thermoplastic resin. Until now, styrene resin modified by blending styrene resin or polyphenylene ether resin is alloyed with engineering plastics such as thermoplastic polyester, polycarbonate resin, polyamide resin, polyimide resin, polyamide imide resin and polyester carbonate resin. Attempts have been made to improve heat resistance, chemical resistance, impact resistance, dimensional stability, moldability, and the like.

However, styrene resins modified with styrene resins and polyphenylene ethers are essentially incompatible with these engineering plastics, and macro phase separation occurs due to poor dispersibility.
In many cases, the purpose of reforming cannot be achieved. Therefore, as a key technology for polymer alloys, a technology has been developed in which various compatibilizers are added to lower the interfacial tension at the phase separation interface, and that the desired properties are exhibited by improving the compatibility of both.

One of the resin compatibilizers is a non-aqueous resin that uses a copolymer composed of a resin portion compatible with each resin, as disclosed in "Industrial Materials 1996 January, 26". A reactive compatibilizer, which introduces a functional group capable of reacting with one resin into a resin compatible with the other resin and excites the reaction during the kneading process to form the copolymer described above. It is roughly divided. Above all, when a reaction-type compatibilizer is applied, the compatibilizer generated by the reaction is easily fixed to the phase separation interface, and the interfacial tension at the phase separation interface can be efficiently reduced. Due to these advantages, various reactive compatibilizers have recently been developed.
However, known reaction-type compatibilizers have low reactivity, and often cannot exhibit a sufficient compatibility improving effect.

[0005] For example, in an alloy of incompatible resins consisting of a polyester resin and a polyphenylene ether resin, W.
B. Lui, et.al, Eur. Polym. J. Vol., 32, No. 1 91-99, 1
995 discloses a method in which polystyrene having an epoxy group introduced is used as a reactive compatibilizer. However, since the compatibilizer utilizes the reaction between the residual functional group at the terminal of the polyester resin and a small amount of epoxy group introduced into the styrene chain, the reaction does not proceed sufficiently in the kneading process, and the The solubility could not be improved. Japanese Patent Application Laid-Open No. Hei 5-9354 discloses an alloy of an incompatible resin composed of a polyamide resin and a polyolefin resin.
No. 91 and JP-A-6-116492 disclose an olefin resin having an acid anhydride only at the terminal.
JP-A-398861 and JP-A-6-116460 disclose that an olefin resin graft-modified with a vinyl monomer having a carboxylic acid group is used as a reactive compatibilizer.

However, all of these are compatibilizers utilizing a reaction between a terminal functional group of a polyamide resin and a small amount of a functional group introduced into an olefin resin, and the reactivity was not sufficient. JP-A-3-199255 discloses a technique of adding a copolymer containing an epoxy group or an oxazolinyl group to a polymer alloy of a polycarbonate having a specific terminal structure and a styrene-based rubber. Since the reaction between the epoxy group or the oxazolinyl group and the terminal of the polycarbonate was used, the reaction did not proceed sufficiently.

[0007]

As described above, in the conventional compatibilizing technique, the effect of improving the compatibility between different resins is low, and the physical properties such as impact resistance are still poor. An object of the present invention is to provide a resin composition having an excellent compatibilizing effect, including improvement in impact resistance, in view of the above situation.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that an aromatic vinyl resin containing a specific rubber-modified aromatic vinyl resin as an essential component (composition) Product) and a composite resin composed of an incompatible thermoplastic resin, wherein one resin is composed of a polymer part having compatibility and the other resin is composed of a polymer part having reactivity. It has been found that by using a specific copolymer resin as a modifier, the impact resistance can be improved, the compatibilizing effect can be improved, and a good appearance can be imparted, and the present invention has been completed.

That is, the invention according to claim 1 of the present invention comprises: (A) a rubber-modified aromatic vinyl-based resin in an amount of 50 to 10;
0 aromatic vinyl resin 90-10 parts by weight content% (B) component; (A) component and the incompatible thermoplastic resin 10
Component (C); 95 to 70% by weight of a vinyl resin part (D) compatible with the component (A), and a polyester resin part (E) 5 reactive with the component (B). ~ 30% by weight
Resin modifier 0.03 to 1 which is a copolymer composed of
A resin composition blended at a ratio of 0 parts by weight;
The rubber-modified aromatic vinyl resin in the component has the following requirements,
(i) the weight average particle diameter of the dispersed particles of the rubbery polymer dispersed in the aromatic vinyl polymer is in the range of 0.4 to 0.9 μm, and the weight-based cumulative particle diameter distribution is 5; % Value is 1.0 μm or less, 95% value is 0.2 μm or more, (ii) the proportion of dispersed particles having a salami structure in all rubbery polymer dispersed particles is 80% by weight or more, and The dispersed particles in which the number of particles of the aromatic vinyl polymer included in the dispersed polymer particles is 20 or less are 70% of the total dispersed particles.
% Or more, and (iii) the ratio of the toluene-insoluble matter to the rubber content satisfies 1.0 to 2.5.

The invention according to claim 2 of the present invention is characterized in that, in the above invention, the component (A) is preferably an aromatic vinyl resin containing 50 to 100% by weight of a rubber-modified aromatic vinyl resin and a polyphenylene ether resin. It is a mixture with a resin. The component (C) in each of the above inventions is a block copolymer of a styrene resin portion (D) and a polyester resin portion (E), and the number average molecular weight (Mn) of the block copolymer is 1,000. ~ 70,000
Is particularly preferable.

Hereinafter, the components of the present invention will be described in detail. First, the component (A) constituting the resin composition of the present invention comprises a rubber-modified aromatic vinyl resin satisfying the following requirements (i) to (iii) as a main component (that is, containing 50 to 100% by weight). Or a mixture of the aromatic vinyl resin and the polyphenylene ether resin.

In particular, the rubber-modified aromatic vinyl resin of the present invention includes (i) a rubber-like polymer dispersed in an aromatic vinyl polymer having a weight average particle diameter of 0.4 to less.
5% value of the weight-based cumulative particle size distribution is in the range of 0.9 μm, and 5% value is 1.0 μm or less, 95% value is 0.2 μm or more, and (ii) salami structure in all rubbery polymer dispersed particles. Is 80% by weight or more, and the number of particles of the aromatic vinyl polymer included in all the rubber-like polymer dispersed particles is 20 or less. 70% or more, and (iii) the ratio of toluene-insoluble matter to rubber content must be 1.0 to 2.5.

The resin composition of the present invention (A)
The component is a resin that is compatible with the vinyl resin part (D) of the resin modifier which is the component (C) of the present invention, and has a hydrogen bond and an acid with the vinyl resin part (D) of the resin modifier. -Resin that interacts between molecules such as base interaction and charge transfer, and missing wi
It is a resin (composition) that is compatible with proper copolymerization known as the principle of ndow.

As a specific index for evaluating compatibility, a vinyl resin (D) and a resin having a χ parameter (known as a compatibility evaluation index of a polymer alloy) of 0.3 or less are used. χ Measurement of parameters is performed by a known measurement method, for example, H.yang, et., alMacromolecules vol.24 521
8 (1991), a method of calculating from glass transition temperature measurement results, RSSteinet., Al Phsica 198
6 137B 194 (laser light, x
This is a value measured by a method such as measurement by (ray, neutron) scattering or a method of calculating from spin relaxation time by solid-state NMR.

The rubber-modified aromatic vinyl resin composition which is the main component of the component (A) of the present invention is used in the presence of a rubber-like polymer in the presence of an aromatic vinyl-based monomer or an optional vinyl-based monomer. By polymerizing other copolymerizable vinyl monomers. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and the like. These may be used alone or in combination of two or more.

In the rubber-modified aromatic vinyl resin of the present invention, other vinyl monomers copolymerizable with the aromatic vinyl monomer include methyl methacrylate, ethyl methacrylate, methyl acrylate, and acrylic Examples include ethyl acrylate, acrylonitrile, methacrylonitrile, methacrylic acid, acrylic acid, maleic anhydride, phenylmaleimide, and halogen-containing vinyl monomers. One of these copolymerizable monomers may be used alone, or two or more thereof may be used in combination, but usually 30% by weight based on the total aromatic vinyl monomer containing styrene. %, Preferably 10% by weight or less.

In the rubber-modified aromatic vinyl resin composition used in the present invention, a rubbery polymer is dispersed and contained in the form of particles. The type of rubbery polymer used is not particularly limited, and polybutadiene, styrene-butadiene copolymer, polyisoprene, butadiene-styrene polyisoprene copolymer, natural rubber, and the like can be used. When polybutadiene is used for the rubbery polymer of the present invention, the microstructure of the polybutadiene portion may be low-cis polybutadiene rubber, high-cis polybutadiene rubber, or low-cis polybutadiene rubber. It may be a mixture of high cis polybutadiene rubber.
The structure of the styrene-butadiene copolymer rubber may be a random type, a block type or a taper type. One of these rubbery polymers can be used alone, or two or more can be used in combination.

The preferred content of the rubbery polymer in the rubber-modified aromatic vinyl resin composition is 4 to 15% by weight,
More preferably, it is in the range of 7 to 15% by weight. If the content of the rubbery polymer is less than 4% by weight, the impact resistance is insufficient, and if it exceeds 15% by weight, the rigidity is reduced to a practical range or less, which is not preferable. In the rubber-modified aromatic vinyl resin composition used in the present invention, the weight average particle diameter of the rubber-like polymer dispersed particles needs to be 0.4 to 0.9 μm, and 0.4 to 0.8 μm Is preferable, and most preferably 0.4 to 0.7 μm. When the weight average particle diameter is less than 0.4 μm or 0.9 μm or more, the impact resistance of the composite resin composition is insufficient.
Here, the weight-average particle diameter refers to a value obtained by taking an electron micrograph of a rubber-modified aromatic vinyl resin by an ultra-thin section method,
In the photograph magnified 00 times, the dispersion rubber particles 1000
It is assumed that the particle diameter of at least one particle is measured and determined by the following equation. The weight average particle diameter ^{_{= Σn i D i 4 / Σn}} i D i 3 ( where n _i is the number of rubbery polymer particles having a particle diameter D _i.)

In order to achieve the object of the present invention, the 5% value of the weight-based cumulative particle size distribution of the rubber-like polymer dispersed particles is 1.0 μm or less, preferably 0.9 μm or less, and the 95% value is 0%. It is necessary to be at least 20 μm, preferably at least 0.25 μm. It is essential that the weight-based cumulative particle size distribution has a 5% value of 1.0 μm or less in order to obtain excellent gloss, and a rubber-like polymer particle having a particle size of 0.20 or less cannot be expected to have a shock absorbing effect. Therefore, 95% value is 0.20
If it is less than μm, the impact resistance decreases. 5% value of the weight-based cumulative particle size distribution of the rubber-like polymer dispersed particles referred to herein,
The 95% value is defined as the particle diameter at which the rubber particles are accumulated from the larger one and the weight-based accumulation rate is 5% of the total as the 5% value of the cumulative particle size distribution. The value is assumed to be 95% of the distribution.

Further, in order to obtain an object in the balance of physical properties of mechanical strength of the present invention, particularly, in impact resistance,
It is necessary to control the dispersed rubber-like polymer particles in a specific dispersion form. That is, it is necessary that the rubber-like polymer dispersed particles have a salami structure. Here, the dispersed particles having a salami structure refer to rubber-like polymer dispersed particles in which two or more particles of the aromatic vinyl polymer are included in the dispersed particles. It is necessary that the proportion of dispersed particles having a salami structure occupying therein is 80% by weight or more. If the proportion of the dispersed particles having a salami structure is less than 80% by weight, the impact resistance is reduced.

Further, the number of particles of the aromatic vinyl polymer contained in the rubber-like polymer-dispersed particles is at most 70% of the total number of dispersed particles. Preferably 8
It needs to be 0% or more. Here, the encapsulating aromatic vinyl-based polymer particles were photographed with an electron micrograph by ultra-thin sectioning of a rubber-modified aromatic vinyl-based resin.
In the photograph magnified 000 times, among the aromatic vinyl polymers included in the rubber-like polymer dispersed particles, it means particles having a minor diameter of 0.3 mm, that is, 0.03 μm or more in the photograph. When the number of particles of the contained aromatic vinyl polymer is 2
If the number of the dispersed particles is 0 or less than 70% of the total dispersed particles, the glossiness of the molded article is reduced.

Further, in the present invention, in order to obtain a desired property in balance of physical properties of mechanical strength, particularly impact resistance, the ratio of the rubber component to the toluene-insoluble component of the rubber-modified aromatic vinyl resin is set to 1. It needs to be in the range of 0 to 2.5. If the ratio is less than 1.0, there is a problem that the impact resistance is significantly reduced. If it is 2.5 or more, the rigidity is greatly reduced, and there is a problem that a satisfactory balance of physical properties cannot be obtained. Here, the toluene-insoluble matter means an insoluble matter when 1 g of the resin is dissolved in 30 ml of toluene.
Usually, the insoluble matter is separated by a centrifugal separator, and the weight of the solid matter obtained by drying is measured.

The rubber-modified aromatic vinyl resin composition of the present invention contains 0.005 to 0.5% by weight of silicone oil.
It is preferred that it is contained. When the content of the silicone oil is less than 0.005% by weight, the effect of improving the impact resistance is reduced. When the content is more than 0.5% by weight, the effect of adding the silicone oil not only reaches a plateau but also when the resin is molded. In some cases, problems such as bleeding on the surface of the molded article to cause poor appearance may occur. The silicone oil used is not particularly limited, but a silicone oil having a surface tension at 25 ° C. in the range of 19 to 22 dyne / cm is particularly effective, and the effect is exhibited by adding a small amount. If the surface tension of the silicone oil is out of the range of 19 to 22 dyne / cm, the impact resistance is undesirably reduced.

In the aromatic vinyl resin referred to as the component (A) of the present invention, the rubber-modified aromatic vinyl resin is 50 to 1
If it is contained in an amount of 00% by weight, another aromatic vinyl-based resin having good compatibility may be mixed. In this case, the aromatic vinyl monomer used as a raw material of the other aromatic vinyl resin is the same as the aromatic vinyl monomer used as a raw material of the rubber-modified aromatic vinyl polymerization. For example, these may be used alone or in combination of two or more. Further, other vinyl monomers which can be similarly copolymerized can be used as long as the effects of the present invention are not impaired.

In the present invention, a mixture of the above-mentioned aromatic vinyl resin and a polyphenylene ether resin having good compatibility at an arbitrary ratio may be used as the component (A). In this case, the mixing ratio of the polyphenylene ether-based resin in the component (A) is not particularly limited, but is 5 to 50% by weight, preferably 10 to 50% by weight.
It is used within the range of 40% by weight. If the compounding ratio exceeds 50% by weight, the moldability is poor, and if it is 5% by weight or less, the effect of improving the physical properties of impact resistance and heat resistance is small.

Here, the polyphenylene ether-based resin (PPE) used for the component (A) of the present invention refers to a resin containing a unit represented by the following general formula (I).

Embedded image General formula (I) (Where Q _{1 to} Q ₄ are each selected from the group consisting of hydrogen, hydrocarbon, or substituted hydrocarbon,
They may be the same or different. )

Preferred examples of the PPE include poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol. No. The method for producing the polyphenylene ether-based resin (PPE) is not particularly limited, and can be produced by a known method. Generally, it is obtained by oxidative polymerization of 2,6-xylenol.

The thermoplastic resin (B) of the present invention refers to a thermoplastic resin incompatible with the component (A). (B)
The thermoplastic resin as the component is exchanged with the polyester resin part (E) of the resin modifier, which is the component (C) of the present invention, between polar bonds such as transesterification, ester-amide exchange, and ester-carbonate exchange. It is preferable that the resin has a functional group that excites a reaction or a hydrogen bond, or a resin having one or more equivalents of polar bonds. Here, one equivalent is the number of functional groups or polar bonds per molecule calculated using the number average molecular weight or the product of the calculated or measured average degree of polymerization and the molecular weight in unit units. Here, the calculation is a value calculated by considering appropriate polymerization kinetics.

Specifically, thermoplastic resins, polycarbonate resins, polyester carbonate resins as resins for exciting ester exchange reaction or ester-carbonate exchange reaction, and polyamide resins, polyimide resins as resins for exciting ester-amide exchange or hydrogen bond, Polyamide imide resin is exemplified.

As an example of the thermoplastic resin of the component (B),
Polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyarylate, polycarbonate resin having a bisphenol derivative skeleton, polyester carbonate resin, 6 nylon, 6, 6, nylon, 11 nylon, 12 nylon, 4, 6 nylon, 12, 12 nylon, Polyamide resins such as 6T6 and 6 nylon (T represents terephthalic acid) and 6T6I nylon (I represents isophthalic acid); thermoplastic resins such as polyimide resins and polyamideimide resins; and mixtures thereof. The thermoplastic resin (B) constituting the resin composition of the present invention is not limited to the above-mentioned resins, but may be a functional group capable of reacting with the polyester part (E) of the resin modifier of the present invention. It is preferable to have one or more polar bonds.

The resin modifier (C) of the present invention is a copolymer composed of a vinyl resin part (D) and a polyester resin part (E), and the vinyl resin part (D) (A)
It must be compatible with the rubber-modified aromatic vinyl resin composition of the component, and the polyester resin part (E) has reactivity with the thermoplastic resin of the component (B). I need to do that. Examples of the copolymer used as the resin modifier of the component (C) include a random copolymer, a graft copolymer, and a block copolymer.
Particularly, a block copolymer is preferable. E. Helfand (J. Chem.
According to Phys. Vol. 57 1812 (1970), it has been reported that the terminal of the molecular chain has a higher probability of being present at the polymer-polymer interface, and that the block copolymer has a higher block copolymer than random and graft copolymers. It is considered that the polymer has higher reactivity and is superior in the compatibilizing effect.

In the resin modifier (C), the ratio of the polyester resin part (E) to the vinyl resin part (D) is 5 to 30% by weight of the polyester resin part (E) and the vinyl resin part (E). D) must be from 95 to 70% by weight. If the proportion of the polyester resin part (E) in the copolymer is less than 5% by weight, the reactivity is low and the compatibilizing effect is impaired. When the proportion of the polyester resin part (E) in the copolymer exceeds 30% by weight, the vinyl resin part (D) and the polyester resin part (E) in the modifier in the composite resin have a phase separation structure. Is formed, and the polyester resin portion (E) cannot be efficiently localized at the interface of the modifier domain, resulting in a decrease in reactivity and a decrease in impact resistance.

The polyester resin part (E) of the copolymer constituting the resin modifier as the component (C) of the present invention may be any one as long as the constituent units are linked by an ester bond. Alternatively, it is a polyester resin composed of a mixture of a dicarboxylic acid residue and a diol residue, or a mixture of an oxycarboxylic acid residue and a dicarboxylic acid residue and a diol residue. An example of the hydroxycarboxylic acid compound as a raw material of the polyester resin part (E) is p
-Hydroxybenzoic acid, p-hydroxyethylbenzoic acid, 2- (4-hydroxyphenyl) -2- (4'carboxyphenyl) propane, and the like. These may be used alone or in combination of two or more. May be used.

Examples of the dicarboxylic acid compound serving as a raw material of the dicarboxylic acid residue include terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 2,6-naphthalene. Dicarboxylic acid, 2,7-naphthalenedicarboxylic acid,
Examples thereof include aromatic dicarboxylic acids such as diphenic acid and aliphatic dicarboxylic acids such as adipic acid, pimelic acid, sebacic acid, malonic acid, succinic acid, malic acid, and citric acid. You may mix and use more than one type.

Next, examples of diol compounds serving as raw materials for diol residues include 2,2'-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as "bisphenol A") and bis (4-hydroxyphenyl). ) Methane, bis (2-hydroxyphenyl) methane, o-hydroxyphenyl-p-hydroxyphenylmethane, bis (4-
Hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl)
Sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4
-Hydroxyphenyl) diphenylmethane, bis (4-
(Hydroxyphenyl) -p-diisopropylbenzene,
Bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5-dimethyl -4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-)
Hydroxyphenyl) sulfide, 1,1-bis (4-
Hydroxyphenyl) ethane, 1,1-bis (3,5-
Dimethyl-4-hydroxyphenyl) ethane, 1,1-
Bis (4-hydroxyphenyl) cyclohexane, 1,
1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4
-Hydroxyphenyl) -1-phenylmethane, 2,2
-Bis (4-hydroxyphenyl) propane, 2,2-
Bis (4-hydroxyphenyl) butane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2 -Bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-chloro-4-hydroxyphenyl)
Propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-hydroxyphenyl) propane, 4,4 '-Biphenol, 3,3', 5,5 '
-Tetramethyl-4,4'-dihydroxybiphenyl,
There are aromatic diols such as 4,4'-dihydroxybenzophenone and aliphatic diols such as ethylene glycol, propylene glycol, 1,4-butanediol, pentamethylene glycol, hydrogenated bisphenol A, and the like. May be used as a mixture of two or more. Particularly, bisphenol A is preferably used.

Examples of the monomer constituting the vinyl resin part (D) of the resin modifier (C) include o-methylstyrene, m-methylstyrene, and styrene monomer.
Alkylized styrenes such as p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, t-butylstyrene, halogenated styrenes such as monochlorostyrene, styrene monomers such as α-methylstyrene, and other As vinyl monomers, lower alkyl esters of acrylic acid or methacrylic acid such as methacrylic acid and methyl acrylate, methacrylic acid and ethyl acrylate, acrylonitrile, polar vinyl monomers such as vinyl chloride, maleic anhydride, n-phenylmaleimide, vinyl naphthalene And the like.

Suitable vinyl resin parts (D) include styrene resins, for example, polystyrene, styrene and acrylonitrile, acrylate, and copolymers of methacrylate and styrene. Note that the present vinyl resin portion may be in a chain shape, and may be branched. The vinyl resin part (D) has -C = C in the main chain.
-May have up to 50% by weight of the repeating unit. It is not preferred that the content of -C = C- in the main chain is 50% by weight or more, since heat resistance is poor and discoloration and gelation occur at high temperatures. -C = C- is preferably 20% by weight or less, more preferably 10% by weight or less, still more preferably 5% by weight or less.
It is desirable that the content be less than 10% by weight to prevent discoloration and gelation.

The molecular weight of the vinyl resin part (D) of the copolymer is not particularly limited, but the number average molecular weight (Mn) is preferably 1,000 to 70,000. If the number average molecular weight is less than 1,000, the mechanical strength may be reduced, and if it exceeds 70,000, the compatibility is reduced and the function as a resin modifier is reduced.

[0039]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be specifically described below. The mixing ratio of the resin composition of the present invention is (A)
The component (A), which is the component (B), is added to the aromatic vinyl resin (composition) of the component, or 90 to 10 parts by weight of a mixture of the aromatic vinyl resin (composition) and the polyphenylene ether resin. It is necessary that the resin composition is composed of 10 to 90 parts by weight of the incompatible thermoplastic resin and 0.03 to 10 parts by weight of the resin modifier (C). When the constituent ratio of the rubber-modified aromatic vinyl resin composition as the component (A) is less than 10 parts by weight, the characteristics of the resin composition are hardly exhibited, and the moldability and impact resistance are hardly expressed. Similarly, if the resin (B) is less than 10 parts by weight, the heat distortion temperature decreases,
It is difficult to reflect the physical properties of the resin (B) component.

If the amount of the resin modifier (C) added to the resin composition is less than 0.03 parts by weight, the reactivity is low and no compatibilizing effect is exhibited. If the amount of the resin modifier exceeds 10 parts by weight, the vinyl resin part (D) and the polyester resin part (E) in the composite resin form a phase-separated structure in the composite resin, and the polyester resin is efficiently produced. The part (E) cannot be unevenly distributed at the interface between the modifier domains, resulting in a decrease in reactivity and a decrease in impact resistance.

Further, additives for various resins can be mixed into the resin composition of the present invention, if necessary. These additives include, for example, heat stabilizers, antioxidants,
Examples include light stabilizers, release agents, lubricants, pigments, flame retardants, plasticizers, antistatic agents, antibacterial and antifungal agents. In addition, for example, a fiber reinforcing material such as glass fiber, metal fiber, potassium whisker, carbon fiber, or a filler reinforcing material such as talc, calcium carbonate, mica, glass flake, milled fiber, metal flake, or metal powder is mixed. May be. The resin composition of the present invention can be produced by melt-kneading the components using various known mixers. As various known mixers, for example, various extruders,
Examples include Brabender, kneaders, and Banbury mixers.

[0042]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the contents of the present invention. In each of the following examples, physical properties were evaluated by the following methods.

Evaluation of impact resistance: An Izod impact test (with a notch) was carried out using a test piece (thickness: 3.2 mm, 6.4 mm) obtained by molding according to ASTM D-256. -Evaluation of gloss: Measurement was performed according to JIS K7105.・ Layer peeling resistance: According to JIS K5400, scratches are made on the molded product at a distance of 1 mm in a square pattern, and a cloth adhesive tape N
o.750 (manufactured by Nitto Denko Corporation) was closely adhered, and the surface was observed after vigorously peeling off.
X: There was lamellar peeling.

The resin modifier (C) used in the following examples was prepared as described below, and the following parts and percentages indicate parts by weight and percentage by weight, respectively. -Resin modifier (C) component: Production example of aromatic polyester-polystyrene block copolymer (PS-b-PAr) 4,4'-azobiscyanovaleric acid as a polymerization initiator and styrene monomer as a monomer Radical polymerization using terminal carboxyl group polystyrene (P
S-COOH). (COOH equivalent = 2.00)
This terminal carboxyl group styrene resin is reacted with 5 times equivalent of bisphenol A in the presence of 5 times equivalent of triphenylphosphine, hexachloroethane and triethylamine with respect to the terminal carboxyl group, and the terminal phenolic styrene resin (PS-OH ) Manufactured. The terminal phenolic styrenic resin (PS-OH), bisphenol A and iso / terephthalic acid dichloride are combined with PS and P
It was added according to the ratio with Ar, and solution condensation polymerization was carried out in the presence of triethylamine and calcium hydroxide. After the completion of the polymerization, a large amount of an aqueous acetic acid solution was added to the reaction solution to remove the unreacted substances to make the reaction solution acidic. After removing the aqueous layer from the acidified reaction solution, a large amount of methanol was added to recover the polymer.
Average molecular weight (Mn) or PS / P as shown in Table 1.
Five types of aromatic polyester-polystyrene block copolymers having different Ars (PS-b-PAr) B, C,
D and E were obtained.

[0045]

[Table 1]

Examples 1 to 6 As the component (A), a rubber content of 13.2% by weight, an average rubber particle diameter of 0.59 μm, and a cumulative particle diameter distribution of 5% value 0.7
5 μm, cumulative particle size distribution 95% value 0.29 μm, ratio of rubber particles having salami structure 96%, ratio of 20 or less contained PS 94%, ratio of toluene-insoluble matter to rubber component 2.
Rubber modified polystyrene (HI) to which 0.05% by weight of silicone oil having a surface tension of 20.9 dyne / cm is added.
PS resin-A), polycarbonate (PC: Novarex 7022A manufactured by Mitsubishi Engineering-Plastics Corporation) as a component (B), and various copolymers shown in Table 1 as a copolymer of a component (C). With the composition shown in Table 2, the mixture was melt-kneaded at a cylinder temperature of 260 ° C. and a screw rotation speed of 100 rpm by a 30 mmφ twin screw extruder manufactured by Ikegai, and pelletized. This composition is applied to Toshiba Machine
Various test pieces were molded at a cylinder temperature of 260 ° C. and a mold temperature of 50 ° C. using a 100 t injection molding machine. Table 2 shows the results of evaluation tests of various physical properties and characteristics using this test piece.
Are shown together.

Example 7 Table 2 shows copolymers shown in Table 2, rubber-modified polystyrene (HIPS) and polyphenylene ether (trade name: Zylon X0101, manufactured by Asahi Kasei) and polycarbonate similar to those in Examples 1 to 6. Examples 1 to 6 in composition
After melt-kneading in the same manner as described above, a test piece was formed. Table 2 shows the characteristic evaluation results.

Comparative Examples 1 to 6 Copolymers of component (C) shown in Table 2 and the same rubber-modified polystyrene and polycarbonate as in Examples 1 to 6 were used.
After melt-kneading in the composition shown in Table 2 in the same manner as in Examples 1 to 6, test pieces were prepared. Table 2 shows the characteristic evaluation results.

Comparative Example 7 As the component (A), the rubber content was 10.0% by weight, the average rubber particle diameter was 1.0 μm, and the cumulative particle diameter distribution was 5%, 1.5 μm.
m, cumulative particle size distribution 95% value 0.6 μm, ratio of rubber particles having a salami structure 98%, ratio of not more than 20 encapsulated PS 65%, ratio of toluene-insoluble matter and rubber component 2.2, surface tension 20. 9 dyne / cm silicone oil 0.0
5% by weight of rubber-modified polystyrene (HIPS resin-B) Polycarbonate (PC: Novalex 7022A, manufactured by Mitsubishi Engineering-Plastics Corporation) as a component (B) and various copolymers shown in Table 1 as a copolymer of a component (C) Each component of the copolymer B was melt-kneaded in the composition shown in Table 2 in the same manner as in Examples 1 to 6, and then a test piece was formed. Table 2 summarizes the results of evaluation tests of various physical properties and characteristics using this test piece.

Comparative Example 8 As the component (A), the rubber content was 12.8% by weight, the average rubber particle size was 0.43 μm, and the cumulative particle size distribution was 5% 0.8.
2 μm, 95% cumulative particle size distribution 0.15 μm, 52% of rubber particles having a salami structure, 93% of 20 or less encapsulated PS, ratio of toluene-insoluble matter and rubber component of 2.
3. Rubber-modified polystyrene (HIP) containing 0.05% by weight of silicone oil having a surface tension of 20.9 dyne / cm
S resin-C) and polycarbonate (PC: Novarex 7022A manufactured by Mitsubishi Engineering-Plastics Corporation) as the component (B), and various copolymers B shown in Table 1 as the copolymer of the component (C). After the components were melt-kneaded in the composition shown in Table 2 in the same manner as in Examples 1 to 6, test pieces were molded. Table 2 summarizes the results of evaluation tests of various physical properties and characteristics using this test piece.

Comparative Example 9 Copolymer B of component (C) shown in Table 2 and a rubber content of 12
% By weight, average rubber particle diameter 2.3 μm, cumulative particle diameter distribution 5% value 3.64 μm, cumulative particle diameter distribution 95% value 1.20
Rubber modified polystyrene (HIPS resin-D) and polycarbonate (brand name Nova) having a particle size of 96%, a ratio of rubber particles having a salami structure of 96%, a ratio of 20 or less included PSs of 50%, a ratio of a toluene insoluble component to a rubber component of 3.3. Rex 7022A, manufactured by Mitsubishi Engineering Plastics)
Was melt-kneaded in the composition shown in Table 2 in the same manner as in Examples 1 to 6, and then a test piece was prepared. Table 2 shows the characteristic evaluation results.

Comparative Example 10 Copolymer F (styrene-maleic anhydride copolymer, trade name: Dailac D332, manufactured by ARCO Chemical), rubber-modified polystyrene (resin-A) and polycarbonate (PC: trade name NOVAREX 7022A) ,
After melt-kneading (manufactured by Mitsubishi Engineering-Plastics) in the composition shown in Table 2 in the same manner as in Examples 1 to 6,
Test specimens were formed. Table 2 shows the characteristic evaluation results.

Comparative Example 11 Copolymer G (polycarbonate-polystyrene-based graft copolymer), rubber-modified polystyrene (resin-A) and polycarbonate (trade name NOVAREX 7022)
A, manufactured by Mitsubishi Engineering Plastics)
After the composition was melt-kneaded in the same manner as in Examples 1 to 6, a test piece was prepared. Table 2 shows the characteristic evaluation results.

[0054]

[Table 2]

From a comparison between Examples 1 to 7 and Comparative Examples 1 to 11, it is recognized that the resin composition of the present invention has an excellent compatibility effect and has particularly high impact resistance.

[0056]

The resin composition of the present invention described above has good compatibility between different kinds of resins and excellent impact resistance. Therefore, it is suitable only for automobiles as a material having a good balance of physical properties such as impact resistance. Not only industrial parts, electronic equipment,
It can be used in a wide range of fields such as general housing equipment and sundries.

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Claims (5)

[Claims] An aromatic vinyl resin containing 50 to 100% by weight of a rubber-modified aromatic vinyl resin.
90 to 10 parts by weight (B) component; thermoplastic resin 10 incompatible with component (A)
Component (C); 95 to 70% by weight of a vinyl resin part (D) compatible with the component (A), and a polyester resin part (E) 5 reactive with the component (B). ~ 30% by weight
Resin modifier 0.03 to 1 which is a copolymer composed of
A resin composition blended at a ratio of 0 parts by weight;
The rubber-modified aromatic vinyl-based resin in the component has the following (i) to
(Iii) requirements, (i) the weight average particle size of the dispersed particles of the rubbery polymer dispersed in the aromatic vinyl polymer is 0.4
And the 5% value of the cumulative particle size distribution on a weight basis is 1.0 μm or less, the 95% value is 0.2 μm or more, and (ii) salami occupying in all rubbery polymer dispersed particles. The ratio of the dispersed particles having a structure is 80% by weight or more, and the dispersed particles in which the number of particles of the aromatic vinyl polymer contained in all the rubbery polymer dispersed particles is 20 or less are all dispersed. A resin composition, which satisfies 70% or more of the particles and (iii) a ratio of a toluene insoluble content to a rubber content of 1.0 to 2.5. 2. The resin composition according to claim 1, wherein the component (A) is a mixture of an aromatic vinyl resin containing 50 to 100% by weight of a rubber-modified aromatic vinyl resin and a polyphenylene ether resin. 3. The component (C) comprises a styrene-based resin part (D).
And a polyester resin part (E), and the number average molecular weight (Mn) of the block copolymer is in the range of 1,000 to 70,000.
The resin composition as described in the above. 4. The polyester resin part (E) of the component (C)
4. The resin composition according to claim 1, which comprises an aromatic dicarboxylic acid residue and an aromatic diol residue. 5. Component (B) is a thermoplastic polyester,
3. The resin composition according to claim 1, wherein the resin composition is at least one resin selected from the group consisting of a polycarbonate resin, a polyamide resin, a polyimide resin, a polyamideimide resin, and a polyester carbonate resin.