JPH07108947B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a thermoplastic resin composition. For more details
The present invention relates to a thermoplastic resin composition containing ABS resin, polyamide, and a specific multi-component copolymer, which is particularly excellent in impact resistance.

(Prior Art) Conventionally, since ABS resin has excellent hardness, impact resistance and moldability, it is used for automobile parts, building materials, electric appliances,
It is used in various fields as various molded products.
However, ABS resins generally have a low heat distortion temperature and are not satisfactory as heat resistant materials.

As a method for improving the heat distortion temperature of the ABS resin, for example, a method of replacing a part of styrene which is an aromatic vinyl monomer with α-methylstyrene, a method of adding a filler, and the like have already been adopted. However, these methods have drawbacks such as reduced impact resistance.

Further, in recent years, a method of improving heat resistance by blending a polyamide with an ABS resin has been proposed. However, ABS resins and polyamides are generally incompatible, and even if they are simply blended, phase separation occurs and impact resistance decreases, so the blended composition is difficult to use as a molding material.

As a means for solving this problem, a compatibilizing agent such as a styrene-acrylonitrile-based copolymer containing glycidyl methacrylate or a styrene-acrylonitrile-based copolymer containing maleic anhydride was added to the ABS resin and polyamide as the third component. A blended thermoplastic resin composition has been proposed (JP-A-62-11760). However, because these compatibilizers react with polyamides,
The flowability and moldability of the thermoplastic resin composition may deteriorate,
Further, there is a defect that gelation occurs during kneading and molding. Further, a thermoplastic resin composition has been proposed in which an ABS resin and a polyamide are blended with a styrene-based copolymer containing a hydroxy group-containing vinyl monomer as a compatibilizer (Japanese Patent Laid-Open No. 1-146956). However, the impact resistance has not been sufficiently improved even by such an invention.

(Problems to be Solved by the Invention) The present invention has an object to provide a thermoplastic resin composition having not only the characteristics of both ABS resin and polyamide but also excellent impact resistance.

(Means for Solving the Problem) As a result of repeated intensive studies, the present inventors focused their attention on the compatibilizers of ABS resin and polyamide to solve the above problems,
As a compatibilizer, a styrene-acrylonitrile copolymer having a hydroxy group and a styrene-acrylonitrile copolymer having an amino group are used in combination, or a styrene-acrylonitrile copolymer having a hydroxy group and an amino group is used. As a result, they have found that a thermoplastic resin composition having a significantly improved impact resistance can be obtained, and completed the present invention.

That is, the present invention relates to a total of 100 parts by weight of ABS resin 20 to 95 parts by weight and polyamide 80 to 5 parts by weight, hydroxy group-containing vinyl monomer 0.1 to 70% by weight, aromatic vinyl monomer 1 to 80% by weight and 1 to 80% by weight of a cyano group-containing vinyl monomer as a constituent component, and the weight ratio of the aromatic vinyl monomer and the cyano group-containing vinyl monomer is
50:50 to 95: 5 multi-component copolymer; 1 to 10 parts by weight, and 0.1 to 70% by weight of amino group-containing vinyl monomer, 1 to 80% by weight of aromatic vinyl monomer and cyano group Containing 1 to 80% by weight of vinyl monomer as a constituent component, and the weight ratio of aromatic vinyl monomer and cyano group-containing vinyl monomer is 50: 5.
0-95: 5 multi-component copolymer; thermoplastic resin composition containing 1-10 parts by weight, ABS resin 20-95 parts by weight, and polyamide 80-5 parts by weight based on 100 parts by weight in total , Hydroxy group-containing vinyl monomer 0.1-70% by weight, amino group-containing vinyl monomer 0.1-70% by weight, aromatic vinyl monomer 1-80% by weight and cyano group-containing vinyl monomer 1-
80% by weight is a constituent component, and the weight ratio of the aromatic vinyl monomer and the cyano group-containing vinyl monomer is 50:50 to 95:
The present invention relates to a thermoplastic resin composition containing 5 to 20 parts by weight of a multi-component copolymer;

In the present invention, the multicomponent copolymer and the multicomponent copolymer are used together as the compatibilizing agent, or the multicomponent copolymer is used.
First, the multicomponent copolymer which is a compatibilizer will be described.

In the present invention, the multi-component copolymer is a hydroxy group-containing vinyl monomer 0.1 to 70 wt%, preferably 2 to 25 wt%, aromatic vinyl monomer 1 to 80 wt%, preferably 30 to 80 wt%, And 1 to 80% by weight of a cyano group-containing vinyl monomer,
Preferably 10 to 35 wt% as an active ingredient, and the weight ratio of the aromatic vinyl monomer and the cyano group-containing vinyl monomer is 50:50 to 95: 5, preferably 65:35 to 80:20. Is.

The hydroxy group-containing vinyl monomer includes 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth).
Acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-2-putylpropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate (addition mole number of ethylene oxide 2 to 10) , Polypropylene glycol mono (meth) acrylate (the number of moles of propylene oxide added is 2 to 10), and the like.
These are used alone or in combination of two or more. Among these, 2-hydroxypropyl (meth) acrylate is preferable. Hydroxy group containing vinyl monomer
If it is less than 0.1% by weight, it has no effect as a compatibilizer and A
The compatibility of BS resin and polyamide is not improved. 70% by weight
If it is more, the impact resistance will be deteriorated.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene and the like, and one of these may be used alone or two or more of them may be used in combination. Of these, it is preferable to use styrene. preferable. When the amount of the aromatic vinyl monomer is less than 1% by weight or more than 80% by weight, the compatibility with the ABS resin becomes poor and the compound does not function as a compatibilizer.

Acrylonitrile as a cyano group-containing vinyl monomer,
Methacrylonitrile and the like can be mentioned, and one of these is used alone, or two or more thereof are used in combination, and of these, it is preferable to use acrylonitrile. The cyano group-containing vinyl monomer is less than 1% by weight, or 80
If it exceeds 5% by weight, the compatibility with the ABS resin becomes poor from the viewpoint of polarity and it does not function as a compatibilizer.

Further, if the weight ratio of the aromatic vinyl monomer and the cyano group-containing vinyl monomer deviates from the range of 50:50 to 95: 5, the ABS resin-
The compatibility of the polyamide is insufficient, and the impact resistance of the resulting thermoplastic resin composition is not sufficiently improved.

In the present invention, the multi-component copolymer is 0.1 to 70% by weight of amino group-containing vinyl monomer, preferably 2 to 25% by weight, 1 to 80% by weight of aromatic vinyl monomer, and preferably 30 to 80% by weight. , And 1 to 80% by weight of the cyano group-containing vinyl monomer, preferably 10 to 35% by weight as an active ingredient, and the weight ratio of the aromatic vinyl monomer and the cyano group-containing vinyl monomer is 50: It is 50 to 95: 5, preferably 65:35 to 80:20.

As the amino group-containing vinyl monomer, 2-N, N-dimethylaminoethyl (meth) acrylate, 2-N, N-diethylaminoethyl (meth) acrylate, 2-N, N-dibutylaminoethyl (meth) acrylate, 2-N, N-dimethylaminopropyl (meth) acrylate, 2-N, N
-Diethylaminopropyl (meth) acrylate, 3-
N, N-dibutylaminopropyl (meth) acrylate,
6-N, N-dimethylaminohexyl (meth) acrylate, 6-N, N-diethylaminohexyl (meth) acrylate and the like can be mentioned, and one of these can be used alone or two or more can be used in combination. When the amount of the amino group-containing vinyl monomer is less than 0.1% by weight, it has no effect as a compatibilizing agent and the compatibility between the ABS resin and the polyamide is not improved. If it is more than 70% by weight, the impact resistance is rather lowered.

Further, the aromatic vinyl monomer and cyano group-containing vinyl monomer of the multi-component copolymer may be the same as those of the multi-component copolymer, and the amount thereof is also the same as that of the multi-component copolymer. Good.

The multi-component copolymer of the present invention is a hydroxy group-containing vinyl monomer 0.1-70% by weight, preferably 2-10% by weight, an amino group-containing vinyl monomer 0.1-70% by weight, preferably 2-10% by weight, Aromatic vinyl monomer 1 to 80% by weight, preferably
30 to 80% by weight and a cyano group-containing vinyl monomer 1 to 80% by weight, preferably 10 to 35% by weight as an active ingredient,
The weight ratio of the aromatic vinyl monomer to the cyano group-containing vinyl monomer is 50:50 to 95: 5, preferably 65:35 to 80:20.

Here, the hydroxy group-containing vinyl monomer, the amino group-containing vinyl monomer, the aromatic vinyl monomer and the cyano group-containing vinyl monomer may be the same as those used in the multi-component copolymer.

Further, in addition to the above-mentioned multi-component copolymer, and the vinyl monomer, a methacrylic acid lower alkyl ester such as methyl methacrylate may be used as an optional monomer, but the compatibility with the ABS resin-polyamide may be used. Considering this, the content is up to 20% by weight or more of the constituents of the multi-component copolymer.

The method for producing the multi-component copolymer is not particularly limited, and various known methods may be used, including any method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.

The number average molecular weight of each of the multicomponent copolymers thus obtained is
It is 3,000 to 100,000, preferably 10,000 to 500000. 3000
If it does not meet the requirements, the impact resistance and heat distortion temperature of the thermoplastic resin composition obtained will decrease, and if it exceeds 1000000, the fluidity will deteriorate.

Next, the thermoplastic resin composition of the present invention will be described.

Various known resins can be used as the ABS resin of the present invention. For example, in the presence of a diene rubber component, a graft copolymer obtained by bulk polymerization, suspension polymerization or emulsion polymerization of a mixed monomer composed of an aromatic vinyl monomer and a cyano group-containing vinyl monomer, Examples thereof include blends of a copolymer obtained from an aromatic vinyl monomer and a cyano group-containing vinyl monomer and a copolymer obtained from a diene monomer and a cyano group-containing vinyl monomer.

Examples of the diene rubber component include polybutadiene, polyisoprene, and various synthetic rubbers such as copolymers of these diene monomers and styrene and acrylonitrile, or natural rubber. As the aromatic vinyl monomer, styrene, α-methylstyrene, p
-Methylstyrene and the like, and examples of the cyano group-containing vinyl monomer include acrylonitrile and methacrylonitrile.

On the other hand, various known polyamides can be used,
For example, nylon-6, nylon-11, nylon-12,
Examples thereof include nylon-6,6, nylon-12,12, nylon-4,6 and nylon-6,12, and copolymers thereof can also be used.

The thermoplastic resin composition of the present invention has a phase ratio of 20 to 95 parts by weight of ABS resin, preferably 50 to 90 parts by weight and 80 to 5 parts by weight of polyamide, preferably 50 to 10 parts by weight to a total of 100 parts by weight. 2 to 20 parts by weight of the multicomponent copolymer as a solubilizer is blended.

If the ABS resin content is less than 20 parts by weight, the impact resistance will decrease, and if it exceeds 90 parts by weight, the heat distortion temperature will not improve. If the polyamide content is less than 5 parts by weight, the heat distortion temperature will not be improved, and if it exceeds 80 parts by weight, the impact resistance will be reduced.

When the compatibilizer is used in combination with the multicomponent copolymer, it is 1 to 10 parts by weight, preferably 4 to 6 parts by weight of the multicomponent copolymer, and 1 to 10 parts by weight, preferably 4 to 6 parts of the multicomponent copolymer.
Parts by weight. When the content of the multicomponent copolymer is less than 1 part by weight, the dispersibility becomes poor. If it is more than 20 parts by weight, the impact resistance is rather lowered.

When the multi-component copolymer is used alone, it is 2 to 20 parts by weight, preferably 8 to 12 parts by weight. When the amount of the multi-component copolymer is less than 2 parts by weight, the compatibility is not improved,
Dispersibility deteriorates. If it is more than 20 parts by weight, the impact resistance is rather lowered.

The compatibilizing agent of the present invention may be used in the range of 2 to 20 parts by weight based on 100 parts by weight of the ABS resin and the polyamide, in addition to the above examples, by appropriately combining the multi-component copolymer.

The method for producing the thermoplastic resin composition of the present invention is AB
It is carried out by melt mixing the S resin, polyamide and compatibilizer. Melt mixing may be performed by a known method,
It is usually performed at 160-260 ℃. Extruder for melt mixing
Any device such as a kneader or Banbury mixer may be used. Also, the order of the melt mixing is arbitrary.
Any method such as a method of melting and mixing the ABS resin, the polyamide and the compatibilizing agent at once, a method of melting and mixing the ABS resin and the polyamide and then mixing with the compatibilizing agent, and any other method may be used. When the multi-component copolymer and the multi-component copolymer are used as the compatibilizing agent, the multi-component copolymer and may be melt-mixed in advance, or may be separately melt-mixed.

The dispersed particle size of the thermoplastic resin composition thus obtained is 1.
It is preferably 0 μm or less.

The thermoplastic resin composition of the present invention has gloss, fluidity, moldability,
In addition to being excellent in workability and heat distortion temperature, impact resistance was greatly improved as compared with conventionally known thermoplastic resin compositions of ABS resin and polyamide.

Therefore, the thermoplastic resin composition of the present invention is not only used in the fields conventionally used, but also in electrical, electromechanical parts,
It can be used in a wide range of fields such as automobile parts.

It is due to the compatibilizing agent of the present invention that such a thermoplastic resin composition of the present invention has excellent impact resistance, but this is because the compatibilizing agent of the present invention forms a dispersion of an ABS resin and a polyamide extremely. It is considered to have the effect of making it fine and further enhancing the adhesive force at the interface between the both.

(Effects of the Invention) The thermoplastic resin composition of the present invention has gloss, fluidity, moldability,
In addition to being excellent in workability and heat distortion temperature, impact resistance was greatly improved as compared with the conventionally known thermoplastic resin composition comprising ABS resin and polyamide.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples, and Comparative Examples, but the present invention is not limited to these Examples. In each example, parts and% are based on weight, and the numerical values in the table are parts by weight.

Production Example 1 equipped with a reflux condenser, a stirrer, a thermometer and a nitrogen inlet tube
2333 parts of ion-exchanged water and polyvinyl alcohol (trade name POVAL 224 (saponification degree 88 mol%) / trade name POVAL 124 (saponification degree 98.5 mol%) = 8/2,
2 parts (made by Kuraray Co., Ltd.) were charged and heated and dissolved while blowing nitrogen. After cooling, 665 parts of styrene, 285 parts of acrylonitrile, 50 parts of 2-hydroxypropylmethacrylate and 10 parts of azobisisobutyronitrile were added and the polymerization reaction was carried out at 75 ° C for 3 hours with vigorous stirring to give a number average molecular weight of 8.7 x 10 ⁴ , a copolymer having a hydroxyl value of 17.2 was obtained. Hereinafter, the copolymer is referred to as a copolymer A.

Production Example 2 630 parts of styrene and acrylonitrile 270 in Production Example 1
Parts, except that 100 parts of 2-hydroxypropyl methacrylate were used, the same procedure as in Production Example 1 was repeated to obtain a number average molecular weight of 1.0.
A copolymer having a viscosity of × 10 ⁵ and a hydroxyl value of 34.5 was obtained. Hereinafter, the copolymer is referred to as a copolymer B.

Production Example 3 560 parts of styrene and 240 of acrylonitrile in Production Example 1
Parts, 2-hydroxypropylmethacrylate 200 parts were replaced by the same procedure as in Production Example 1, except that the number average molecular weight was 1.15.
A copolymer having a viscosity of × 10 ⁵ and a hydroxyl value of 69.2 was obtained. Hereinafter, the copolymer is referred to as a polymer C.

Production Example 4 In Production Example 1, 665 parts of styrene and acrylonitrile 2
85 parts, 2-N, N-diethylaminoethyl methacrylate 5
Except for replacing 0 part, the same procedure as in Production Example 1 was carried out to obtain a copolymer having a number average molecular weight of 2.0 × 10 ⁵ and an amine value of 12.0. Hereinafter, the copolymer will be referred to as polymer D.

Production Example 5 630 parts of styrene and acrylonitrile 270 in Production Example 1
Part, 2-N, N-diethylaminoethyl methacrylate 100
Except for replacing parts, the same procedure as in Production Example 1 was carried out to obtain a copolymer having a number average molecular weight of 1.45 × 10 ⁵ and an amine value of 27.2. Less than,
The copolymer is referred to as polymer E.

Production Example 6 560 parts of styrene and 240 of acrylonitrile in Production Example 1
Part, 2-N, N-dimethylaminoethyl methacrylate 200
Except for replacing parts, the same procedure as in Production Example 1 was carried out to obtain a copolymer having a number average molecular weight of 1.19 × 10 ⁵ and an amine value of 57.2. Hereinafter, the copolymer is referred to as a polymer F.

Production Example 7 630 parts of styrene and acrylonitrile 270 in Production Example 1
Parts, 50 parts of 2-hydroxypropyl methacrylate, and 50 parts of 2-N, N-dimethylaminoethyl methacrylate were further added, and the same procedure as in Production Example 1 was repeated to obtain a number average molecular weight of 2.0 × 10 ⁵ and a hydroxyl value. A copolymer having 17.2 and an amine value of 12.0 was obtained. Hereinafter, the copolymer is referred to as a polymer G.

Examples 1 to 10 and Comparative Examples 1 to 7 Polyamide (nylon-6, brand name Ube nylon 1013
B, Ube Industries, Ltd., ABS resin (trade name DENKA GR-
2000, manufactured by Denki Kagaku Co., Ltd., and the copolymers A to G obtained in Production Examples 1 to 7 were mixed in a ratio as shown in Table 1 and then using a KRC S-1 kneader manufactured by Kurimoto Iron Works. Were kneaded at 230 ° C. and pelletized. The pellets were molded into a 5 ″ × (1/2) ″ × (1/8) ″ molded product by an injection molding machine and the following physical properties were evaluated. The results are shown in Table 2.

(1) Dispersibility A part of the molded product was cut out, treated with formic acid to dissolve the polyamide, and a sample was prepared. The obtained sample was observed for the dispersed particle diameter (μm) with a field emission scanning electron microscope (S-800 manufactured by Hitachi, Ltd.).

(2) Izod impact strength The value at 23 ° C was measured using an Izod impact tester manufactured by Toyo Seiki Seisakusho in accordance with the Izod impact test method of JIS K7110.

Claims (3)

[Claims] 1. 20 to 95 parts by weight of ABS resin and 80 polyamide
To 100 parts by weight of total 5 parts by weight, 0.1 to 70% by weight of vinyl monomer containing hydroxy group, 1 to 80% by weight of aromatic vinyl monomer and 1 to 80% by weight of vinyl monomer containing cyano group. % As a constituent component, and the weight ratio of the aromatic vinyl monomer and the cyano group-containing vinyl monomer is
50:50 to 95: 5 multi-component copolymer; 1 to 10 parts by weight, and 0.1 to 70% by weight of amino group-containing vinyl monomer, 1 to 80% by weight of aromatic vinyl monomer and cyano group Containing 1 to 80% by weight of vinyl monomer as a constituent component, and the weight ratio of aromatic vinyl monomer and cyano group-containing vinyl monomer is 50: 5.
A thermoplastic resin composition comprising 0 to 95: 5 multi-component copolymer; 1 to 10 parts by weight. 2. ABS resin 20 to 95 parts by weight and polyamide 80
To 5 parts by weight, for a total of 100 parts by weight, hydroxy group containing vinyl monomer 0.1 to 70% by weight, amino group containing vinyl monomer 0.1 to 70% by weight, aromatic vinyl monomer 1 to 80 parts by weight % And cyano group-containing vinyl monomer 1
80% by weight is a constituent component, and the weight ratio of the aromatic vinyl monomer and the cyano group-containing vinyl monomer is 50:50 to 95:
5. A thermoplastic resin composition containing 5 to 20 parts by weight of a multi-component copolymer; 3. The thermoplastic resin composition according to claim 1, wherein the hydroxy group-containing vinyl monomer is hydroxyalkyl acrylate or hydroxyalkyl methacrylate.