JPH09217006A - Heat-resistant thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition capable of giving moldings excellent in heat distortion resistance, impact resistance, molding fluidity and appearance, by incorporating kaolin in a composition containing a rubber component subjected to particle size enlargement treatment. SOLUTION: This composition is obtained by incorporating (E) 0.1-30 pts.wt. of kaolin in a total of 100 pts.wt. of (A) 5-95 pts.wt. of a polyamide resin, (B) 5-95 pts.wt. of an unsaturated carboxylic acid-contg. copolymer made form 40-80wt.% of an aromatic vinyl compound, 15-50wt.% of a vinyl cyanide compound, 0.1-20wt.% of an unsaturated carboxylic acid compound and 0-30wt.% of another copolymerizable vinyl compound, and (C) 5-50 pts.wt. of a graft copolymer produced by graft copolymerization of 60-5wt.% of a vinyl compound in the presence of 40-95wt.% of particle enlarged rubber 0.1-2.0μm in average particle size prepared by particle enlargement treatment through incorporating 100wt.% of a rubber latex with (D) 0.1-15wt.% of an acid group-contg. copolymer latex 0.05-0.5μm in average particle size.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel heat-resistant thermoplastic resin which is excellent in heat distortion resistance, impact resistance and surface appearance, and is excellent in molding fluidity. More specifically, it relates to a heat-resistant thermoplastic resin composition comprising a styrene resin using a rubbery polymer obtained by enlarging rubber, a polyamide resin, and kaolin.

[0002]

2. Description of the Related Art Polyamide resins are used in electric and automobile parts because they are excellent in heat distortion resistance, rigidity, chemical resistance, etc., but further improvement in impact resistance and water resistance is desired. ing. On the other hand, A, which is a typical rubber-reinforced resin
BS resin is used for automobiles, electricity, and sundries parts because it has excellent impact resistance and workability, but chemical resistance,
Further improvement in heat distortion resistance and rigidity is desired. Attempts have been made to blend a polyamide resin and an ABS resin to make the best use of their characteristics, but originally, the compatibility separation between the polyamide resin and the ABS resin is very poor, and a molded product made of the mixture is Dispersion of the two-component resin becomes non-uniform, and only those that cannot be used practically, such as poor surface appearance, delamination, and reduced impact resistance can be obtained.

Therefore, attempts have been made to modify the compatibility between the polyamide resin and the ABS resin by adding a compatibilizer and modifying the ABS resin. For example, a method of reacting a polyamide component graft-copolymerized with a monomer containing an unsaturated carboxylic acid with an amine terminal of a polyamide (Japanese Patent Laid-Open No. 4-4120).
7-6284), a method of introducing styrene-maleic anhydride as a compatibilizing agent (JP-A-56-50931), and the like. There is also disclosed a method of blending a modified styrene resin obtained by graft-copolymerizing styrene, acrylonitrile and an unsaturated carboxylic acid with a rubber component to polyamide (Japanese Patent Laid-Open Nos. 63-179957 and 63-182369). Although the compatibility of the polyamide resin and the ABS resin can be improved and the impact resistance can be improved by these methods, the heat distortion resistance is still at an insufficient level.

In order to improve impact resistance, it is known as a general method to increase the content of the rubber component in the resin, but this method does not improve impact resistance but heat deformation resistance. Also, there is a drawback that the molding fluidity is deteriorated, and as a result, the overall balance of physical properties is deteriorated.

As a means for improving heat resistance, a method of adding a copolymer resin containing an imide compound as a third component (Japanese Patent Publication No. 61-60098, JP-A No. 62-22).
844) and the like have been proposed. Although the heat distortion resistance is certainly improved by such a method, there is a problem that the impact resistance and the molding fluidity are remarkably lowered.

Regarding the type of rubber of the rubber-like polymer used in the rubber-reinforced resin such as ABS resin, a wide variety of rubbers are used, but the most widely used one is the diene (co) polymer. And a rubber composed of an acrylic ester (co) polymer. The diene rubber and acrylate rubber are usually produced by emulsion polymerization and can be obtained in the form of latex. However, the particle diameter of the rubber obtained by emulsion polymerization is 0.1 μm or less unless a special operation is performed, and the particle diameter is too small as a graft copolymer for a rubber-reinforced resin. Therefore, various methods have been implemented or proposed in order to obtain a rubber latex having a desired large particle size. One is a method of producing a rubber latex having a large particle size by a polymerization operation. The other is a method in which rubber having a small particle size obtained by ordinary emulsion polymerization is coagulated and enlarged to have a large particle size.

The former method is a method in which rubber particles are coalesced and enlarged during polymerization to obtain large particles, but the biggest drawback of this method is that the polymerization time is long and the productivity is extremely poor.
It is not an industrially advantageous method. In the latter method, the latex diameter is at most about 0.2 μm by adding an inorganic salt or an acid to the rubber latex, and in many cases, it cannot be said that the particle diameter is appropriate as a rubber-reinforced resin. Further, when large particles are produced by this method, a large amount of agglomerates are produced, which is difficult to carry out industrially.

[0008] As an improvement of this method, for example, Japanese Patent Laid-Open No.
There is a method disclosed in Japanese Patent No. 25655. That is, it is a method in which an acid group-containing copolymer latex composed of a polyalkyl acrylate in the core portion and a copolymer of an alkyl acrylate and an unsaturated acid in the shell portion is added to a rubber latex having a pH of 7 or more to enlarge the particles. Certainly, this method can produce a rubber having a large particle diameter of about 0.3 μm. However, in this method, a large amount of agglomerate is generated during the production of the acid group-containing copolymer latex itself, and the rate of expansion of the rubber during the enlargement process is increased. 0.3μ with good reproducibility in small-scale experiments where mixing of latex is possible in a short time.
Although it is possible to produce a rubber having a large particle diameter of m or more, in an industrial apparatus in which thorough mixing takes time, local enlargement occurs, which often causes variation in particle diameter.
The ABS resin / polyamide resin alloy resin composition containing the rubbery polymer has a drawback that the mechanical properties are unstable.

[0009]

DISCLOSURE OF THE INVENTION The present invention solves the above problems and provides a molded article excellent in heat distortion resistance, impact resistance and surface appearance, and at the same time, heat resistant thermoplastic having excellent molding fluidity. A resin is provided.

[0010]

Means for Solving the Problems As a result of earnest research for solving the above problems, the present inventors have found that polyamide resin (A)
An aromatic vinyl compound, a vinyl cyanide compound, an unsaturated carboxylic acid compound, and, if necessary, an unsaturated carboxylic acid-containing copolymer (B) obtained from another vinyl compound copolymerizable therewith, and A thermoplastic resin composition prepared by blending an enlarged rubber-containing graft copolymer (C) having a specific average particle size and a kaolin (D), which has been enlarged using an acid group-containing copolymer latex, is easily molded. It can be processed, and its molded product has high thermal deformation resistance, and has well-balanced physical properties such as impact resistance, chemical resistance, rigidity, surface hardness, paintability, and water resistance, as well as molding fluidity and the appearance of molded products. The inventors have found that it is a novel heat-resistant thermoplastic resin composition excellent in, and completed the present invention.

That is, the present invention provides the following components (A) 5 to 95:
Parts by weight, component (B) 5 to 95 parts by weight and component (C) 5
To 50 parts by weight, and 0.1 to 30 parts by weight of component (D) is added to 100 parts by weight of (A), (B) and (C) in total, and a heat resistant thermoplastic resin composition. It is about. (A) Polyamide resin, (B) Unsaturated carboxylic acid-containing copolymer composed of the following components: aromatic vinyl compound 40 to 80% by weight, vinyl cyanide compound 15 to 50% by weight, unsaturated carboxylic acid compound 0.
1 to 20% by weight, other copolymerizable vinyl compound 0 to
30% by weight, (C) the following graft copolymer: 100% by weight (solid content) of rubber latex, the following acid group-containing copolymer latex (having an average particle size of 0.05 to 0.5 μm) ( S) is added in an amount of 0.1 to 15% by weight (solid content), and the average particle diameter obtained by the enlargement treatment is 0.1.
(S) an acid group-containing copolymer latex composed of the following components, obtained by graft-polymerizing 60 to 5% by weight of a vinyl compound in the presence of 40 to 95% by weight of a bloated rubber having a size of 2.0 μm. (A) 5 to 25% by weight of at least one unsaturated acid monomer selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid and crotonic acid, and (b) at least an alkyl group having 1 to 12 carbon atoms. 5 to 30% by weight of one kind of alkyl acrylate monomer, (c) the number of carbon atoms of the alkyl group is 1 to 1
2 at least one alkyl methacrylate monomer 2
0 to 80% by weight, (d) an aromatic vinyl compound copolymerizable with the above (a), (b) and (c), a compound having two or more polymerizable functional groups in the molecule, and vinyl cyanide At least one monomer selected from the group consisting of compounds 0
-40% by weight, (D) Kaolin.

Polyamide resin (A) used in the present invention
Is an aliphatic polyamide such as polyamide 6, polyamide 6,6, polyamide 6,10, polyamide 11, polyamide 12, polyamide 6,12; aromatic polyamide,
Examples thereof include polyhexamethyleneamine terephthalamide, polyhexamethylenediamine isophthalamide, and the like, and a mixture or a copolymer of two or more kinds of these can also be used. Further, impact-resistant polyamide blended with acid-modified polyolefin or polyamide elastomer which is a block copolymer of polyethylene glycol and polyamide can be used. Among them, especially polyamide 6,
The use of polyamide 6,6 is preferred.

The unsaturated carboxylic acid-containing copolymer (B) used in the present invention comprises an aromatic vinyl compound of 40 to 80% by weight, a vinyl cyanide compound of 15 to 50% by weight, and an unsaturated carboxylic acid compound of 0.1 to 50% by weight. It is a copolymer composed of 20% by weight and 0 to 30% by weight of another copolymerizable vinyl compound.

If the amount of the aromatic vinyl compound exceeds 80% by weight, the chemical resistance and impact resistance decrease, and if it is less than 40% by weight, the moldability decreases. If the amount of the vinyl cyanide compound exceeds 50% by weight, the thermal stability at the time of molding is deteriorated, and the coloring by heating is severe, and if it is less than 15% by weight, the chemical resistance and impact resistance are deteriorated. In addition, the unsaturated carboxylic acid compound is 20
If the content is more than 10% by weight, the thermal stability at the time of molding is deteriorated and the coloring due to heating is severe, and if it is less than 0.1% by weight, the compatibility with polyamide is deteriorated and delamination occurs on the surface of the molded product. When the amount of the other copolymerizable vinyl compound exceeds 30% by weight, the balance between heat resistance and impact resistance becomes insufficient.

The aromatic vinyl compound used in the unsaturated carboxylic acid-containing copolymer (B) includes styrene and α-
Methyl styrene, chlorostyrene, methyl styrene, etc. are illustrated. In particular, the use of α-methylstyrene is preferable from the viewpoint of improving heat resistance. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Examples of the unsaturated carboxylic acid compound include acrylic acid and methacrylic acid. Examples of other copolymerizable vinyl compounds include methacrylic acid such as methyl methacrylate, ethyl methacrylate, methyl acrylate, and ethyl acrylate, alkyl esters of acrylic acid, and maleimide compounds such as maleimide and phenylmaleimide. To be done. The aromatic vinyl compound, vinyl cyanide compound, unsaturated carboxylic acid compound, and other copolymerizable vinyl compound are used alone or in combination of two or more kinds.

The unsaturated carboxylic acid-containing copolymer (B) is
For example, it can be manufactured as follows. That is, α
-Methyl styrene was previously charged together with water and an emulsifier, and after being sufficiently emulsified, acrylonitrile and other monomers were continuously added dropwise in very small amounts, and α-methylstyrene was always 80% by weight in the polymerization system. As described above, the desired copolymer can be obtained by keeping the amount of α-methylstyrene in excess of 90% by weight or more. In this case, the unsaturated carboxylic acid compound may be charged in advance with α-methylstyrene, or may be added by mixing with acrylonitrile. It is also possible to prepare by dividing into pre-preparation and additional preparation. It is also possible to add a part of α-methylstyrene. In this case, α to be charged first
-The amount of methylstyrene is 50 parts by weight or more and 90 parts by weight or less based on 100 parts by weight of all the monomers. When producing the copolymer (B), 90% by weight of α-methylstyrene is used.
If it is more than 60% by weight, the chemical resistance and impact resistance are lowered, and if it is less than 60% by weight, the heat distortion resistance is lowered, which is not preferable.

One of the important points in the present invention is to use an enlarged rubber component which has been enlarged with an acid group-containing copolymer latex. In the graft copolymer (C), the acid group-containing copolymer latex (S) is the following (a), (b),
An acid group-containing copolymer latex prepared by copolymerizing (c) and (d). (A) 5 to 25% by weight of at least one unsaturated acid monomer selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid and crotonic acid, and (b) the carbon number of the alkyl group is 1
5 to 30% by weight of at least one alkyl acrylate monomer of to 12 and (c) the number of carbon atoms of the alkyl group is 1 to 12
At least one alkyl methacrylate monomer of 20
From 80% by weight, (d) an aromatic vinyl compound copolymerizable with the above (a), (b) and (c), a compound having two or more polymerizable functional groups in the molecule and a vinyl cyanide compound At least one monomer selected from the group consisting of 0 to 4
0% by weight.

In the graft copolymer (C), the unsaturated acid monomer (a) used in the acid group-containing copolymer latex (S) is acrylic acid, methacrylic acid, itaconic acid or crotonic acid. Yes, acrylic acid and methacrylic acid are particularly preferable. These may be used alone or in combination of two or more.

As the alkyl acrylate monomer (b) having an alkyl group having 1 to 12 carbon atoms, an ester of acrylic acid and an alcohol having a straight or side chain having 1 to 12 carbon atoms is used. , Ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like can be exemplified, and those having an alkyl group having 1 to 8 carbon atoms are particularly preferable. These can be used alone or 2
Used in combination of more than one species. As the alkyl methacrylate monomer (c) having an alkyl group having 1 to 12 carbon atoms, an ester of methacrylic acid and an alcohol having a straight chain or a side chain having 1 to 12 carbon atoms is used, such as methyl methacrylate and methacrylic acid. Ethyl, propyl methacrylate,
Examples thereof include butyl methacrylate and 2-ethylhexyl methacrylate, and particularly preferably an alkyl group having 1 to 8 carbon atoms. These may be used alone or in combination of two or more.

Preferred monomers (d) copolymerizable with the monomers (a), (b) and (c) are styrene,
Aromatic vinyl monomers such as α-methylstyrene and p-methylstyrene can be exemplified, and styrene and α-methylstyrene are particularly preferable. These may be used alone or in combination of two or more. Other copolymerizable monomers (d) include compounds having two or more polymerizable functional groups in the molecule, such as allyl methacrylate, polyethylene glycol dimethacrylate, and triallyl trimellitate. , Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. These may be used alone or in combination of two or more.

When polymerizing the acid group-containing copolymer latex (S) used for enlarging the rubber latex in the graft copolymer (C), 5-40% by weight of (S), preferably, 8 to 35% by weight and -95 ° C ≤ Tg
Low Tg of ≦ 40 ° C., preferably −80 ° C. ≦ Tg ≦ 30 ° C.
After polymerizing the monomer part (S1) which becomes the copolymer of
The balance of (S) is 95 to 60% by weight, preferably 92 to 65
% By weight and −20 ≦ Tg ≦ 80 ° C., preferably −1
A method of polymerizing the monomer portion (S2) to be a copolymer having a high Tg of 0 ≦ Tg ≦ 70 ° C. is desirable from the viewpoints of the amount of agglomerate reduction and the ability to expand when producing the acid group-containing copolymer latex.

In polymerizing the acid group-containing copolymer latex (S) used for expanding the rubber latex in the graft copolymer (C), 5 to 90% by weight of (S), preferably, After polymerizing the monomer part (S3) of 10 to 70% by weight and low unsaturated acid content, the balance of (S) is 95 to 10% by weight, preferably 90 to 30% by weight, and unsaturated. The monomer portion (S4) having a high acid content is converted to the above (S
The method of polymerizing so that the weight ratio a / b between the unsaturated acid content a in 3) and the unsaturated acid content b in the above (S4) is in the range of 0.05 to 0.95 is one of It is preferable from the point. Particularly preferably, a / b = 0.15 to 0.85. Further, the unsaturated acid content in the monomer portion (S4) is preferably 10% by weight or more, and particularly preferably 15% by weight or more, from the viewpoint of the ability to expand. The proportion of the unsaturated acid monomer (a) in the acid group-containing copolymer is 5 to 25% by weight, preferably 8 to 23% by weight. If it is 5% by weight or less, there is substantially no enlargement ability, and if it exceeds 25% by weight, the polymerization of the acid group-containing copolymer latex is not impossible,
It is not suitable for industrial production because agglomerates are generated and latex viscosity increases during polymerization. (A) The remaining monomer to be copolymerized with the unsaturated acid monomer is
Basically, they are (b) alkyl acrylate and (c) alkyl methacrylate. The proportion of (b) alkyl acrylate is 5 to 30% by weight, preferably 8 to 28% by weight. If it is less than 5% by weight, the hypertrophic capacity will decrease,
If it exceeds, the amount of agglomerates during the production of the acid group-containing copolymer latex increases. The proportion of the alkyl methacrylate (c) is 20 to 80% by weight, preferably 25 to 75% by weight, and outside this range, the hypertrophic capacity is reduced. The amount of the copolymerizable monomer (d) is 0 to 40% by weight, preferably 0 to 35% by weight. If it exceeds 40% by weight, the hypertrophic ability is reduced. Further, in the case of a monomer having two or more polymerizable functional groups in the molecule, it is preferable to use it in the range of 0 to 3% by weight, and when it exceeds 3% by weight, the hypertrophic ability is increased. Tends to decline.

The acid group-containing copolymer latex (S) used for expanding the rubber latex in the graft copolymer (C) is (a) 5 to 25% by weight of acrylic acid and / or methacrylic acid, b) The alkyl group has 1 to 8 carbon atoms.
5 to 30% by weight of at least one alkyl acrylate, and (c) at least 1 having 1 to 8 carbon atoms in the alkyl group.
20-80% by weight of seed alkyl methacrylate, (d)
Those obtained by polymerizing 0 to 40% by weight of styrene and / or α-methylstyrene are preferable.

The acid group-containing copolymer latex (S) is produced by emulsion polymerization. The emulsifier used in the polymerization is mainly a sulfonic acid type or sulfuric acid ester type emulsifier, and examples thereof include sodium alkylbenzene sulfonate, sodium paraffin sulfonate, sodium dialkylsulfosuccinate, and sodium alkyl sulfate.
These may be used alone or in combination of two or more.
A carboxylic acid-based emulsifier can be used supplementarily. Emulsifiers of this type include higher fatty acid alkali metal salts such as sodium oleate, sodium palmitate, potassium stearate, rosin acid alkali metal salts, and alkenyl succinic acid alkali metal salts, which may be used alone or in combination of two or more. Used. The amount of emulsifier used is
The amount is preferably 0.05 to 5 parts by weight (100 parts by weight with respect to the monomer). The emulsifier may be charged all at once at the beginning of the polymerization, or a part of the emulsifier may be used at the beginning and the rest may be added intermittently or continuously during the polymerization. The particle size of the acid group-containing copolymer latex can be adjusted by changing the method of adding the emulsifier.

The particle size of the acid group-containing copolymer latex is 0.05 to 0.5 μm, preferably 0.06 to 0.4 μm.
m. If the particle size is less than 0.05 μm, the hypertrophic ability is low, and if it exceeds 0.5 μm, the agglomerates remarkably increase.

As the polymerization initiator, either a thermal decomposition type initiator or a redox type initiator can be used, and both can be used in combination. Specific examples of the former include potassium persulfate and ammonium persulfate. Examples of the latter include systems such as cumene hydroperoxide-sodium formaldehyde sulfoxylate-iron salt. These may be used alone or in combination of two or more. As for the polymerization initiator, the whole amount may be charged all at once at the initial stage of the polymerization, or a part thereof may be used at the initial stage and the rest may be added intermittently or continuously during the polymerization. There is no limitation on the use of chain transfer agents such as t-dodecyl mercaptan, n-dodecyl mercaptan, and terpinolene to control the molecular weight, but 0.01 to 2 parts by weight is used from the viewpoint of reducing agglomerates during hypertrophy. Preferably.

In the polymerization of the acid group-containing copolymer latex (S), the monomer mixture may be charged all at once at the initial stage of polymerization, or a part thereof may be initially charged and the rest intermittently during the polymerization. Alternatively, it may be added continuously, or the entire amount may be added intermittently or continuously during the polymerization, but continuous addition is preferable from the viewpoint of heat removal. When the polymerization is performed by adding the monomer, the composition of the added monomer does not always have to be the same.

PH of rubber latex used for hypertrophy treatment
The pH is not particularly limited, but is preferably pH 7 or higher, more preferably pH 9 or higher, from the viewpoint of promoting hypertrophy. The gelation of rubber is not particularly limited, but 70% or more of rubber is preferable from the viewpoint of mechanical properties. A rubber with a low gel content or a rubber without a gel content and a rubber with a high gel content can be used together.

The enlargement treatment was carried out by adding the acid group-containing copolymer latex (S) to 100% by weight of rubber latex (solid content).
It is achieved by adding 1 to 15% by weight (solid content), preferably 0.3 to 12% by weight, and mixing. When the addition amount of the acid group-containing copolymer latex is less than 0.1% by weight, cohesive enlargement does not substantially occur. On the other hand, if the amount added exceeds 15% by weight, undesired phenomena such as an increase in agglomerates during enlargement occur. There is no particular limitation on the method of adding the acid group-containing copolymer latex (S) during the enlargement treatment. It may be added all at once in a short time or may be added continuously over time. The type of acid group-containing copolymer latex used for enlargement is not limited to one kind. It is also possible to use two or more kinds of acid group-containing copolymer latexes having different swelling capacities to obtain a swelling rubber having a two-peak distribution or a wide particle size distribution. Although the treatment temperature for enlargement is not particularly limited, it is preferably 40 to 90 ° C., particularly preferably 50 to 80 ° C. while stirring, in order to enhance the enlargement ability.

In the enlargement treatment, it is desirable to use an inorganic salt in an amount of 0.01 to 5% by weight, preferably 0.03 to 4% by weight, in addition to the acid group-containing copolymer latex in order to enhance the enlargement ability. By adding an inorganic salt, the hypertrophic effect can be improved. As the inorganic salt, an alkali metal salt such as sodium chloride or sodium sulfate or an oxyacid salt such as potassium alum is used, and these are used alone or in combination of two or more kinds.

The pH during the enlargement treatment is on the alkaline side (that is,
The pH may be 7 or more), but it is preferable to adjust the pH to 9 or more since the rate of enlargement is improved. The pH may be adjusted by adding an appropriate amount of one or more compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate and sodium hydrogen carbonate.

The rubber concentration in the rubber latex used for the enlargement treatment is also an important factor. The rubber concentration is preferably 1
It is 0 to 60% by weight, more preferably 15 to 50% by weight. It is possible to control the enlarged particle size by adjusting the rubber concentration, and the final particle size distribution differs depending on the composition of the acid group-containing copolymer latex, but by decreasing the rubber concentration the enlarged particle size becomes small. The higher the rubber concentration, the larger the enlarged particle size and the more agglomerates.

It is also possible to add an emulsifier during the enlargement treatment to change the surface coverage of the rubber latex particles and change the particle diameter after enlargement. That is, by adding an emulsifier to increase the coverage of the emulsifier on the surface, the enlarged particle size can be made smaller than in the case where no emulsifier is added.

The graft copolymer (C) is obtained by graft-polymerizing 60 to 5% by weight of a copolymerizable vinyl compound in the presence of 40 to 95% by weight of the enlarged rubber obtained by the above treatment. It is a copolymer. If the bloated rubber exceeds 95% by weight, the impact resistance and oil resistance decrease, and 40% by weight
If it is less than 1, the impact resistance is lowered.

The rubber latex used for the enlargement treatment includes diene type, acrylic acid ester type, olefin type,
Rubber such as silicone can be used, but diene is 50
A diene rubber containing at least wt% is particularly preferable, and examples of the diene rubber include polybutadiene, acrylonitrile-butadiene copolymer, styrene-butadiene copolymer, butyl acrylate-butadiene copolymer, and the like.
These may be used alone or in combination of two or more.

As the graft copolymerizable vinyl compound, aromatic vinyl compounds, vinyl cyanide compounds, unsaturated carboxylic acid alkyl ester compounds, unsaturated carboxylic acid compounds and other copolymerizable vinyl compounds are used. You can As the aromatic vinyl compound, vinyl cyanide compound and unsaturated carboxylic acid compound, the same ones as those used for the unsaturated carboxylic acid-containing copolymer (B) can be used. Examples of unsaturated carboxylic acid alkyl ester compounds include methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate and the like. Examples of other copolymerizable vinyl compounds include maleimide compounds such as maleimide and phenylmaleimide. These are used alone or in combination of two or more.

The average particle size of the enlarged rubber in the graft copolymer (C) is preferably 0.1 to 2.0 μm. More preferably, the average particle size is 0.25 to 1.0 μm.
If it is less than 0.1 μm, the impact resistance of the thermoplastic resin composition is insufficient, and if it exceeds 2.0 μm, the appearance of the molded article of the thermoplastic resin composition is poor.

The unsaturated carboxylic acid-containing copolymer (B) and the graft copolymer (C) are preferably obtained by emulsion polymerization, but are not necessarily limited to emulsion polymerization. Examples include bulk polymerization, suspension polymerization, solution polymerization and combinations thereof, that is, emulsion-suspension polymerization, emulsion-bulk polymerization. A usual method can be applied to the emulsion polymerization. That is, the compound may be reacted in an aqueous medium in the presence of a radical disclosing agent. At this time, the above compounds may be used as a mixture or, if necessary, dividedly used. Further, the addition method of the above compound may be added all at once or may be added sequentially, and is not particularly limited. Examples of the radical initiator include water-soluble or oil-soluble peroxides such as potassium persulfate, ammonium persulfate, cumene hydroperoxide, and paramenthane hydroperoxide, which may be used alone or in combination of two or more. Used. In addition, as the polymerization accelerator, the polymerization degree regulator, and the emulsifier, those used in the known emulsion polymerization method may be appropriately selected.

A known method may be used to obtain a dry resin from the obtained latex. At that time, a latex of the unsaturated carboxylic acid-containing copolymer (B) and the latex of the graft copolymer (C) may be mixed and then a dry resin may be obtained, or resins may be separately obtained and mixed in a powder state. Good. As a method of obtaining a resin from the latex, for example, hydrochloric acid, sulfuric acid,
A method is used in which an acid such as acetic acid and a metal salt such as calcium chloride, magnesium chloride and aluminum sulfate are added to coagulate the latex, followed by dehydration and drying. The mixed resin of the unsaturated carboxylic acid-containing copolymer (B) and the graft copolymer produced as described above can exhibit the high compatibility with the polyamide resin (A) while maintaining the characteristics of the ABS resin. It is a thing.

Another important point in the present invention is to use kaolin (D). Kaolin is an aluminum silicate-based mineral, and kaolinite, nacrite, dickite, halloysite, hydrohalloysite, etc. are exemplified in the present invention. These are used alone or in combination of two or more. Is preferable, and calcined kaolin which is an anhydride is particularly preferable. The average particle size of kaolin is preferably 0.1 to 4.0 μm, more preferably 0.2 to 2.0 μm.
If it is less than 0.1 μm, the effect of improving rigidity is not sufficient, and
When it exceeds 0 μm, the surface gloss and impact resistance of the molded product are deteriorated, which is not preferable.

The characteristics of the heat-resistant thermoplastic resin in the present invention vary depending on the mixing ratio of the polyamide resin (A) and the unsaturated carboxylic acid-containing copolymer (B), but in the present invention, (A) 5 to 95 parts by weight, (B) 5 to 95 parts by weight, (C) 5 to 50 parts by weight, and 0.1 to 10 parts by weight of kaolin (D) to 100 parts by weight of (A), (B) and (C).
30 parts by weight, preferably 0.5 to 20 parts by weight is compounded.
If the polyamide resin (A) is less than 5 parts by weight, the chemical resistance will decrease, and if it exceeds 95 parts by weight, the water resistance will decrease. If the amount of the unsaturated carboxylic acid-containing copolymer (B) is less than 5 parts by weight, the heat resistance will decrease, and if it exceeds 95 parts by weight, the chemical resistance will decrease. If the amount of the graft copolymer (C) is less than 5 parts by weight, the impact resistance will decrease, and if it exceeds 50 parts by weight, the fluidity during processing will decrease. If the content of kaolin (D) is less than 0.1 parts by weight, the effect of improving rigidity and heat distortion resistance is not sufficient, and if it exceeds 30 parts by weight, surface gloss, impact resistance, and molding fluidity are greatly reduced.

Granulation and molding of the heat-resistant thermoplastic resin composition of the present invention can be carried out by known methods. That is, polyamide resin (A), unsaturated carboxylic acid-containing copolymer (B), graft copolymer (C), kaolin (D)
Are blended using a blender such as a Henschel mixer, and then melt-mixed in an extruder to obtain pellets. When the unsaturated carboxylic acid-containing copolymer (B) and the graft copolymer (C) are in the form of a mixed powder recovered by a mixed latex, the mixed resin, the polyamide resin (A) and the kaolin (D) are mixed with each other. It may be blended to obtain pellets. Such pellets can be subjected to injection molding, extrusion molding, blow molding and the like.

The heat-resistant thermoplastic resin composition of the present invention contains not only antioxidants, heat stabilizers and lubricants which are well known, but also UV absorbers, pigments, antistatic agents and flame retardants, if necessary. The flame retardant aids can be used alone or in combination of two or more. Furthermore, mechanical properties such as elastic modulus,
To improve heat resistance, glass fiber, carbon fiber, calcium carbonate, talc, and other fillers other than kaolin may be added. These can be added alone or in combination of two or more.

[0044]

The present invention will be described below with reference to examples, but these are merely examples and the present invention is not limited to these. Unless otherwise specified, "part" means part by weight and "%" means% by weight. In the following description, the abbreviations represent the following substances, respectively. BA: Butyl acrylate BMA: Butyl methacrylate MAA: Methacrylic acid α-MeSt: α-Methylstyrene St: Styrene AN: Acrylonitrile MMA: Methyl methacrylate CHP: Cumene hydroperoxide t-DM: t-Dodecyl mercaptan PBd: Polybutadiene PBA : Polybutyl acrylate

Examples 1 to 11 and Comparative Examples 1 to 10 (1) Production of unsaturated carboxylic acid-containing copolymer (B) A stirrer, a reflux condenser, a nitrogen inlet, a monomer inlet, and a thermometer were installed. The following materials were charged into the reactor. Water 250 parts Sodium formaldehyde sulfoxylate 0.4 parts Ethylenediaminetetraacetic acid disodium 0.01 parts Ferrous sulfate 0.0025 parts Sodium dioctylsulfosuccinate 2.0 parts After heating and stirring at 60 ° C, the proportions shown in Table 1 The monomer mixture was continuously added dropwise over 6 hours together with cumene hydroperoxide as an initiator and t-dodecyl mercaptan as a polymerization degree regulator. After completion of the dropwise addition, stirring was further continued at 60 ° C. for 1 hour to terminate the polymerization, and an unsaturated carboxylic acid-containing copolymer (B-1) was obtained. For comparison, a copolymer (B-2) containing no unsaturated carboxylic acid was similarly obtained.

[0046]

[Table 1]

(2) Production of graft copolymer (C) (a) Production of acid group-containing copolymer latex (S) An acid group-containing copolymer latex for enlargement was produced as follows. The following substances were charged into a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer inlet, and a thermometer. Water 200 parts Sodium dioctyl sulfosuccinate 0.2 parts Sodium formaldehyde sulfoxylate 0.4 parts Ethylenediaminetetraacetate disodium 0.01 parts Ferrous sulfate 0.0025 parts While stirring the reactor under nitrogen flow up to 65 ° C. The temperature was raised. After reaching 65 ° C., the monomers shown in Table 2 were continuously added dropwise over 6 hours. After completion of the dropwise addition, stirring was continued at 65 ° C. for 1 hour to complete the polymerization.

[0048]

[Table 2]

(B) Production of polybutadiene rubber The following substances were charged in a 100-liter polymerization machine. Water 200 parts Sodium persulfate 0.2 parts t-Dodecyl mercaptan 0.2 parts After removing air in the polymerization machine with a vacuum pump, the following substances were charged. Sodium oleate 1 part Sodium rosinate 2 parts Butadiene 100 parts The temperature of the system was raised to 60 ° C. to initiate polymerization. The polymerization was completed in 12 hours, and the conversion rate was 96%. The obtained rubber latex had an average particle size of 70 nm and a pH of 9.5.

(C) Enlargement treatment The polybutadiene rubber obtained in (b) above was enlarged as follows. On the rubber latex (b), the acid group-containing latex (S-1), (S-2) and (S) obtained in (a)
-3) was added at a ratio shown in Table 3 at 25 ° C. in a predetermined amount, and then heated and stirred to raise the temperature to 60 ° C. Stirring was continued at that temperature for 1 hour to complete the enlargement (H-1) to (H-4).
For comparison, two types of PBd rubbers having different average particle diameters which are not subjected to the enlargement treatment are used (H-5) to (H-
6) was obtained.

[0051]

[Table 3]

(D) Production of graft copolymer The following substances were charged in a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer inlet and a thermometer. Water 250 parts Sodium formaldehyde sulfoxylate 0.4 parts Ethylenediaminetetraacetic acid disodium 0.01 parts Ferrous sulfate 0.0025 parts Hypertrophic rubber Amount described in Table 4 After heating and stirring at 60 ° C., the ratio shown in Table 4 The monomer mixture was continuously added dropwise over 5 hours together with the initiator cumene hydroperoxide and the polymerization degree controlling agent tertiary decyl mercaptan. After the dropping is completed, 60 ℃
The stirring was continued for 1 hour to complete the polymerization to obtain graft copolymers (C-1) to (C-6). For comparison,
Two types of PBd with different average particle diameters that do not undergo enlargement treatment
Similarly for rubber, the graft copolymer (C-
7) to (C-8) were obtained.

[0053]

[Table 4]

(E) Production of Blend of Carboxylic Acid-Containing Copolymer (B) and Graft Copolymer (C) The unsaturated carboxylic acid-containing copolymer (B) obtained in the above (1), Graft copolymer (C) obtained in the above (2)
Of the above latex are mixed uniformly at a ratio shown in Table 5, a phenolic antioxidant is added, coagulated with an aqueous solution of magnesium chloride, washed with water, dehydrated and dried, and then grafted with an unsaturated carboxylic acid-containing copolymer (B). Blends (Y-1) to (Y-11) with the copolymer (C) were obtained. For comparison,
The copolymer (B-2) containing no unsaturated carboxylic acid obtained in the above (1) is similarly compounded with the graft copolymer (C) (Y-10) and (Y- 11) was obtained.

[0055]

[Table 5]

(F) Production of thermoplastic resin composition Polyamide resin (A), kaolin (D), talc, and blends (Y-1) to (Y-11) obtained in the above (e).
And are mixed uniformly at a predetermined ratio shown in Tables 6 and 7,
Pelletized at a set temperature of 270 ° C using a vent type twin-screw extruder (TEX-44, L / D = 38.5, manufactured by Japan Steel Works, Ltd.), and an injection molding machine (manufactured by Japan Steel Works Co., Ltd., J
150E-P) set temperature 250 ℃, mold temperature 70 ℃
Was injection-molded to prepare a test piece, which was used for measurement of physical properties and evaluation of appearance of the molded body. The results are shown in Tables 6 and 7.

The physical properties were measured and the appearance of the molded product was evaluated by the following methods. Heat distortion temperature (HDT) ASTM D-648, 18.6 kg / cm ² (° C) Izod impact strength ASTM D-256, 23 ° C, notched (kg ・ cm /
cm)

High-speed surface impact test Test equipment: Hydroshot HTM-, manufactured by Shimadzu Corporation
1 Support frame diameter: 50.8mm Striker diameter: 12.7mm Punching speed: 13m / s Measuring temperature: 23 ℃ Test piece shape: 150mm x 100mm x 3mm The center of the test piece is punched out with a striker, and the total energy required (J) It was evaluated by.

Measurement of Spiral Flow Using the pellets prepared in (f), a spiral flow measuring mold [square (thickness 3 mm × width 10 mm), spiral shape] was measured with an injection molding machine (FANUC FAS-150B). Spiral flow length (mm) at a cylinder setting temperature of 250 ° C, mold temperature of 40 ° C and injection pressure of 1000 kg / cm ^2.
Was evaluated.

Evaluation of appearance of molded product The appearance (existence of uneven gloss, delamination, etc.) of the test piece prepared in (f) was visually evaluated. Good: No uneven gloss or delamination is observed. X: Uneven gloss and delamination are observed.

[0061]

[Table 6]

[0062]

[Table 7]

[0063]

INDUSTRIAL APPLICABILITY As described above, the heat-resistant thermoplastic resin composition of the present invention contains the rubber component subjected to the expansion treatment, and by adding kaolin, the same rubber component as that of the conventional rubber component is obtained. Provided is a molded product which is excellent in thermal deformation resistance and impact resistance, molding fluidity, and appearance even in a content. That is, since it has a high impact resistance in addition to a high heat distortion resistance, it is possible to reduce the rubber content as compared with the conventional case, so that higher heat distortion resistance and molding fluidity are further improved.

Claims (11)

[Claims] 1. The following components (A) 5 to 95 parts by weight, components (B) 5 to 95 parts by weight and components (C) 5 to 50 parts by weight, and (A), (B) and (C). ) 100 in total
A heat-resistant thermoplastic resin composition obtained by adding 0.1 to 30 parts by weight of component (D) to parts by weight. (A) Polyamide resin, (B) Unsaturated carboxylic acid-containing copolymer composed of the following components: aromatic vinyl compound 40 to 80% by weight, vinyl cyanide compound 15 to 50% by weight, unsaturated carboxylic acid compound 0.
1 to 20% by weight, other copolymerizable vinyl compound 0 to
30% by weight, (C) the following graft copolymer: 100% by weight of rubber latex (solid content), the following acid group-containing copolymer latex (having an average particle size of 0.05 to 0.5 μm) ( S) is added in an amount of 0.1 to 15% by weight (solid content), and the average particle diameter obtained by the enlargement treatment is 0.1.
(S) an acid group-containing copolymer latex composed of the following components, obtained by graft-polymerizing 60 to 5% by weight of a vinyl compound in the presence of 40 to 95% by weight of a bloated rubber having a size of 2.0 μm. (A) 5 to 25% by weight of at least one unsaturated acid monomer selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid and crotonic acid, (b) at least an alkyl group having 1 to 12 carbon atoms 5 to 30% by weight of one kind of alkyl acrylate monomer, (c) the number of carbon atoms of the alkyl group is 1 to 1
2 at least one alkyl methacrylate monomer 2
0 to 80% by weight, (d) an aromatic vinyl compound copolymerizable with the above (a), (b) and (c), a compound having two or more polymerizable functional groups in the molecule, and vinyl cyanide At least one monomer selected from the group consisting of compounds 0
-40% by weight, (D) Kaolin. 2. The heat-resistant thermoplastic resin composition according to claim 1, wherein the aromatic vinyl compound in the unsaturated carboxylic acid-containing copolymer (B) is α-methylstyrene. 3. The acid group-containing copolymer latex (S) used for expanding the rubber latex in the graft copolymer (C) is 5-40% by weight of (S) and -95.
After polymerizing the monomer part (S1) to be a low Tg copolymer of ℃ ≤ Tg ≤ 40 ℃, the balance of (S) is 95-60 wt% and high Tg of -20 ≤ Tg ≤ 80 ℃. The monomer part (S2) which becomes the copolymer of 1. is polymerized.
The heat-resistant thermoplastic resin composition described. 4. The acid group-containing copolymer latex (S) used for expanding the rubber latex in the graft copolymer (C) is 5 to 90% by weight of (S) and is unsaturated. After polymerizing the low acid content monomer portion (S3), (S)
Of the residual 95% to 10% by weight of the monomer part (S4) having a high unsaturated acid content, the weight of the unsaturated acid content a in (S3) and the unsaturated acid content b in (S4). The heat-resistant thermoplastic resin composition according to any one of claims 1 to 3, which is polymerized so that the ratio a / b is in the range of 0.05 to 0.95. 5. The acid group-containing copolymer latex (S) used for expanding the rubber latex in the graft copolymer (C) has an unsaturated acid content of 10 in the monomer portion (S4).
The heat resistant thermoplastic resin composition according to claim 4, wherein the heat resistant thermoplastic resin composition is polymerized so as to be contained in an amount of not less than wt%. 6. The rubber latex in the graft copolymer (C) is a diene rubber latex, an acrylic ester rubber latex or a mixture thereof.
The heat-resistant thermoplastic resin composition according to any one of 5 above. 7. The heat resistant heat according to any one of claims 1 to 6, wherein the enlarged rubber in the graft copolymer (C) is an enlarged rubber having an enlarged average particle size of 0.25 to 1.0 μm. Plastic resin composition. 8. The kaolin (D) is contained in an amount of 0.5 to 2 with respect to 100 parts by weight of the polyamide resin (A), the unsaturated carboxylic acid-containing copolymer (B) and the graft copolymer (C) in total.
It is 0 weight part, The heat resistant thermoplastic resin composition of any one of Claims 1-7. 9. The average particle size of kaolin (D) is 0.1 to 10.
It is 4.0 micrometers, The heat resistant thermoplastic resin composition of any one of Claims 1-8. 10. The average particle diameter of kaolin (D) is 0.2.
The heat-resistant thermoplastic resin composition according to any one of claims 1 to 8, wherein the heat-resistant thermoplastic resin composition has a thickness of from 2.0 to 2.0 μm. 11. The heat resistant thermoplastic resin composition according to claim 1, wherein the kaolin (D) is calcined kaolin.