JPH078954B2 - Thermoplastic resin composition and antistatic molding using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel thermoplastic resin composition having excellent antistatic properties and an antistatic molding using the same, and more specifically, a thermoplastic resin and a polyamideimide. The present invention relates to a thermoplastic resin composition containing an elastomer as a basic resin component and having continuous antistatic properties and excellent mechanical properties, and an antistatic molding using the same.

Conventional technology Conventionally, thermoplastic resins such as polystyrene resins, polyacrylic resins, polyolefin resins such as polyethylene and polypropylene, polyamide resins, polyester resins, polyacetal resins are inexpensive and have high mechanical strength and rigidity. It has been widely used in many fields depending on its physical properties and economic value because it has good mechanical properties and moldability.

However, these resins have relatively high surface resistance,
It has a drawback that static electricity is easily charged due to friction. For example, when polystyrene resin is used as a material for electronic / electrical device parts such as video cassettes, IC cards, copiers, TVs, etc., when it is used as a housing material for home electric appliances and OA equipment, or when it is used as a housing material for electrostatic charging. It has a drawback that it causes an unfavorable situation such as the generation of static electricity and the adhesion of dust to cause dirt. Polyacrylic resins, polyethylene, polypropylene, and the like also have problems such as being easily soiled when used in lighting equipment, various containers, and the like.
Further, when polyester or polyamide is used as clothing or a sheet, there is a drawback that static electricity charged by friction discharges at the time of desorption and causes discomfort.

Therefore, in these thermoplastic resins, it has been desired to develop a material having an antistatic property without impairing the desirable characteristics inherent to the resin.

As a method for imparting antistatic properties to these thermoplastic resins, for example, a method of kneading a surfactant or coating on the surface is known, but in such a method, the antistatic property present on the surface is prevented. The agent is easily removed by washing with water or rubbing, and it is difficult to impart a permanent antistatic property. In order to improve the impact resistance and antistatic property of the polystyrene resin, various methods of adding a polyamide elastomer to the polystyrene resin have been proposed (JP-A-59-1939).
59, JP-A-60-23435, JP-A-63-95251, JP-A-63-97653).

By the way, as such a polyamide elastomer, a hard segment is a polyamide, a soft segment is a polyether and a polyether ester amide in which both segments are linked by an ester bond, a polyether amide in which both segments are linked by an amide bond, or a soft segment Although polyester amides whose segments are polyesters and the like are used, these polyamide elastomers have a drawback that they have low compatibility with polystyrene resins.

In order to improve the compatibility with such a polyamide elastomer, it has been proposed to improve the impact resistance by using a vinyl copolymer obtained by copolymerizing a vinyl monomer containing a carboxyl group (Japanese Patent Laid-Open No. Sho 61-206). 59-193959), the polyamide elastomer must be used in an amount of 40% by weight or more, and the rigidity is unavoidably reduced. Further, a composition comprising 5 to 80 parts by weight of a polyether ester amide and 95 to 20 parts by weight of a vinyl copolymer containing a carboxyl group has been proposed, which improves compatibility and imparts antistatic property. However, in order to obtain a practical antistatic performance, the amount of polyetheresteramide added is large and the flexural modulus is not sufficient.

Further, a composition comprising a polyether ester amide, a rubber-modified polystyrene resin and a carboxyl group-containing vinyl copolymer can provide a molded article having antistatic properties and luster (JP-A-63-95251), It is also known that by finely dispersing a polyamide elastomer in a polystyrene resin in an amount of 0.01 to 10 μm, delamination is eliminated and antistatic property is imparted (JP-A-63-97653).

In addition, polyether ester amides, polyether amides, or polyester amides have been investigated as polyamide elastomers to be mixed with polystyrene resins. However, the polyether amide used in these uses a complicated and expensive polyether diamine, which is disadvantageous in cost.
In addition, the polyester polyamide has low hydrophilicity, and it is difficult to exhibit the antistatic effect.

In particular, because polyetheresteramide is made from relatively inexpensive polyoxyalkylene glycol,
It is advantageous in terms of cost, and attempts have been made to use it and to improve the flexural modulus (Japanese Patent Laid-Open No. 63-95251). However, the polyether ester amide does not always have sufficient heat resistance, and even when kneaded with a polystyrene resin, if the time of exposure to high temperature during molding becomes long, the mechanical properties of the obtained molded product and Physical properties such as antistatic property may deteriorate.

On the other hand, as a method for imparting a permanent antistatic property to a polyacrylic resin, for example, (1) a vinyl copolymer having a polyoxyethylene chain and a sulfonate, carboxylate or quaternary ammonium salt structure is used. Method of kneading with acrylic resin (JP-A-55-36237, JP-A-63-637)
39), and (2) polyether ester amide with methyl methacrylate-butadiene-styrene copolymer (MBS
Resin) and methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS resin) are kneaded (JP-A-62-119256).

However, in the method (1), the vinyl copolymer to be blended is expensive because it uses a special vinyl monomer, and the polyacrylic resin blended with this is unavoidably expensive to manufacture. Especially JP-A-55-3623
The method described in Japanese Patent No. 7 has a drawback in that a large amount of the vinyl copolymer is mixed and it is unavoidable that the original heat resistance of the polyacrylic resin is deteriorated. On the other hand, in the above method (2), amorphous polyetheresteramide and MBS are used.
The refractive index of the resin or MABS resin is 0.02 or less, and the transparency of the obtained composition is maintained, but the degree of freedom in combination is low, and the refractive index of polymethylmethacrylate, which is a typical polyacrylic resin, is It has the drawback of being difficult to match and of impairing transparency.

By the way, a polyacrylic resin is characterized by excellent transparency, and when a polymer compound is kneaded in order to impart permanent antistatic property to the polyacrylic resin, the compatibility is poor and the transparency is low. There are many things that can be done Further, even if a material having good transparency is obtained, a sufficient antistatic effect may not be obtained or the heat resistance may be deteriorated. Furthermore, when a polymer compound having a complicated structure is produced in order to exert a sufficient antistatic effect, the production cost becomes high, and it is not possible to obtain an inexpensive polyacrylic resin having antistatic properties.

Further, a composition obtained by kneading a polyamide elastomer with a polyacetal resin for the purpose of improving antistatic properties and impact resistance is also known (Japanese Patent Laid-Open No. 1971752/1984).
61-183345). The polyacetal resin has a strong tendency to decompose at a temperature higher than 200 ° C., and in the examples of the publication,
Only 12-nylon type polyamide elastomers with a melting point equal to or lower than that of polyacetal resin are used. However, the composition obtained by kneading the 12-nylon type polyamide elastomer is not sufficient in antistatic property.

Further, also with respect to polyolefin resins, a composition containing a polyamide elastomer in order to improve dyeability and antistatic property is known (JP-A-58-120812).

Generally, a 6-nylon type polyamide elastomer is considered to be preferable to a 12-nylon type polyamide elastomer in order to impart antistatic performance.
The 6-nylon-based polyamide elastomer does not always have sufficient heat resistance when added to a resin that requires a high kneading temperature or molding temperature, and is difficult to finely disperse when kneading with a resin having a low melting point. The toughness of the resulting composition may decrease. Therefore, it is the actual situation that a thermoplastic elastomer that gives a thermoplastic resin composition having excellent mechanical properties and permanent antistatic properties has not been known so far.

SUMMARY OF THE INVENTION Under the circumstances, the present invention provides a thermoplastic resin composition having excellent mechanical properties and permanent antistatic property using a thermoplastic elastomer, and an antistatic agent using the same. The purpose of the present invention is to provide a flexible molded article.

Means for Solving the Problems In order to develop a thermoplastic resin composition that gives a molded article having excellent physical properties, the present inventors have developed a thermoplastic elastomer containing a thermoplastic resin and polyoxyethylene glycol as a main soft segment. As a result of intensive research on blending with, polyoxyalkylene glycol containing polyoxyethylene glycol as a main component as a soft segment, and at least one of trivalent or tetravalent such as caprolactam and trimellitic acid or pyromellitic acid. Polyamideimide elastomer having a hard segment of a polyamideimidecarboxylic acid obtained from an aromatic polycarboxylic acid capable of forming an imide ring and an organic diisocyanate compound has heat resistance, and a polystyrene resin, a polyolefin resin, a polyresin. Acrylic resin, Polya Good compatibility with thermoplastic resins such as cetal-based resins, capable of exhibiting an excellent antistatic effect in a relatively small amount, and the melting point of the polyamide-imide elastomer mainly depends on the proportion of the hard segment and the molecular weight. By adjusting the amount of the diisocyanate compound, the melting point can be changed without impairing the heat resistance, that is, the melting point can be lowered by increasing the amount of the organic diisocyanate compound used, and as a result, various thermoplastic resins can be obtained. It has been found that the compatibility with and the toughness of the thermoplastic resin composition can be greatly improved, and the present invention has been completed based on this finding.

That is, the present invention includes (A) a thermoplastic resin, and (B)
(A) caprolactam, (b) trivalent or tetravalent aromatic polycarboxylic acid or an acid anhydride thereof capable of forming at least one imide ring, (c) organic diisocyanate compound and (d) number average molecular weight of 500 to Polyoxyalkylene glycol containing at least 50% by weight of 4000 polyoxyethylene glycol, the amount of component (b) being (c)
A polymer at a temperature of 30 ° C., which is obtained by polymerizing the components and the component (d) in a substantially equimolar amount to each other and in a proportion such that the amount of the component (d) is 35 to 85% by weight of the elastomer. A transparent polyamide-imide elastomer having a relative viscosity of 1.5 or more in cresol is contained in a weight ratio of 70:30 to 99: 1, and depending on the case, the total amount of the components (C), (A) and (B) is contained. A thermoplastic resin composition containing at least one selected from an organic electrolyte and an inorganic electrolyte in an amount of 10 parts by weight or less per 100 parts by weight, and a thermoplastic resin composition comprising the same, having a durability of less than 1.0 × 10 ¹⁴ Ω / □. The present invention provides an antistatic molded article characterized by having a certain surface resistance.

Hereinafter, the present invention will be described in detail.

Examples of the thermoplastic resin as the component (A) in the composition of the present invention include polystyrene resin, polyacrylic resin,
Polyolefin resin such as polyethylene and polypropylene, polyacetal resin, polyphenylene ether resin, polycarbonate resin, polyamide resin,
Examples thereof include polyester resins and blends thereof.

As the polystyrene resin, for example, rubber-reinforced polystyrene resin, styrene-butadiene-acrylonitrile copolymer (ABS resin), styrene-rubber copolymer- (meth) methyl acrylate (MBS resin), styrene-acrylonitrile copolymer ( AS resin) and styrene monomer as the main components, and other vinyl monomers such as methyl methacrylate, methyl acrylate, maleimide, acrylamide and the like are copolymerized at random, block or graft polymer.

Further, a rubber-reinforced polystyrene resin and a styrene-polybutadiene blend of styrene-butadiene copolymer or hydrogenated styrene-butadiene copolymer, a polyblend of ABS resin and polycarbonate resin, a polyblend of ABS resin and acrylic resin, ABS It may be a compound obtained by blending a polystyrene resin with another thermoplastic resin such as a polyblend of a resin and a vinyl chloride resin.

The rubber-reinforced polystyrene resin is industrially produced by dissolving a rubber-like substance in a styrene monomer and performing bulk or bulk suspension polymerization. As the rubber-like substance, polybutadiene, styrene-butadiene copolymer and the like are used. Usually, the rubber-like substance is dispersed in the styrene resin in the form of particles having an average particle diameter of 0.5 to 5 μm.

Further, those in which a part of styrene units constituting these polystyrene-based resins are substituted with α-methylstyrene units, p-methylstyrene units, pt-butylstyrene units and the like are also included.

Further, in order to improve the affinity with the polyamide-imide elastomer, a polystyrene resin containing a carboxyl group, an epoxy group, an oxazoline group, an amide group, a hydroxyl group, an amino group or the like can be preferably used. There is no particular limitation on the method of introducing these functional groups into the polystyrene resin, but acrylic acid, methacrylic acid, fumaric acid, maleic acid, 2-hydroxyethyl methacrylate, and 2-hydroxy that are copolymerizable with the styrene monomer. Functionality of ethyl acrylate, 3-hydroxypropyl methacrylate, maleic anhydride, itaconic anhydride, chloromaleic anhydride, 2-isopropylaminoethylstyrene, aminoethyl acrylate, aminopropyl methacrylate, vinyl oxazoline, glycidyl methacrylate, glycidyl acrylate, etc. A monomer having a group is added at the time of polymerization of the polystyrene resin and copolymerized. Alternatively, it can be obtained by mixing a copolymer of these monomers and styrene with the above-mentioned polystyrene resin.

It is not always clear in what mechanism the antistatic effect is exhibited when such a functional group-containing polystyrene resin is kneaded with a polyamideimide elastomer, but it is not completely compatible without delamination. It was found that they have an excessive compatibility to the extent that they do not exist, and that they exhibit an excellent antistatic effect and mechanical properties.

The content of the functional group in the functional group-containing polystyrene resin is preferably 0.05 to 10% by weight, more preferably 0.1.
Is selected in the range of up to 5% by weight. This content is 0.05% by weight
If it is less than 10% by weight, the effect of improving the mechanical properties due to the introduction of the functional group is not sufficiently exhibited, and if it exceeds 10% by weight, the antistatic effect is lowered, which is not preferable. When the functional group is a carboxyl group, the compatibilizing action is particularly strong, and the amount of the carboxyl group in the polystyrene resin is preferably 0.05 to 4% by weight, more preferably 0.1 to 2% by weight. When the amount of the carboxyl group is less than 0.05% by weight, the affinity with an elastomer having a high polyamideimide content, particularly an elastomer containing 60% by weight or more of polyamideimide is reduced, resulting in a reduction in impact strength and a reduction in elongation. If it exceeds 4% by weight, the affinity with the polyamide-imide elastomer increases,
Elastomers are extremely finely dispersed, and close to complete compatibility,
In such a state, the antistatic effect is unlikely to be exhibited, which is not preferable.

Examples of the polyacrylic resin include polymethylmethacrylate (MMA resin), rubber-reinforced polymethylmethacrylate, methylmethacrylate-butadiene-styrene copolymer (MBS resin), methylmethacrylate-acrylonitrile-butadiene-styrene copolymer. Polymers (MABS resin) and polymers obtained by copolymerizing 60% by weight or more of methyl methacrylate with 40% by weight or less of another copolymer vinyl monomer may be mentioned. These may be used alone, You may use it in combination of 2 or more type. Examples of the copolymerizable vinyl monomer include ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, styrene, and the like. Examples include α-methylstyrene, acrylonitrile, acrylic acid, methacrylic acid, fumaric acid, maleic acid and itaconic acid.

Examples of the polyolefin resin include polyethylene, polypropylene, ethylene-propylene copolymers and polymers obtained by copolymerizing these with other vinyl monomers, and examples of the polyacetal resin include, for example, oxymethylene homopolymer and mainly. Oxymethylene copolymers consisting of oxymethylene units and containing in the main chain oxyalkylene units having 2 to 8 adjacent carbon atoms are used.

Examples of the polyamide resin include polycondensates of dicarboxylic acids and diamines, polycondensates of aminocarboxylic acids, ring-opening polymers of cyclic lactams, and the like.
-Nylon, 4.6-nylon, 6.6-nylon, 6
・ Aliphatic polyamides such as 10-nylon, 11-nylon, and 12-nylon, aliphatic-aromatic polyamides such as poly (hexamethylene terephthalamide), poly (hexamethylene isophthalamide), poly (tetramethylene isophthalamide), and These copolymers and mixtures can be mentioned.

Examples of the polyester resin include polyethylene terephthalate, polyethylene terephthalate-polyethylene isophthalate copolymer, polybutylene terephthalate,
Polybutylene terephthalate-polybutylene isophthalate copolymer or other aliphatic glycol-polycondensation product of aromatic dicarboxylic acid, a part of aromatic dicarboxylic acid of the polycondensation product is adipic acid, sebacic acid or other aliphatic dicarboxylic acid And the like.

Examples of the polycarbonate resin include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl).
Examples thereof include those obtained by reacting propane or 2,2-bis (4-hydroxy-3,5-dichlorophenyl) alkanes with phosgene or diphenyl carbonate, and the like, and if necessary, the polycarbonate resin and other thermoplastic resins. You may use it as a blend with.

Further, as the polyphenylene ether resin, for example, a compound represented by the general formula (Wherein R ¹ and R ² are each a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, an aryl group such as 1
A homopolymer consisting of a repeating unit represented by the formula: (R ³ in the formula, R ^4, R ⁵ and R ⁶ are each a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, a monovalent residue such as an aryl group, R ⁵ and R ⁶ and a repeating unit represented by (which cannot be hydrogen atoms at the same time).

As a typical example of the polyphenylene ether homopolymer,
Poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, Poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4
-Phenylene) ether, poly (2-methyl-6-n-)
Butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether,
Poly (2-methyl-6-chloro-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl, 1,
4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether and the like can be mentioned.

Examples of the polyphenylene ether copolymer include those represented by the general formula (Wherein R ³ , R ⁴ , R ⁵ and R ⁶ have the same meanings as described above), an alkyl-substituted phenol such as 2,3,6-trimethylphenol and a monoalkylphenol such as cresol are used together. Examples thereof include a polyphenylene ether-based copolymer mainly composed of a polyphenylene ether structure obtained by polymerization. In addition, polyphenylene ether / acrylonitrile-butadiene-styrene copolymer, polybutylene terephthalate / polystyrene, polyphenylene ether / polybutylene terephthalate, polyamide / acrylonitrile-butadiene-styrene copolymer, polyolefin / polyamide, polyolefin / polybutylene terephthalate, polyolefin / Polycarbonate, polyolefin / polyoxymethylene,
Blends of polyolefin / polyphenylene sulfide, polyarylate / polybutylene terephthalate, polyphenylene ether / polyamide and the like can also be used.

In the composition of the present invention, the thermoplastic resin as the component (A) may be used alone or in combination of two or more.

The polyamide-imide elastomer used as the component (B) in the composition of the present invention is (a) caprolactam, (b) a trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring, or these acids. Obtained by reacting an anhydride, (c) an organic diisocyanate compound, and (d) a polyoxyalkylene glycol containing at least 50% by weight of polyoxyethylene glycol having a number average molecular weight of 500 to 4000, and It is a multi-block type copolymer in which a polyamide imide that is a hard segment obtained from the component (b) and the component (c) and a glycol that is the component (d) that is a soft segment are linked by an ester bond.

As the trivalent aromatic polycarboxylic acid used as the component (b), that is, the aromatic tricarboxylic acid, specifically, 1,2,4-trimellitic acid, 1,2,5-naphthalenetricarboxylic acid, 2,6,7-naphthalenetricarboxylic acid, 3,
3 ', 4-diphenyltricarboxylic acid, benzophenone-
3,3 ', 4-tricarboxylic acid, diphenylsulfone-3,
3 ', 4-tricarboxylic acid, diphenyl ether-3,3', 4
-Tricarboxylic acids and the like.

Further, as the tetravalent aromatic polycarboxylic acid, that is, the aromatic tetracarboxylic acid, specifically, pyromellitic acid,
Diphenyl-2,2 ', 3,3'-tetracarboxylic acid, benzophenone-2,2', 3,3'-tetracarboxylic acid, diphenylsulfone-2,2 ', 3,3'-tetracarboxylic acid, diphenyl ether -2,2 ', 3,3'-tetracarboxylic acid and the like can be mentioned.

The aromatic polycarboxylic acid or its acid anhydride as the component (b) may be used alone or in combination of two or more, and the organic diisocyanate compound as the component (c) and the component (d) may be used. Is used in a substantially equimolar amount, that is, 0.9 to 1.1 times the molar amount of the glycol.

Examples of the organic diisocyanate compound used as the component (c) include hexamethylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and diphenylmethane diisocyanate. These diisocyanate compounds may be used alone or in combination of two or more.

By using these organic diisocyanate compounds, a heterogeneous structure is introduced into the hard segment, the melting point of the hard segment can be lowered and the crystallization temperature can be lowered, and it is easy to perform fine dispersion during kneading with the thermoplastic resin. And it becomes possible to control the fluidity during molding. Further, the introduction of the imide ring increases the thermal decomposition temperature and improves the thermal stability during kneading.

The amount of the organic diisocyanate compound as the component (c) to be used is preferably an equimolar amount or less with respect to the glycol as the component (d). If it is used in excess of this amount, the melting point becomes too low depending on the composition. Then, the mechanical properties of the composition are deteriorated, which is not preferable.

Polyamideimide, which is a hard segment, is involved in the heat resistance, strength, hardness, and compatibility of the thermoplastic resin of the elastomer, and the content of polyamideimide in this elastomer is in the range of 15 to 65% by weight. is necessary. If this content is less than 15% by weight, the strength of the elastomer will be low, and the impact strength will be low when kneaded with the thermoplastic resin, which is not preferable, and if it exceeds 65% by weight, the compatibility with the thermoplastic resin will be poor. Or, the antistatic effect is lowered, which is not preferable. Particularly in the case of a polyacrylic resin, the content of the hard segment has a great influence, and for example, in order to maintain transparency by kneading with the MMA resin, the content of the hard segment is preferably 40% by weight or less.

The number average molecular weight of the polyamideimide is preferably in the range of 500 to 3000, more preferably 500 to 2000. If the number average molecular weight is less than 500, the melting point may be low and the heat resistance may be insufficient, and if it exceeds 3000, the compatibility of the elastomer with the thermoplastic resin tends to decrease, which is not preferable.

In the composition of the present invention, polyoxyalkylene glycol containing 50% by weight or more of polyoxyethylene glycol is used as the component (d) in the polyamideimide elastomer, but from the viewpoint of antistatic property, polyoxyethylene glycol is used. Is preferably used alone.

The number average molecular weight of the polyoxyethylene glycol used must be in the range of 500 to 4000. When it is less than 500, although depending on the composition of the elastomer, the melting point may be lowered and the heat resistance may be insufficient, which is not preferable. On the other hand, when it exceeds 4000, it becomes difficult to form a tough elastomer, and when kneaded with a thermoplastic resin, impact strength and rigidity may decrease, which is not preferable.

The polyoxyalkylene glycol that can be used in combination with the polyoxyethylene glycol is less than 50% by weight of the glycol component and has a number average molecular weight of 500 to 4000, polyoxytetramethylene glycol, modified polyoxytetramethylene glycol, polyoxypropylene. Glycol and the like can be used.

As modified polyoxytetramethylene glycol,-(CH ₂ ) _{4 of} ordinary polyoxytetramethylene glycol is used.
The thing which replaced a part of -O- with -RO- is mentioned. Here, R is an alkylene group having 2 to 10 carbon atoms,
For example, ethylene group, 1,2-propylene group, 1,3-propylene group, 2-methyl-1,3-propylene group, 2,2-dimethyl-1,3-propylene group, pentamethylene group, hexamethylene group, etc. Is mentioned. The modification amount is not particularly limited, but is usually selected in the range of 3 to 50% by weight. The amount of modification and the type of the alkylene group are appropriately selected depending on the required properties of the thermoplastic resin composition, such as low temperature impact resistance and heat resistance.

This modified polyoxytetramethylene glycol can be produced by, for example, copolymerization of tetrahydrofuran and diol using a heteropolyacid as a catalyst, copolymerization of cyclic ether which is a diol or a condensation product of diol, and butanediol.

The polyamide-imide elastomer used in the composition of the present invention is preferably polymerized homogeneously, and the homogeneity of this elastomer can be judged by its transparency. Regarding the method for producing the polyamide-imide elastomer, any method may be used as long as it can produce a homogeneous amide-imide elastomer, and for example, the following method is used.

That is, (a) caprolactam, (b) aromatic polycarboxylic acid component, (c) organic diisocyanate compound component and (d) glycol component are contained in the amount of (b) component (c).
The components and the component (d) are mixed at a ratio that is substantially equimolar to the total amount of the components, and while maintaining the water content in the resulting polymer at 0.1 to 1% by weight, 150 to 300 ° C, more preferably 180 to 280
It is a method of polymerizing at ℃. In this method, the reaction temperature can be raised stepwise during the dehydration condensation.

At this time, some caprolactam remains unreacted, but this is distilled off under reduced pressure and removed from the reaction mixture. The reaction mixture after removing the unreacted caprolactam can be further polymerized, if necessary, by post-polymerization under reduced pressure at 200 to 300 ° C, more preferably 230 to 280 ° C.

In this reaction method, esterification and amidation are simultaneously caused in the course of dehydration condensation to prevent coarse phase separation, thereby producing a homogeneous and transparent elastomer. It has excellent compatibility with a thermoplastic resin, and when kneaded with a thermoplastic resin, it exhibits an excellent antistatic effect and mechanical properties, and can give a composition transparent to a polyacrylic resin. Of.

Esterification reaction and polymerization of caprolactam are caused at the same time, and each reaction rate is controlled,
In order to obtain a transparent and homogeneous elastomer, it is preferable to remove the produced water from the system and keep the water content of the reaction system in the range of 0.1 to 1% by weight for polymerization. . If the water content exceeds 1% by weight, the polymerization of caprolactam takes precedence to cause coarse phase separation, while if it is less than 0.1% by weight, the esterification takes precedence and caprolactam does not react to obtain an elastomer having a desired composition. I can't. This water content is appropriately selected within the above range depending on the physical properties desired for the elastomer.

Further, in this reaction, the water content in the reaction system may be gradually decreased as the reaction progresses, if desired. The control of the water content can be performed by controlling the reaction conditions such as the reaction temperature, the flow rate of the inert gas introduced, and the degree of pressure reduction, and changing the structure of the reactor.

Although the degree of polymerization of the polyamide-imide elastomer used in the composition of the present invention can be arbitrarily changed as necessary,
It is necessary to adjust so that the relative viscosity measured at 30% at 0.5% (weight / volume) in meta-cresol is 1.5 or more. If it is lower than 1.5, mechanical properties cannot be sufficiently expressed, and even when kneaded with a thermoplastic resin,
Mechanical properties may be insufficient. The preferred relative viscosity is
It is 1.6 or more.

In addition, as another polymerization method, a method in which (b) an aromatic polycarboxylic acid component and (c) an organic diisocyanate compound component are first reacted, and then (a) caprolactam and (d) a glycol component are combined and reacted Alternatively, (a) a part of caprolactam, (b) an aromatic polycarboxylic acid component and (c) an organic diisocyanate compound component are reacted, and then (a) caprolactam and (d) glycol component are further added. A method of adding and reacting can also be used. Polymerization by these methods makes it possible to prevent phase separation during polymerization and obtain a transparent elastomer. An esterification catalyst can be used as a polymerization accelerator when producing a polyamide-imide elastomer.

Examples of the polymerization accelerator include phosphoric acid, polyphosphoric acid,
Phosphorus compounds such as metaphosphoric acid; Tetraalkyl orthotitanates such as tetrabutyl orthotitanate; Tetraalkoxyzirconium zirconium such as tetrabutylzirconium; Tin-based catalysts such as dibutyltin oxide and dibutyltin laurate; Manganese-based catalysts such as manganese acetate;
Preferable are antimony-based catalysts such as antimony trioxide; lead-based catalysts such as lead acetate. The catalyst may be added at the beginning of the polymerization or in the middle of the polymerization.

Further, in order to enhance the thermal stability of the obtained polyamide-imide elastomer, various heat aging inhibitors, stabilizers such as antioxidants can be used, and these can be used at the initial stage, the middle stage, or the final stage of polymerization. You may add. It can also be added after the polymerization and before the kneading of the thermoplastic resin.

Examples of the heat resistance stabilizer include N, N'-hexamethylene-bis (3,5-di-t-butyl-4-hydroxycinnamic acid amide) and 4,4'-bis (2,6-di-amide). t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t
-Butylphenol) and various hindered phenols; N, N'-bis (β-naphthyl) -p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, poly (2,2,4-trimethyl) 1,2-dihydroquinoline) and other aromatic amines; copper salts such as copper chloride and copper iodide; sulfur compounds such as dilauryl thiodipropionate and phosphorus compounds.

The ratio of the thermoplastic resin as the component (A) to the polyamide-imide elastomer as the component (B) in the composition of the present invention must be in the range of 70:30 to 99: 1 by weight, When the amount of the component is less than this, a sufficient antistatic effect cannot be obtained, and when the amount is more than this, the rigidity becomes insufficient.

In the composition of the present invention, an organic electrolyte or an inorganic electrolyte may be optionally added as the component (C) in order to further improve the antistatic property. By using the polyamide-imide elastomer of the component (B) and the electrolyte of the component (C) together, a composition having more excellent antistatic properties can be obtained due to a synergistic effect.

Examples of the organic electrolyte exhibiting such an effect include an organic compound having an acidic group, a metal salt thereof, an organic ammonium salt, an organic phosphonium salt, or the like. Examples of the organic compound having an acidic group or a metal salt thereof include aromatic compounds such as dodecylbenzenesulfonic acid, p-toluenesulfonic acid, dodecyldiphenyletherdisulfonic acid, naphthalenesulfonic acid, a condensate of naphthalenesulfonic acid and formalin, and polystyrenesulfonic acid. Alkyl sulfonic acids such as group sulfonic acids and lauric sulfonic acids, organic carboxylic acids such as stearic acid, lauric acid and polyacrylic acid, organic phosphoric acids such as diphenyl phosphite and diphenyl phosphate and their alkali metal salts, alkaline earth Examples thereof include metal salts.

Although the effect is exhibited in the form of free acid, it is preferable to use it in the form of a salt of an alkali metal or an alkaline earth metal,
For example, sodium, lithium, potassium, magnesium, calcium salts and the like are preferable.

Examples of the organic ammonium salt include quaternary ammonium salts such as trimethyloctylammonium bromide, trimethyloctylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride and trioctylmethylammonium bromide, and examples of the organic phosphonium salt include amyl. Examples thereof include quaternary phosphonium salts such as triphenylphosphonium bromide and tetrabutylphosphonium bromide.

On the other hand, as the inorganic electrolyte, periodic table Ia, Ib, IIa, IIb,
Group VIIa and VIII metal nitrates, hydroxides, halides,
Rhodan salts, sulfates, phosphates, carbonates and the like,
Specifically, AgNO ₃ , Ca (NO ₃ ) ₂ , KBr, KNCS, KNO ₃ , LiN
O ₃ , LiCl, NaBr, Na ₂ CO ₃ , NaH ₂ PO ₄ , Cu (NO ₃ ) ₂ , ZnSO ₄ ,
Examples thereof include Zn (NO ₃ ) ₂ , MgCl ₂ , Mg (NO ₃ ) ₂ , MnCl ₂ and Ni (NO ₃ ) ₂ .

These electrolytes may be used alone or in combination of two or more, and may be appropriately selected depending on the properties of the thermoplastic resin, the composition of the polyamide-imide elastomer, the purpose of use, and the like. Organic sulfonates are particularly suitable for polyacrylic resin compositions that require transparency.

In the composition of the present invention, the addition amount of the electrolyte of the component (C), which is optionally used, is 10 parts by weight or less, preferably 0.01 part by weight or less, relative to 100 parts by weight of the total amount of the components (A) and (B). To 10 parts by weight, more preferably 0.1 to 5 parts by weight. If this amount is less than 0.01 parts by weight, the effect of the additive is not sufficiently exerted, and if it exceeds 10 parts by weight, the impact strength is reduced, and the corrosion mold deposit of the mold is expressed,
It is not preferable because it causes deterioration of appearance. Among these electrolytes, organic electrolytes are preferable to inorganic electrolytes in terms of mold corrosion and appearance.

The composition of the present invention contains various optional components such as pigments, dyes, reinforcing fillers, heat stabilizers, antioxidants, nucleating agents, lubricants, plasticizers, if desired, within a range that does not impair the object of the present invention. , An ultraviolet absorber, a release agent, a flame retardant, and other polymers can be contained in any process such as a kneading process or a molding process.

As the reinforcing filler, for example, glass fiber, carbon fiber, fibrous reinforcing agent such as potassium titanate, mica, talc, clay, calcium silicate, calcium carbonate, glass foil, glass beads, other polymer particles or the like. There are flaky fillers, among which, among these,
Glass fiber and mica are particularly preferable.

Further, examples of the flame retardant used for imparting flame retardancy to the thermoplastic resin composition include organic halogen-based, organic phosphorus-based, and metal hydroxide.

The composition of the present invention comprises a mixture of the component (A), the component (B) and optionally the component (C) and various additive components, which are prepared by a known method such as a Banbury mixer,
It can be prepared by a method of kneading using a mixing roll, a uniaxial or biaxial extruder, or the like. The kneading temperature at this time is preferably in the range of 180 to 280 ° C.

For electrolytes with a high melting point, it is better to dissolve the electrolyte in a solvent such as water, alcohol, or dimethylformamide in advance and then add this solution dropwise to the ventro of the extruder to disperse the electrolyte uniformly. It is advantageous because a composition having good antistatic effect, mechanical properties and appearance can be obtained.

The thermoplastic resin composition thus obtained is a known method generally used for molding thermoplastic resins, for example, injection molding, extrusion molding, blow molding, vacuum molding, inflation molding, film molding, sheet molding. , Foamed sheet molding, foamed bead molding and the like.

A molded article obtained from the composition of the present invention thus obtained is provided with a continuous antistatic property, and the shape thereof is not particularly limited, and for example, Fine Chemical Report No. 10 issued by Chunichisha Co., Ltd. New trends in plastic materials for electrical and electronic equipment "(published on September 20, 1988) II, equipment edition, can be molded into parts of equipment of any shape described on pages 14 to 114.

As such, for example, VTR cassette tape case, half, reel, reel flange, window, etc., audio cassette tape half, case, window, etc., copy machine top cover, original pressing cover, internal cover, Front cover, operation surface cover, charging insulator, paper storage box,
Paper storage box cover, paper guide, copy paper tray, TV cabinet, front frame, back cover, escutcheon, speaker box, terminal board, telephone housing, handset case, vacuum cleaner body case, dust case, Storage case, rotating hose,
Extension tube hose, upper lid, filter box, fan propeller fan, front cover, rear cover, air conditioner front panel, propeller fan, cross flow fan, wind direction adjusting plate, terminal cover, filter, chassis, control panel, Decorative covers, semiconductor device IC packages, micro-floppies,
Examples include disk cases, optical disk cartridges and the like, exterior housings for office machine printers, display panels, paper guides, connectors, platen knobs, printer bodies, cassette covers, cassette guides, and the like.

In recent years, there has been a strong demand for higher performance of the above-mentioned equipment and parts thereof, and a strong demand for excellent antistatic properties. In addition to preventing dust due to electrification and preventing noise and dropout, the problem is to prevent the tape from becoming entangled or stopped due to running for a long time like a VTR cassette tape. Furthermore, it is required that these antistatic effects last for a long period of time and that the effects are not lost even by washing with water.

At the same time, lightweight and high mechanical strength are required, and good appearance as a molded product is also essential.

The molded product produced using the composition of the present invention has all of these characteristics, and further, it is possible to reduce the cost and has great industrial significance.

EFFECTS OF THE INVENTION The thermoplastic resin composition of the present invention comprises a thermoplastic resin and a polyamide-imide elastomer as basic resin components, and has characteristics such as having permanent antistatic property and excellent mechanical properties. However, it is widely used as a molding material capable of imparting the function of preventing electrostatic charging to various components such as home appliances such as video, televisions, cleaners, copying machines, and lighting equipment, OA equipment, and housings.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples.
The invention is in no way limited by these examples.

The physical properties of the composition and the elastomer were determined according to the methods described below.

(1) Tensile strength and tensile elongation: Use a dumbbell piece of 1/8 inch thickness according to ASTM D638,
It was measured at 23 ° C. and 55% RH.

However, since the elastomer and the nylon resin are apt to absorb moisture, they were vacuum dried at 80 ° C. for 3 hours, transferred into a desiccator, taken out of the sample in a thermostatic chamber at 23 ° C. and 55% RH, and measured for tensile strength and tensile elongation. For the elastomer, a dumbbell piece with a thickness of 1 mm was used.

(2) Flexural modulus: 1/8 inch thick test piece according to ASTM D790, 23
It was measured at ℃ and 55% RH.

(3) Izod impact strength: Measured at 23 ° C. and 55% RH using a notched test piece having a thickness of 1/8 inch according to ASTM D256.

(4) Charge voltage test: A static Honest meter (manufactured by Shishido Shokai) was used to apply a static voltage of 8 KV, and after the voltage was removed, the time at which the charge voltage of the sample was halved was measured at 23 ° C. and 55% RH.

(5) Relative viscosity of elastomer: Measured in meta-cresol under the conditions of 30 ° C. and 0.5 wt / vol%.

(6) Thermal decomposition temperature of elastomer: The weight reduction temperature was measured at a temperature rising rate of 10 ° C / min using a differential thermal balance.

(7) Haze number of elastomer: Using a sheet with a wall thickness of 1 mm, in accordance with ASTM D1003-61,
It measured using the haze meter.

(8) Surface resistivity: Using a flat plate having a thickness of 1/8 inch, it was measured under the following conditions with a hyper-insulator SN-10E type manufactured by Toa Denpa Kogyo Co., Ltd.

(A) After molding, the state was adjusted for 24 hours under the conditions of 23 ° C. and 55% RH and then measured (surface resistivity of initial value).

(B) After molding, the surface was immersed in running water for 10 minutes to remove water from the surface, adjusted for 24 hours under conditions of 23 ° C. and 55% RH, and then measured (surface resistivity after washing with water).

(C) After molding, after standing for 150 days at 23 ° C. and 55% RH, measurement was performed (surface resistivity on the 150th day).

(9) Tobacco ash adhesion test: 100% 1/8 inch thick flat plate used for surface resistivity measurement with gauze
After rubbing, as shown in the figure, the flat plate 3 was placed on a strip (1/4 inch thick) 2 having cigarette ash 1 placed therein, and then evaluated according to a standard.

◎: No cigarette ash ○: A small amount of cigarette ash ×: A lot of cigarette ash (10) VTR cassette tape running test: 120 minutes tape for S-VHS on molded VTR cassette half Incorporation was repeated, and reproduction and rewinding were continuously repeated for 10 days, a running test was performed, and then evaluation was performed according to the standard. In addition, as the molded body, 10 pieces of the same resin composition are used,
The test was performed.

◯: All 10 tapes were good for 10 days. X: Tape running was stopped even in the case of one sample. The test pieces for measuring physical properties were obtained by using the pellets obtained in Examples and Comparative Examples with an injection molding machine. , 1/8 inch thick flat plate (vertical 90 mm,
A test piece having a width of 50 mm), 1/8 inch, and 1/4 inch was molded and used.

The thermoplastic resins and electrolytes used in the examples and comparative examples are as follows.

A-1: Polystyrene resin containing 12% by weight of butadiene rubber A-2: Polystyrene resin (melt flow index 2.3 g / 10 mm measured at 200 ° C, 5 kg) A-3: Copolymerization of 8% by weight of methacrylic acid Polystyrene resin A-4: ABS resin Stylak ABS A-4130 [Asahi Kasei Kogyo Co., Ltd.] A-5: AS resin Slylac AS 783 [Asahi Kasei Kogyo Co., Ltd.] A-6: 1% by weight Polystyrene resin containing oxazoline group (XUS-40056-01 manufactured by Dow Chemical Co., Ltd.) A-7: Methyl methacrylic acid resin Delpet 80N [manufactured by Asahi Kasei Corporation] A-8: Polyacetal resin Tenac 3010 [Asahi Chemical Industry ( Co., Ltd.] A-9: Polyamide resin A-1030 BRT [Unitika Co., Ltd.] A-10: Polybutylene terephthalate resin Toray PBT 1401 [Toray Co., Ltd.] A-11: Polycarbonate resin Tafflon A-2700 [Idemitsu] Petrochemical Co., Ltd.] A-12: Polyphenylene ether [η sp / c = 0.56 (chloroform 0.5% solution) poly (2,6-dimethylphenylene-1,4-ether)] A-13: Styron QH405 (manufactured by Asahi Kasei Corporation, high-impact polystyrene) A-14 : Crystalline ethylene-propylene block copolymer [ethylene unit content 9% by weight, MFI (ASTM D1238) 8.0] A-15: ABS resin Styrac A-7970 [Asahi Kasei Kogyo KK] A-16: AS Resin Stylak 767 [Asahi Kasei Co., Ltd.] A-17: Polycarbonate resin 7025A [Mitsubishi Kasei Co., Ltd.] A-18: ABS resin Stylak A-8930 [Asahi Kasei Co., Ltd.] C-1: Sodium dodecylbenzene sulfonate C-2: Potassium bromide C-3: Potassium thiocyanate C-4: Tetrabutylammonium chloride C-5: Amylphenylphosphonium chloride Production Examples 1 to 3 Polyamideimide elastomer (B-1 to B
-3) 500 ml equipped with a manufacturing stirrer, nitrogen inlet and distillation tube
In a separable flask, 97 g of caprolactam, 90 g of polyoxyethylene glycol with a number average molecular weight of 1490, 16.4 g of trimellitic acid, 4.5 of diphenylmethane diisocyanate.
2 g (diisocyanate / glycol molar ratio 0.3) of N, N '
-Hexamethylene-bis (3,5-di-t-butyl-4-
(Hydroxycinnamic acid amide) (trade name "Irganox"1098; antioxidant) was charged with 0.3 g, and nitrogen was 50 ml / m.
After being melted at 150 ° C while flowing in, polymerization was carried out at 260 ° C for 4 hours. After 1 hour, 2 hours, and 4 hours from the temperature of 260 ° C., the water content in the reaction solution was 0.7, 0.5, and 0.3% by weight, respectively. Next, after adding 0.3 g of tetrabutyl orthotitanate, the pressure was gradually reduced to 1 Torr and unreacted caprolactam was distilled out of the system. Further, polymerization was carried out at the same temperature under a pressure of 1 meter or less for 2 hours to obtain a pale yellow transparent elastomer (B-1) (haze number 45%). This elastomer has polyoxyethylene glycol segment 49
% By weight, the relative viscosity was 1.95, the tensile strength and the elongation were 420 Kg / cm ² , 750%, and the hardness was 38 in Shore D. The melting point, crystallization temperature and thermal decomposition temperature are shown in Table 1.

In the same manner as in Production Example 1, containing 49% by weight of a polyoxyethylene glycol segment having a number average molecular weight of 1490,
Elastomer (B-2) with a molar ratio of diphenylmethane diisocyanate / polyoxyethylene glycol of 0.5, 0.
05 elastomer (B-3) was manufactured. Its melting point, crystallization temperature and thermal decomposition temperature are shown in Table 1.

Production Example 4 Production of Polyamideimide Elastomer (B-4) In the same manner as in Production Example 1, 61.4 g of caprolactam, 90 g of polyoxyethylene glycol having a number average molecular weight of 1490, 1.5 g of diphenylmethane diisocyanate and 12.8 g of trimellitic anhydride were reacted. A transparent elastomer containing 60% by weight of a polyoxyethylene glycol segment was obtained (42% haze). This elastomer has a strength of 300 kg / cm
² , the elongation was 970%, the thermal decomposition starting temperature was 328 ° C, and the melting point was 181 ° C.

Production Example 5 Production of Polyamideimide Elastomer (B-5) In a reactor similar to that of Production Example 1, 100 g of polyoxyethylene glycol having a number average molecular weight of 1980, 45 g of caprolactam, 1.3 g of diphenylmethane diisocyanate and 10.7 g of trimellitic anhydride were added to a poly ( Charged with 0.3 g of 2,2,4-trimethyl-1,2-dihydroquinoline) (trade name: Nocrac 224; antioxidant), 4 at 250 ° C while flowing nitrogen at 50 ml / min.
Reacted for hours. During that time, the water content in the reaction system was 0.8 to 0.3% by weight. Then, the pressure was reduced at 260 ° C to distill off the unreacted caprolactam, the pressure was returned to normal pressure with nitrogen, 0.3 g of tetrabutoxyzirconium was added, and the pressure was reduced again to 260
Polymerized at 1 ° C and 1 torr for 4 hours, transparent with a pale yellow color (haze number 30
%) Elastomer was obtained. This elastomer contains 70% by weight of polyoxyethylene glycol segment,
The relative viscosity was 2.1, the thermal decomposition starting temperature was 325 ° C., the melting point was 172 ° C., the strength was 280 kg / cm ² , and the elongation was 1100%.

Production Example 6 Production of Polyamideimide Elastomer (B-6) Polyoxyethylene glycol 70 having a number average molecular weight of 1980
g, number average molecular weight 2040 polyoxytetramethylene glycol 30.9 g, caprolactam 56.3 g pyromellitic anhydride 1
3.2 g and hexamethylene diisocyanate 1.7 g were polymerized in the same manner as in Production Example 5 to obtain a pale yellow elastomer containing 65% by weight of polyoxyalkylene glycol segment (haze number 37%). This elastomer has a relative viscosity
1.96, melting point 191 ℃, thermal decomposition starting temperature 328 ℃, strength 37kg / c
It had a m ² and an elongation of 930%.

Production Example 7 Production of Polyamideimide Elastomer (B-7) In a 10-liter stainless steel reactor equipped with a stirrer, a nitrogen inlet and a distillation pipe, 2.23 kg of caprolactam and a number average molecular weight.
Charge 1980 polyethylene glycol 2.20 kg, trimellitic anhydride 224 g, diphenylmethane diisocyanate 13.9 g and N, N'-hexamethylene-bis (3,5-di-t-butyl-4-hydroxycinnamic acid amide) 8 g together. , 15
It was heated to 0 ° C. and melted. Then under a reduced pressure of 300 torr 25
The temperature was raised to 0 ° C and polymerization was carried out for 4 hours. Thereafter, the pressure was gradually reduced to 1 Torr, and 0.64 kg of unreacted caprolactam was distilled out of the system. Further, 6 g of tetra-n-butoxyzirconium was added, and polymerization was carried out at 260 ° C. under a reduced pressure of 1 Torr or less for 2 hours. The resulting elastomer is transparent (38% haze),
Polyethylene glycol segment content 55% by weight, relative viscosity 1.9, melting point 209 ℃, thermal decomposition start temperature 327 ℃
And tensile strength and elongation are 350 kg / cm ² and 850, respectively.
% And hardness Shores A and D were 91 and 33, respectively.

Production Example 8 Production of Polyamideimide Elastomer (B-8) In the same manner as in Production Example 1, polyoxyethylene glycol having a number average molecular weight of 800, 70 g, caprolactam 109 g, trimellitic anhydride 21.9 g and diphenylmethane diisocyanate 6.6 g were reacted, Polyoxyethylene glycol segment content 40% by weight, relative viscosity 1.83, haze number 58%,
Melting point 208 ℃, Thermal decomposition start temperature 329 ℃, Strength 520kgcm ² , Elongation
630% elastomer was obtained.

Production Example 9 Production of Polyamideimide Elastomer (B-9) The distillation tube of the apparatus of Production Example 1 was replaced with a reflux condenser, and 167 g of caprolactam, 33.2 g of adipic acid and 6 g of water were charged, and 260
By reacting at 6 ° C. for 6 hours, a polycapramide having a terminal carboxyl group was produced. This product had a number average molecular weight of 883 as measured by acid value.

In the apparatus of Production Example 1, 40 g of the above polyamide, 96 g of polyoxyethylene glycol (number average molecular weight 2010), antioxidant [N, N'-hexemethylene-bis (3,5-di-t-butyl-
4-hydroxycinnamic acid amide), trade name, Irganox 1098] 0.3 g and tetrabutyl orthotitanate 0.2 g
Was charged, melted at 240 ° C., depressurized and polymerized at 1 torr for 2 hours, and further at 1 torr and 260 ° C. for 9 hours, and coarse phase separation occurred during the polymerization.

The melt became milky white and was not transparent until the end of the polymerization, and the obtained elastomer was light brown, opaque and brittle. The thermal decomposition start temperature of the elastomer is 29
It was 1 ° C.

Examples 1 to 15 Thermoplastic resins, elastomers and additives were mixed in the proportions shown in Table 3, and kneaded and extruded at a temperature shown in Table 2 with a single-screw extruder (30 mm dullage screw, L / D = 26), Pelletized through a cooling passage. This pellet at 80 ℃ 3
After vacuum drying for an hour, injection molding was performed under the conditions shown in Table 2 to prepare test pieces for measuring physical properties. All showed excellent gloss. Table 3 shows the measured physical property values.

Comparative Examples 1 to 9 According to Examples 1 to 15, the kneaded and extruded composition having the composition shown in Table 3 was injection-molded and the physical properties were measured. The results are shown in Table 3.

Examples 16 to 18 and Comparative Example 10 In the same manner as in Examples 1 to 15, the acrylic resin compositions shown in Table 4 were prepared, injection molded, and the physical properties were measured. The results are shown in Table 4.

For comparison, comparative compositions shown in Table 4 were prepared,
Injection molding was performed and physical properties were measured. The results are also shown in Table 4.

Example 19 The test pieces obtained in Examples 1, 3, and 9 were washed with water, and then subjected to a charging voltage test. As a result, the same antistatic performance as that before water washing was shown in 3, 3 and 2 seconds, respectively. In addition, these are 55% RH, 23
After standing for 6 months at 0 ° C., a charging voltage test was carried out to show 3 seconds, 4 seconds, and 2 seconds, respectively, and the antistatic performance was unchanged from the initial state.

Example 20 The compositions of Example 15 and Comparative Example 2 were injection-molded at 250 ° C., and after being retained in the cylinder of an injection molding machine at 250 ° C. for 20 minutes, the surface gloss of the injection-molded products was measured. Those of Example 15 were 90% and 84%, respectively, and the gloss was almost unchanged. Those of Comparative Example 2 were 73% and 37%, respectively. The latter had some rough skin.

Examples 21 to 23 Polystyrene resins, elastomers and electrolytes were mixed in the proportions shown in Table 5, and a twin screw extruder having a screw diameter of 30 mm (AS30 type, manufactured by Nakatani Machinery Co., Ltd.) was used, and the cylinder temperature was 230 ° C. Melt kneading with screw rotation speed 75 rpm, 10 kg
After extruding at an extrusion rate of / hr to form three strands, the strand was cooled to about 30 ° C with water. Next, the cooled strands were granulated to obtain pellets of polystyrene resin composition. After drying the pellets at 80 ° C for about 3 hours in a gear oven, injection molding was performed under the conditions of a cylinder temperature of 220 ° C and a mold temperature of 60 ° C to prepare a surface resistivity measuring test piece having excellent gloss. . The measurement results of physical properties are shown in Table 5. Further, the pellets produced as described above were injection-molded to prepare and evaluate molded bodies shown in Table 6. The results are shown in Table 6. The injection molding was carried out at a cylinder temperature of 220 ° C and a mold temperature of 60 ° C in Example 21, a cylinder temperature of 240 ° C and a mold temperature of 45 ° C in Example 22, and a cylinder temperature of 270 ° C and a mold temperature of 70 ° C in Example 23. I went there.

Comparative Example 11 Polystyrene resin, elastomer, and other additives
The mixture was mixed in the proportions shown in the table, and in the same manner as in Example 22, a test piece and a molded body shown in Table 6 were prepared and evaluated. The results are shown in Tables 5 and 6.

Example 24 Polyphenylene ether [ηsp / c = 0.56 (chloroform
0.5 wt% solution) poly (2,6-dimethylphenylene-1,
4-ether)], Stylon QH405 [Asahi Kasei Co., Ltd.
High-impact polystyrene], a stabilizer (manufactured by ADEKA ARGUS CORPORATION, mark AO-30), a polyamide-imide elastomer B-4 and an electrolyte in a ratio shown in Table 7,
Using a twin-screw extruder with a screw diameter of 30 mm (AS-30 type, manufactured by Nakatani Machinery Co., Ltd.), melt kneading was performed at a cylinder temperature of 250 ° C. and a screw rotation speed of 75 rpm, and then extrusion was performed at an extrusion speed of 10 kg / hr. It was made into three strands and then cooled to about 30 ° C. with water. Then, the cooled strand was granulated to obtain pellets of the polyphenylene ether resin composition.

The pellets were dried in a gear oven at 80 ° C. for 3 hours and then injection-molded under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C. to prepare test pieces for measuring physical properties and surface resistivity. All showed excellent gloss. The physical properties of these test pieces were evaluated. The results are shown in Table 7.

Further, the pellets were injection-molded under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C. to prepare molded products shown in Table 8, and the antistatic property, appearance and mechanical properties were evaluated. The results are shown in Table 8.

Comparative Example 12 Polyphenylene ether, Styron QH405, a stabilizer (manufactured by ADEKA ARGUS CORPORATION, mark AO-30) and an electrolyte were mixed at a ratio shown in Table 7, and the same as in Example 24, shown in a test piece and Table 8. A molded body was prepared and various evaluations were performed.
The results are shown in Tables 7 and 8.

Example 25 A crystalline ethylene-propylene block copolymer [ethylene unit content 9% by weight, MFI (ASTM D1238) 8.0], polyamideimide elastomer B-4 and an electrolyte were mixed in a ratio shown in Table 9 and uniaxially extruded. The mixture was kneaded and extruded at 240 ° C. with a machine (screw with 30 mm dullage, L / D = 26), and pelletized through a cooler. After drying the pellets in a gear oven at 80 ° C. for 3 hours, injection molding was performed under the following conditions to prepare test pieces for measuring physical properties. All showed excellent gloss.

Cylinder temperature: 230 ℃ Mold temperature: 50 ℃ Ejection pressure: 500kg / cm ² Ejection time: 15 seconds Cooling time: 15 seconds Table 9 shows the measurement results of physical properties.

Further, the pellets were molded into a molded body shown in Table 10 and evaluated. The results are shown in Table 10.

Comparative Example 13 To 100 parts by weight of the polyolefin resin used in Example 25,
The molded product containing 0.3 to 0.5 parts by weight of the nonionic antistatic agent had fog on the surface of the molded product. In addition, the whitening phenomenon and stickiness of the surface of the molded product, which was added with 0.5 part by weight, were observed over time.

With respect to those to which 0.5 parts by weight of the nonionic antistatic agent was added, test pieces and molded products shown in Table 9 were prepared in the same manner as in Example 25, and various evaluations were performed. The results are shown in Tables 9 and 10.

Examples 26 and 27 Polyamideimide elastomer and acrylic resin of the types and amounts shown in Table 11 were mixed, and an electrolyte, a hindered amine light stabilizer [2,2,6,6-tetramethyl-4-
Piperidyl) sebacate, trade name SANOL LS770, Sankyo Co., Ltd.], benzotriazole type UV absorber [2-
(5-methyl-2-hydroxyphenyl) benzotriazole, trade name Tinuvin P, manufactured by Ciba Geigy]
After blending in the amount shown in the table, with a vented 40 mmφ extruder,
Melt kneading and extrusion were performed at a resin temperature of 250 ° C. to form pellets.

Next, using an injection molding machine, a molded body shown in Table 12 was prepared at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C., and evaluated. The results are shown in Table 12.

[Brief description of drawings]

The figure is an explanatory view showing a method of a cigarette ash adhesion test for a molded body, in which reference numeral 1 is cigarette ash, 2 is a strip, and 3 is a test flat plate.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C08L 33/08 LJE 53/00 LLZ 59/00 LMP 67/02 LPK 69/00 LPQ 71/12 LQP 77/00 LQT

Claims (5)

[Claims] 1. A thermoplastic resin (A), (B) (a) caprolactam, (b) a trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring, or an acid anhydride thereof. , (C) an organic diisocyanate compound, and (d) a polyoxyalkylene glycol containing at least 50% by weight of a polyoxyethylene glycol having a number average molecular weight of 500 to 4000, wherein the amount of the (b) component is (c) component ( in meta-cresol at a temperature of 30 ° C., which is obtained by polymerizing in a molar amount substantially equal to the total amount of the component d) and in such a proportion that the amount of the component (d) is 35 to 85% by weight with respect to the elastomer. The relative viscosity is
A transparent polyamide-imide elastomer of 1.5 or more is contained in a weight ratio of 70:30 to 99: 1, and in some cases, 10 parts by weight per 100 parts by weight of the total amount of the components (C), (A) and (B). A thermoplastic resin composition comprising at least 1 part by weight or less selected from an organic electrolyte and an inorganic electrolyte. 2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is at least one selected from polystyrene resins, polyacrylic resins, polyolefin resins and copolymer resins thereof. . 3. The polystyrene resin is a carboxyl group,
The thermoplastic resin composition according to claim 2, which has at least one functional group selected from an oxazoline group, an epoxy group, a hydroxyl group, an amino group, and an amide group. 4. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is at least one selected from polyamide resins, polyester resins, polyphenylene ether resins, polyacetal resins and polycarbonate resins. . 5. An antistatic molding comprising the thermoplastic resin composition according to claim 1 and having a persistent surface resistance of less than 1.0 × 10 ¹⁴ Ω / □.