JP2836848B2 - Thermoplastic elastomer composition and molded article thereof - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel thermoplastic elastomer composition containing a styrene-based or olefin-based thermoplastic elastomer and a polyamideimide elastomer as basic resin components, and an antistatic property obtained therefrom. It relates to a molded article.

2. Description of the Related Art A styrene-based or olefin-based thermoplastic elastomer such as a hydrogenated product of a block copolymer composed of a vinyl aromatic compound and a conjugated diene compound, a so-called hydrogenated block copolymer or a blend or copolymer of polypropylene and EPDM is Since it can be easily processed by the same molding means as general-purpose resins and has the same elasticity as vulcanized rubber or silicone rubber, it can be used as a substitute for vulcanized rubber or silicone rubber, or laminated with a rigid resin It is widely used as a molding material for home appliances, electronics products, OA equipment, interior and exterior parts for automobiles, furniture, sports goods, medical supplies, and the like.

However, when this is used as a material for electronic parts such as video cassettes, IC cards, copiers, televisions, and electric appliance parts, there is a drawback that static electricity is generated and charged, which causes obstacles such as adhesion of dust and discharge. Therefore, there has been a demand for the development of a molding material having an antistatic property in addition to the inherent desirable characteristics of the molding compound.

By the way, in general, in order to impart antistatic properties to an elastomer, it is performed to add a conductive filler or an antistatic agent such as carbon black or carbon fiber. It is inevitable to be colored dark, cannot be used when a material having a light color tone is required, and has a drawback that a sustained effect cannot be obtained by adding an antistatic agent.

Problems to be Solved by the Invention The present invention provides a styrene-based or olefin-based thermoplastic elastomer without coloring, imparts a permanent antistatic property, and is widely used for electronic parts and electric appliance parts without any obstacle. The purpose of the present invention is to provide a usable molding material.

Means for Solving the Problems The present inventors have found that a hydrogenated product of a predetermined block copolymer,
The modified product and / or olefin-based thermoplastic elastomer was subjected to various studies to impart antistatic properties. As a result, polyoxyethylene glycol was used as a soft segment, and caprolactam and trimellitic acid or pyromellitic acid were used. A polyamideimide elastomer having a polyamideimidedicarboxylic acid as a hard segment obtained from an aromatic polycarboxylic acid capable of forming at least one imide ring is a hydrogenated product of a predetermined block copolymer, a modified product thereof and / or an olefin. Having compatibility with the thermoplastic thermoplastic elastomer, and also having heat resistance, it has been found that when blended in a relatively small amount, it is possible to impart a continuous antistatic property without impairing its desirable properties, The present invention has been accomplished based on this finding.

That is, the present invention relates to (A) hydrogenation of a block copolymer comprising at least two polymer blocks mainly composed of vinyl aromatic compound units and at least one polymer block mainly composed of conjugated diene compound units. (B) (a) caprolactam, (b) a trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring, (c) ) Polyoxyethylene glycols or polyoxyalkylene glycol mixtures based on polyoxyethylene glycol and optionally used (d)
The content of the component (c) obtained from at least one of diamines having 2 to 10 carbon atoms is 30 to 85% by weight, and the temperature is 30%.
A polyamide imide elastomer having a relative viscosity at 1.5 ° C. of 1.5 or more, and a thermoplastic elastomer composition comprising a weight ratio of 70:30 to 97: 3, and 1.0 × 10 ¹⁴ obtained by molding the same. An object of the present invention is to provide an antistatic molded article having a persistent surface resistivity of less than Ω / □.

 Hereinafter, the present invention will be described in detail.

The hydrogenated product of the predetermined block copolymer used as the component (A) of the composition of the present invention is a known product (“Plastics”, Vol. 30, No. 3, page 6), and is a vinyl aromatic compound. A block copolymer consisting of at least two polymer blocks mainly composed of a group compound unit (hereinafter referred to as block X) and at least one polymer block mainly composed of conjugated diene compound units (hereinafter referred to as block Y). It is a block copolymer in which polystyrene such as a product obtained by hydrogenation is used as a hard phase and a conjugated diene compound is used as a soft phase. Here, “mainly” is used for the vinyl aromatic compound unit and the conjugated diene compound unit.
By means that these units represent more than 50% by weight of the total monomer units, preferably more than 70% by weight.

Accordingly, the block X is a copolymer of a vinyl aromatic compound polymer block or a vinyl aromatic compound containing more than 50% by weight, preferably 70% by weight or more of a vinyl aromatic compound and a hydrogenated conjugated diene compound. Having the structure of a coalesced block, and the block Y comprises more than 50% by weight, preferably 70% by weight, of the hydrogenated conjugated diene compound polymer block or hydrogenated conjugated diene compound.
It has a structure of a copolymer block of a hydrogenated conjugated diene compound and a vinyl aromatic compound containing at least 10% by weight. The block X mainly composed of a vinyl aromatic compound and the block Y mainly composed of a hydrogenated conjugated diene compound are each composed of a hydrogenated conjugated diene compound or a vinyl aromatic compound in a molecular chain in each polymer block. The distribution of the group III compound may be random, tapered (in which the monomer component increases or decreases along the molecular chain), partially block-shaped, or an arbitrary combination thereof.
When there are more than one, each polymer block may have the same structure or different structures.

As the vinyl aromatic compound constituting the hydrogenated block copolymer, for example, one or more kinds are selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, and the like. Styrene is preferred.
Examples of the conjugated diene compound before hydrogenation constituting the hydrogenated conjugated diene compound include, for example, butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-
One or more of butadiene and the like are selected, but butadiene, isoprene and a combination thereof are particularly preferred. The polymer block mainly composed of a conjugated diene compound before hydrogenation can be arbitrarily selected in the microstructure of the block. For example, in a polybutadiene block, the 1,2-microstructure has 20 to 50% ,
Preferably it is 25-45%.

From these blocks X and Y, for example, X-Y-X, Y- X-Y-X, has a (X-Y) ₄ Si, block structure, such as X-Y-X-Y, The content of the vinyl aromatic compound is 5 to 60% by weight, preferably 10 to 50% by weight.
A range of weight percent is chosen.

The number average molecular weight of the hydrogenated block copolymer having the above structure is 5,000 to 1,000,000, preferably 10,000 to
The molecular weight distribution [the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn)] is 10 or less, more preferably from 800,000 to 30,000 to 500,000. Further, the molecular structure of the hydrogenated block copolymer may be linear, branched, radial, or any combination thereof.

These block copolymers may be obtained by any production method as long as they have the above-mentioned structure. For example, according to the method described in JP-B-40-23798, a vinyl aromatic compound-conjugated diene compound block copolymer is produced in an inert solvent using a lithium catalyst or the like. No. 8704, JP-B-43-6636, or JP-A-59-1332
According to the method described in Japanese Patent Publication No. 03-203, hydrogenation can be carried out in an inert solvent in the presence of a hydrogenation catalyst to produce the hydrogenated block copolymer used in the present invention. At this time, at least 80% of the aliphatic double bond based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer is hydrogenated, and the polymer block mainly comprising the conjugated diene compound is morphologically converted to olefin. Can be converted into a polymer compound block. Also, block X
The hydrogenation rate of the aromatic double bond based on the vinyl aromatic compound copolymerized in the block Y as required is not particularly limited, but the hydrogenation rate is preferably 20% or less. The amount of unhydrogenated aliphatic double bonds contained in the hydrogenated block copolymer can be easily known by an infrared spectrophotometer, a nuclear magnetic resonance apparatus, or the like.

The component (A) of the composition of the present invention may be a modified product of the above-mentioned hydrogenated block copolymer, which is obtained, for example, by adding an organic unsaturated compound such as maleic anhydride to the hydrogenated block copolymer. The carboxylic acid is obtained by adding 0.02 to 30% by weight, preferably 0.05 to 20% by weight, according to information.

Also, olefin-based thermoplastic elastomers are known (see “Plastics” above), and examples thereof include a blend or a copolymer of polypropylene and EPDM or a partially crosslinked product thereof.

Next, the polyamideimide elastomer of the component (B) of the composition of the present invention comprises (a) caprolactam, (b) a trivalent or tetravalent polycarboxylic acid, and (c) polyoxyethylene glycol or polyoxyethylene glycol. A polyamide imide comprising a mixture of a polyoxyalkylene glycol other than polyoxyethylene glycol and a hard segment is obtained from the component (a) and the component (b), which is a glycol of the component (c) which is a soft segment. And a multi-block copolymer linked by an ester bond.

As the component (b), a trivalent or tetravalent aromatic carboxylic acid capable of reacting with an amino group to form at least one imide ring or an anhydride of these carboxylic acids is used.

As the trivalent tricarboxylic acid used as the component (b), specifically, 1,2,4-trimellitic acid, 1,2,5-naphthalene tricarboxylic acid, 2,6,7-naphthalene tricarboxylic acid, 3 , 3 ', 4-diphenyltricarboxylic acid, benzophenone-3,3', 4-tricarboxylic acid, diphenylsulfone-3,3 ', 4-tricarboxylic acid, diphenylether-
3,3 ', 4-tricarboxylic acid and the like.

Further, as the tetravalent carboxylic acid, specifically, pyromellitic acid, diphenyl-2,2 ', 3,3'-tetracarboxylic acid, benzophenone-2,2', 3,3'-tetracarboxylic acid And diphenylsulfone-2,2 ', 3,3'-tetracarboxylic acid and diphenylether-2,2', 3,3'-tetracarboxylic acid.

These carboxylic acids are used in a substantially equimolar amount to the glycol component (c), that is, in a range of 0.9 to 1.1 times mol.

Polyamide imide, which is a hard segment, contributes to heat resistance, strength, hardness and compatibility with the hydrogenated block copolymer of the elastomer, and the polyamide imide content in the elastomer is 15 to 70% by weight. %. If the content is less than 15% by weight, the strength in the elastomer will be low, and when kneaded with the hydrogenated block copolymer, the mechanical strength will be low. Thus, if it exceeds 70% by weight, the affinity will be poor. Or the antistatic effect is lowered.

The number average molecular weight of the polyamideimide is 500 or more and 3000 or less, more preferably 500 or more and 2000 or less. If the number average molecular weight of the polyamide imide is less than 500, the melting point is lowered and the heat resistance is lowered, and if it is more than 3,000, the compatibility with the hydrogenated block copolymer is lowered, which is not preferable.

In the composition of the present invention, in order to improve heat resistance, an imide ring is further introduced into the polyamideimide (d).
When a diamine is used in combination, the carboxylic acid is used in a molar amount of 0.9 to 1.1 times the total molar number of the glycol component (c) and the diamine component (d).

Examples of the diamine of the component (d) include ethylene diamine, tetramethylene diamine, hexamethylene diamine, and phenylenediamine. This amount is preferably not more than 1 mol of the glycol component (c). If the amount is more than this, it is difficult to obtain a homogeneous elastomer, and the compatibility with the hydrogenated block copolymer decreases. Not preferred.

As the component (c) in the polyamideimide elastomer, polyoxyethylene glycol or a mixture of polyoxyethylene glycol and a polyoxyalkylene glycol other than polyoxyethylene glycol is used.

The number average molecular weight of the polyoxyethylene glycol used is not particularly limited, but is preferably in the range of 500 to 5,000. If it is less than 500, it depends on the composition of the elastomer, but it is not preferable because the melting point may be low and the heat resistance may be insufficient. On the other hand, if it exceeds 5,000, it is difficult to form a tough elastomer, and when kneaded with the hydrogenated block copolymer, the impact strength and the rigidity may be lowered, which is not preferable.

Examples of the polyoxyalkylene glycol which can be used in combination with the polyoxyethylene glycol include polyoxytetramethylene glycol having a number average molecular weight of 500 to 5,000, modified polyoxytetramethylene glycol, polyoxypropylene having a number average molecular weight of less than 50% by weight of the glycol component. Glycol or the like can be used.

As the modified polyoxytetramethylene glycol,
The usual polyoxytetramethylene glycol-(C
H ₂ ) _4- O- has been partially substituted with -R-0-. Here, R is an alkylene group having 2 to 10 carbon atoms, for example, an ethylene group, a 1,2-propylene group, a 1,3-
Propylene group, 2-methyl-1,3-propylene group, 2,2-
Examples include a dimethyl-1,3-propylene group, a pentamethylene group, and a hexamethylene group. The amount of modification 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 according to the required characteristics of the thermoplastic elastomer composition, such as low-temperature impact resistance and heat resistance.

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

Regarding the method for producing the polyamide-imide elastomer used in the composition of the present invention, any method may be used as long as there is a method capable of producing a homogeneous amide-imide elastomer. For example, the following method is used.

A polymer formed by mixing the caprolactam component (a), the aromatic polycarboxylic acid component (b) and the glycol component (c) in such a ratio that the component (b) and the component (c) become substantially equimolar. This is a method of polymerizing at 150 to 300 ° C, more preferably 180 to 280 ° C, while keeping the water content in the solution at 0.1 to 1% by weight. In the present method, the reaction temperature can be raised stepwise during the dehydration condensation.

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

In this reaction method, esterification and amidation occur simultaneously in the course of dehydration condensation, thereby preventing coarse phase separation and thereby producing a homogeneous and transparent elastomer. This is a hydrogenated product of the block copolymer,
It has excellent compatibility with the modified product and / or the olefin-based thermoplastic elastomer, and exhibits excellent antistatic effect and mechanical properties when kneaded with a polystyrene-based resin.

In order to cause the esterification reaction and the polymerization of caprolactam at the same time, and to control the respective reaction rates, to obtain a transparent and homogeneous elastomer, remove the generated water out of the system, The polymerization is preferably carried out while keeping the water content of the reaction system in the range of 0.1 to 1% by weight. If the water content exceeds 1% by weight, the polymerization of caprolactam takes precedence to cause coarse phase separation, whereas if it is less than 0.1% by weight, esterification takes precedence and caprolactam does not react, and an elastomer having a desired composition can be obtained. Absent. The water content is appropriately selected within the above range according to the physical properties desired for the elastomer.

In this reaction, if desired, the water content in the reaction system may be gradually reduced as the reaction proceeds. The control of the water content can be performed by controlling reaction conditions such as a reaction rate, an introduction flow rate of an inert gas, and a degree of pressure reduction, or by changing a reactor structure.

The degree of polymerization of the polyamide-imide elastomer used in the present invention can be arbitrarily changed as necessary, but the relative viscosity measured at 30 ° C. at 0.5% (weight / volume) in meta-cresol is 1.5 or more. Is preferred. If it is lower than 1.5, the mechanical properties cannot be sufficiently exhibited, and even when kneaded with the hydrogenated block copolymer, the mechanical properties may be insufficient. This is particularly preferably 1.6 or more.

When the diamine (d) is used in combination, it can be carried out in one of a method of reacting in one step and a method of reacting in two steps. The former is a method in which caprolactam (a), carboxylic acid component (b), glycol component (c), and diamine component (d) are simultaneously charged and reacted. Also,
The latter is a method in which the carboxylic acid component (b) and the diamine component (d) are reacted first, and then the caprolactam (a) and the glycol component (c) are reacted together.

In producing the polyamide-imide elastomer, an esterification catalyst can be used as a polymerization accelerator.

Examples of the polymerization accelerator include phosphorus compounds such as phosphoric acid, polyphosphoric acid, and metaphosphoric acid; tetraalkyl orthotitanates such as tetrabutyl orthotitanate; tin-based catalysts such as dibutyltin oxide and dibutyltin laurate; and manganese-based catalysts such as manganese acetate. A catalyst is preferably an antimony-based catalyst such as antimony trioxide; a lead-based catalyst such as lead acetate. The catalyst may be added at the beginning of the polymerization or at the middle of the polymerization.

Further, in order to enhance the thermal stability of the obtained polyamideimide elastomer, various kinds of stabilizers such as a heat-resistant anti-aging agent and an antioxidant can be used. It may be added. Also, after polymerization, it can be added before kneading with the hydrogenated block copolymer.

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

The ratio of the component (A) to the component (B) in the composition of the present invention needs to be in the range of 70:30 to 97: 3 by weight, and if the component (B) is less than this, it is sufficient. If the antistatic effect is not obtained, and if it is more than this, rubber elasticity will be insufficient.

For the composition of the present invention, a method of kneading a mixture of the component (A) and the component (B) using a known method, for example, using a Banbury mixer, a mixing roll, a single-screw or twin-screw extruder, or the like can be used. The kneading temperature at this time is 180-2
It is preferable to carry out in the range of 80 ° C.

It was found that when the polyamideimide elastomer and an electrolyte such as sodium dodecylbenzenesulfonate were used in combination in the composition of the present invention, a remarkable synergistic effect was exhibited in the antistatic effect. Examples of the organic electrolyte exhibiting such effects include an organic compound having an acidic group, a metal salt thereof, an organic ammonium salt, and an organic phosphonic acid.
Examples of the organic compound having an acidic group or its metal salt include aromatic compounds such as dodecylbenzenesulfonic acid, paratoluenesulfonic acid, dodecyldiphenyletherdisulfonic acid, naphthalenesulfonic acid, a condensate of naphthalenesulfonic acid and formalin, and polystyrenesulfonic acid. Aliphatic sulfonic acids, alkylsulfonic acids such as laurylsulfonic acid, stearic acid, lauric acid, organic carboxylic acids such as polyacrylic acid, organic phosphoric acids such as diphenyl phosphite, diphenyl phosphate and alkali metal salts thereof,
Alkaline earth metal salts. The effect is also exhibited in the form of a free acid, but it is preferable to use it as a salt of an alkali metal or an alkali metal earth. 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 trimethyloctyl ammonium bromide, trimethyloctyl ammonium chloride, cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, and trioctyl methyl ammonium bromide.Examples of the organic phosphonium salt include amyl triphenyl Examples include quaternary phosphonium salts such as phosphonium bromide and tetrabutylphosphonium bromide. AgNO ₃ , BeSO ₄ , CaCl ₂ , Ca (N
O ₃ ) ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ , CoCl ₂ , CrCl ₃ , CsCl, Cu
Cl ₂ , Cu (NO ₃ ) ₂ , CuSO ₄ , FeCl ₂ , KBr, KH ₂ PO ₄ , KNC
S, KNO ₃ , LiCl, LiOH, LiNO ₃ , MgCl ₂ , Mg (NO ₃ ) ₂ , Mg
_{SO 4, MnCl 2, MnSO 4} , NH 4 Cl, NH 4 NO 3, (NH 4) 2 SO 4, NaB
r, Na ₂ CO ₃ , NaH ₂ PO ₄ , NaNO ₃ , NiSO ₄ , Pb (NO ₃ ) ₂ , PrC
_{l 3, RbCl, RbNO 3,} Zn (NO 3) 2, etc. ZnSO ₄ and the like.

These electrolytes are added in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the total of the components (A) and (B).
5 parts by weight. If the amount is less than 0.01 part by weight, the effect of the additive is not obtained, and if the amount exceeds 10 parts by weight, the impact strength is reduced, the mold corrosion, the appearance of mold deposit, the appearance is deteriorated, etc., which is not preferable.

Among the electrolytes, an organic electrolyte is more preferable than an inorganic electrolyte in terms of mold corrosiveness and appearance.

In the resin composition of the present invention, other components such as a pigment, a dye, a reinforcing property, a filler, a heat stabilizer, an antioxidant, a nucleating agent, a lubricant, a plasticizer, and an ultraviolet ray within a range not detracting from the substance. Absorbents, release agents, flame retardants, other resins, polymers, etc.
It can be contained in any process such as a kneading process and a molding process.

The thermoplastic elastomer composition of the present invention thus obtained is molded by a known method generally used for molding a thermoplastic resin, such as injection molding, extrusion molding, blow molding, or vacuum molding. be able to.

The molded article of the present invention is characterized in that it has a surface resistivity of less than 1.0 × 10 ¹⁴ Ω / □ and exhibits a continuous antistatic property.

This surface resistivity is measured according to ASTM D-257. In the present invention, the term "having a continuous antistatic property" means that after molding, after standing for at least 90 days at 23 ° C. and 50% RH, or immersing in running water for 10 minutes after molding, the surface moisture is removed. , 23 ° C. and 50% RH for 24 hours, the surface resistivity is 10.0 times the initial value, preferably 5.0 times.
Means not to exceed double.

There is no particular limitation on the shape of the molded article of the present invention, for example,
Fine Chemical Report No.10 issued by Chunichisha Co., Ltd.
"New trends in plastic materials for electrical and electronic equipment" (Showa
(Issued September 20, 1988) II. Equipment It can be molded into parts of equipment of any shape described on pages 14 to 114.

Such objects include, for example, VTR cassette tape case halves, reels, reel flanges, windows, etc., audio cassette tape halves, cases, windows, etc., copier top covers, document holding covers, internal covers, front covers, etc. Telephone cabinets, front frames, back covers, escutcheons, speaker boxes, terminal boards, etc., for covers, operation covers, charging insulators, paper storage boxes, paper storage box covers, paper guides, copy paper trays, etc. Housing, handset case, vacuum cleaner body case, dust case, storage case, rotating hose,
Extension pipe hose, upper lid, filter box, etc., propeller fan of fan, front cover, after back cover, front panel of air conditioner, propeller fan, cross flow fan, wind direction adjustment plate, terminal cover, filter chassis, control panel, Makeup bags,
IC device package for semiconductor devices, case for micro floppy disk, cartridge for optical disk, etc., housing for office machine printer, display panel, paper guide, connector, platen knob, printer body,
A cassette cover, a cassette guide or the like can be shown.

In recent years, the above-mentioned devices and their components have been required to have high performance, and excellent antistatic performance has been strongly required. The challenge is not only to prevent dust due to electrification and to prevent noise and dropout, but also to prevent tape entanglement and running stop due to long tape running, such as VTR cassette tape. Further, it is required that these antistatic effects be maintained for a long time or not be lost even by washing with water.

The composition of the present invention can be used as it is for these various uses, or can be suitably used for obtaining a so-called soft touch molded product having an inner layer of another resin and an outer layer of the composition of the present invention by various multilayer molding means. At the same time, it is used not only for electric, electronic and home appliances, but also as a material for automobile interiors, exteriors, sporting goods, and medical foods.

FIG. 1 is a perspective view showing one example of a molded article of the present invention, and FIG.
The figure is a sectional view showing the laminated structure, which is formed by an inner layer 1 made of polyethylene resin and an outer layer 2 made of the composition of the present invention.

Effects of the Invention The composition of the present invention has a styrenic or olefinic thermoplastic elastomer, has good moldability, without deteriorating mechanical properties, and can provide a molded article having excellent antistatic properties, and Since there is no inconvenience caused when carbon black, carbon fiber or an antistatic agent is blended, it can be widely used as a molding material in various industrial fields.

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

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

(1) Charge voltage test: 8 KV using a static honest meter (anato Shokai)
After applying a static voltage, and after removing the voltage, the time at which the charged voltage of the sample was reduced by half was measured at 23 ° C. and 55% RH.

(2) Relative viscosity of elastomer: Measured in metacresol at 30 ° C. and 0.5 wt / vol%.

(3) Thermal decomposition temperature of the elastomer: The weight loss temperature was measured at a heating rate of 10 ° C./min using a differential thermobalance.

(4) Surface resistivity: Measured according to ASTM D-257 using a super-insulation meter SM-10E manufactured by Toa Denpa Kogyo Co., Ltd.

Production Example 1: Production of polyamide-imide elastomer (B-1) 500 ml equipped with a stirrer, nitrogen inlet and distillation tube
In a separable flask, 144 g of polyoxyethylene glycol (number average molecular weight 2010), 18.7 g of trimellitic anhydride
g, caprolactam 68.2 g and poly (2,2,4-trimethyl-1,2-dihydroquinoline) (trade name: Nocrack 224:
Add 0.4 g of antioxidant and mix at 100 ° C while stirring.
Dehydration was performed under reduced pressure of 1 Torr or less for 0 minutes. Then nitrogen is added to 60
The temperature was raised to 260 ° C. while flowing at a rate of ml / min, and polymerization was carried out for 4 hours. Thereafter, the pressure was gradually reduced at the same temperature, and unreacted caprolactam was distilled out of the system. Then, tetrabutyl titanate 0.1.
4 g was added, the pressure was reduced to 1 Torr, and the mixture was polymerized for 7 hours to obtain a pale yellow transparent elastomer.

This elastomer has a polyoxyethylene glycol content of 72% by weight, a polyamideimide having a number average molecular weight of 800, a relative viscosity of 2.25, and a tensile strength of 290 kg / c.
m ² and elongation were 1200%.

The thermal decomposition onset temperature, 10% weight loss temperature, and 30% weight loss temperature of this elastomer were 350 ° C and 425%, respectively.
° C and 443 ° C.

In addition, the amount of water in the polymerization system after 1, 2, and 4 hours from the start of the reaction at 260 ° C. was 0.7% by weight, 0.6% by weight, and 0.6% by weight.

Production Example 2: Polyamideimide elastomer (B-2) 500 ml equipped with a stirrer, a nitrogen inlet and a distillation tube
In a separable flask, caprolactam 40 g, polyoxyethylene glycol (number average molecular weight 2040) 91 g, trimellitic anhydride 11.2 g, hexamethylene diamine 1.5 g
(Molar ratio to polyoxyethylene glycol 0.
3), 0.15 g of phosphoric acid and 0.2 g of “Nocrack 224” were charged, and reacted at 260 ° C. for 4 hours while flowing nitrogen at 70 ml / min. Next, after unreacted caprolactam was distilled off under reduced pressure, 0.3 g of teraisopropylisotitanate was added and reacted at 1 Torr for 5 hours to obtain a yellow transparent elastomer.

This elastomer contains 72% by weight of polyoxyethylene glycol, has a relative viscosity of 1.90, and has a tensile strength of 295 kg / cm.
^2. Tensile elongation is 1020%, the thermal decomposition onset temperature, 10% weight loss temperature, and 30% weight loss temperature are 350 ° C and 403%, respectively.
° C and 438 ° C.

Examples 1 to 5 As the component (A), 40% by weight of styrene and butadiene were used.
A hydrogenated product of a block copolymer having a number average molecular weight of 50,000 consisting of 60% by weight and B-1 or B as a component (B)
These were mixed at a ratio shown in Table 1 to prepare a thermoplastic elastomer composition.

Next, using a twin screw extruder (manufactured by Nakatani Machinery Co., Ltd.) having a screw diameter of 30 mm, the composition was heated to a cylinder temperature of 270.
After melting and kneading at 250 ° C, screw rotation speed 250rpm, 5kg /
Extrusion was performed at a discharge rate of hr, and the three strands were cooled to about 30 ° C. with running water and pelletized. 80 ℃
For 3 hours in a gear oven. In order to obtain a test piece for measuring physical properties and surface resistivity, the above-mentioned pellets were molded at a cylinder temperature of 220 ° C. and a mold temperature of 60 ° C. using a 5 oz. Injection molding machine [manufactured by Toshiba Machine Co., Ltd.]. The physical properties of the obtained test piece were measured and evaluated.

 Table 1 shows the results.

Comparative Example A commercially available antistatic example (Kao Electro Stripper) was added to 98 parts by weight of the same component (A) as used in Examples 1 to 5.
A test piece was prepared in the same manner as in Examples 1 to 5 by adding 2 parts by weight, and the physical properties were measured. Table 1 shows the results.

Examples 6 to 8 Instead of the component (A) used in Examples 1 to 5, styrene was used.
Number average molecular weight 5 consisting of 40% by weight and 60% by weight of butadiene
A hydrogenated product of a 000 block copolymer modified with 1% by weight of maleic anhydride (A-1), 35% by weight of styrene
A mixture of 100 parts by weight of a hydrogenated block copolymer having a number average molecular weight of 120,000 and 65 parts by weight of butadiene mixed with 40 parts by weight of polypropylene and 70 parts by weight of paraffin oil (A-
2) Or 100 parts by weight of the same hydrogenated block copolymer mixed with 45 parts by weight of polypropylene, 90 parts by weight of paraffin oil, and 80 parts by weight of calcium carbonate (A-3). B) A molded product was produced in the same manner as in Examples 1 to 5 except that 10 parts by weight of the component was added. Table 2 shows the results.

Examples 9 to 11 In the same manner as in Example 4, the following components were used as the A component.

Manufactured by Asahi Kasei Kogyo Co., Ltd., Tufprene A (Example 9), manufactured by Asahi Kasei Kogyo Co., Ltd., Asaflex 810 (Example 10),
Sumitomo TPE-1500 manufactured by Sumitomo Chemical Co., Ltd. (Example 11) The surface resistivity of the obtained test piece was measured.
After 150 days, the value was 1 × 10 ¹⁰ Ω / □ or less.

Example 12 An adapter and a multilayer die are attached to a stationary 55 m / m extruder and a mobile 50 m / m extruder manufactured by Plastics Industry Laboratory. 55m
/ m Extruder hopper Suntech HD manufactured by Asahi Kasei Corporation
(High density polyethylene) B-770 (Density 0.955, M10.2)
And the pellets obtained in Example 8 were charged into a 50 m / m extruder hopper to form a multilayer parison, thereby obtaining a hollow molded article having the shape shown in FIG.

Table 3 shows the results of evaluating the physical properties of the obtained molded body.

Example 13 Using a two-color injection molding machine made of Nissei Resin, a push button or key top having an outer layer of a hydrogenated block copolymer and an inner layer of an ABS layer was molded. That is, first, a stylac ABS183 manufactured by Asahi Kasei Kogyo Co., Ltd. was partly molded into a two-color molding die, which was then inserted into another die, and the pellet obtained in Example 7 was injected into the remaining part. Molded and integrated. The thickness of each layer was 1.5 mm. The physical properties of the obtained molded body were evaluated, and the results are shown in Table 3.

Example 14 90 m / m extruder manufactured by Toshiba Machine Co., Ltd., an adapter for a 65 m / m extruder, a multi-manifold die, a take-up machine, using a multilayer sheet facility having a winder, and a 90 m / m extruder hopper. Asahi Kasei Polypro M7200 (MFI 1.5g / 10MIN.)
The pellets obtained in Example 8 were charged into a 65 m / m extruder hopper to produce a multilayer sheet. The thickness of the polypropylene layer was 3.6 m / m, and the thickness of the elastomer layer was 2.4 m / m.
This sheet was molded into a carrying case for a video camera using a vacuum molding machine manufactured by Asano Laboratories. The elastomer layer was on the inside of the case, but had moderate cushioning.

 Table 3 shows the physical properties of the obtained molded body.

In addition, the surfaces of these compacts were rubbed 100 times with gauze,
The ash adhesion test on the cigarettes at a distance of / 4 inch showed only slight adhesion in any case.

[Brief description of the drawings]

FIG. 1 is a perspective view of one example of the molded article of the present invention, and FIG. 2 is a cross-sectional view of the same molded article.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08L 21/00 C08L 23/00-23/36 C08L 53/02

Claims (4)

(57) [Claims] 1. A hydrogenated block copolymer comprising (A) at least two polymer blocks mainly composed of vinyl aromatic compound units and at least one polymer block mainly composed of conjugated diene compound units. Or (B) (a) caprolactam, (b) a trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring, and (c) Polyamideimide obtained from polyoxyethylene glycol or a polyoxyalkylene glycol mixture mainly composed of polyoxyethylene glycol, having a component (c) content of 30 to 85% by weight and a relative viscosity at a temperature of 30 ° C. of 1.5 or more. A thermoplastic elastomer composition comprising an elastomer and a weight ratio of 70:30 to 97: 3. 2. A hydrogenated block copolymer comprising (A) at least two polymer blocks mainly composed of vinyl aromatic compound units and at least one polymer block mainly composed of conjugated diene compound units. Or (B) (a) caprolactam, (b) a trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring, or (c) a modified product thereof and / or an olefin-based thermoplastic elastomer. The content of the component (c) obtained from at least one of polyoxyethylene glycol or a polyoxyalkylene glycol mixture mainly composed of polyoxyethylene glycol and (d) a diamine having 2 to 10 carbon atoms, wherein the content of the component (c) is 30 to 85% by weight. And a polyamideimide elastomer having a relative viscosity of 1.5 or more at a temperature of 30 ° C. in a weight ratio of 70:30 to 97: 3. A thermoplastic elastomer composition characterized by the following. 3. The thermoplastic elastomer composition according to claim 1, comprising at least one electrolyte selected from an organic electrolyte and an inorganic electrolyte. 4. An antistatic molded article comprising the thermoplastic elastomer composition according to claim 1 and having a persistent surface resistivity of less than 1.0 × 10 ¹⁴ Ω / □.