JPH04348150A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition having excellent permanent antistatic properties, mechanical characteristics and corrosion resistance of metal, comprising a polyamide elastomer, a styrenic thermoplastic resin, a modified vinyl-based polymer and a polyamide resin. CONSTITUTION:A thermoplastic resin composition comprising 100 pts.wt. total amounts of (A) 1-40 pts.wt. polyether ester amide or polyether amide, (B) 98-5 pts.wt. styrenic thermoplastic resin (preferably HI-PS resin or ABS resin), (C) 0-50 pts.wt. modified vinyl-based polymer containing 0.1-20 pts.wt. one or more functional groups selected from carboxyl group, epoxy group, amino group, hydroxyl group, polyalkylene oxide group and a catalyst thereof, (D) 1-90 pts.wt. polyamide resin, preferably nylon 66 having 1.1-5 relative viscosity, preferably further (E) 0.01-10 pts.wt. inorganic salt (preferably alkaline earth metal salt or hydrotalcite) selected from alkali alkaline earth) metal, transition metal and aluminum metal.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is a thermoplastic resin that has antistatic properties and has excellent mechanical properties such as impact resistance, heat resistance, chemical resistance, and corrosion resistance of metals caused by corrosive gases. Regarding the composition.

0002

[Prior Art] Synthetic polymer materials have excellent mechanical properties,
Due to its workability, it is used in a wide range of fields and is an electrical insulator. If these materials are provided with antistatic properties in addition to their mechanical strength, their uses can be further expanded. In other words, copy machines, facsimile machines, word processors, etc. that need to be prevented from being damaged by static electricity.
Applications can be expanded to electronic and electromechanical parts for personal computers, televisions, video tapes, etc., and various dustproof parts.

[0003] As a method for improving the antistatic properties of synthetic polymer materials, a hydrophilic rubber-like polymer obtained by copolymerizing a conjugated diene or/and an acrylic ester with a vinyl monomer having an alkylene oxide group is used. A method obtained by graft polymerizing a vinyl monomer or vinylidene monomer to (
JP-A No. 55-36237) and a composition formed by blending polyether ester amide with a rubber-reinforced styrene resin and a modified vinyl polymer containing a carboxyl group (
JP-A No. 62-241945), etc., have achieved practical antistatic properties.

0004

[Problems to be Solved by the Invention] However, the antistatic resin obtained by graft polymerizing the hydrophilic rubbery polymer described in JP-A No. 55-36237 does not contain a special hydrophilic rubbery polymer. However, since the method of production is complicated, the mechanical properties of the resulting resin are poor, and the corrosion resistance of metals is poor, making it unsatisfactory. Further, although the composition described in JP-A-62-241945 has excellent mechanical properties such as impact resistance, it is not sufficiently satisfactory in preventing corrosion of metals.

[0005] An object of the present invention is to provide an antistatic resin which has permanent antistatic properties and is excellent in mechanical properties represented by impact resistance and anticorrosion properties for metals.

[0006]

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present invention achieves the above objects efficiently by blending a polyamide elastomer, a styrene thermoplastic resin, and a polyamide resin. This discovery led to the present invention.

That is, the present invention comprises (A) 1 to 40 parts by weight of polyamide elastomer, (B) 98 to 5 parts by weight of styrene thermoplastic resin, (C) carboxyl group, epoxy group,
0 to 50 parts by weight of a modified vinyl polymer containing at least one functional group selected from amino groups, hydroxyl groups, polyalkylene oxide groups, or derivatives thereof, and (D) 1 to 90 parts by weight of polyamide resin (( A)+(
B) + (C) + (D) (total of 100 parts by weight).

The present invention will be explained in detail below.

In the present invention, (A) polyamide elastomer is a polyether ester obtained by the reaction of (a) a polyamide-forming component and (b) a polyether ester-forming component consisting of poly(alkylene oxide) glycol and dicarboxylic acid. amide, and (a) a polyamide-forming component and (b) a poly(alkylene oxide) glycol obtained by aminating or carboxylating both ends of the poly(alkylene oxide) glycol, and a polyether-forming component consisting of a dicarboxylic acid or diamine. It is an ether amide.

(a) As the polyamide-forming component, specifically, ω-aminocaproic acid, ω-aminoenanthate, ω-aminocaprylic acid, ω-aminopergonic acid, ω-
aminocapric acid, and 11-aminoundecanoic acid,
Aminocarboxylic acids such as 12-aminododecanoic acid or lactams such as caprolactam, enantlactam, capryllactam and laurolactam and hexamethylenediamine-adipate, hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate. Salts of diamine-dicarboxylic acids are mentioned, and caprolactam, 12-aminododecanoic acid, and hexamethylenediamine-adipate are particularly preferably used.

(b) Poly(
An example of an alkylene oxide) glycol is poly(
Ethylene oxide) glycol, poly(1,2-propylene oxide) glycol, poly(1,3-propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, block or random of ethylene oxide and propylene oxide copolymers and block or random copolymers of ethylene oxide and tetrahydrofuran,
Also used are those in which both ends are aminated or carboxylated. Among these, poly(ethylene oxide) glycol and poly(ethylene oxide) glycol, which is aminated or carboxylated at both ends, are particularly preferably used because of their excellent antistatic properties. In this case, poly(
The number average molecular weight of glycol (alkylene oxide) is 20
A range of 0 to 10,000, particularly 400 to 6,000, is preferred in terms of excellent polymerizability.

The dicarboxylic acid component used in the present invention preferably has 4 to 20 carbon atoms. Specifically, terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, and 3-sulfonate. Aromatic dicarboxylic acids such as sodium isophthalate, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4'-dicarboxylic acid, and succinic acid, oxalic acid, adipine acids, sebacic acid and dodecanedioic acid (
Examples include aliphatic dicarboxylic acids such as decane dicarboxylic acid), especially terephthalic acid, isophthalic acid, 1,4
-Cyclohexanedicarboxylic acid, sebacic acid, adipic acid and dodecanedioic acid are preferably used from the viewpoint of polymerizability, color tone and physical properties.

Examples of diamine components include aromatic, alicyclic, and aliphatic diamines. Among them, hexamethylene diamine, which is an aliphatic diamine, is preferably used for economical reasons.

The ratio of (a) polyamide-forming component/(b) polyether ester-forming component or polyether-forming component of the (A) polyamide elastomer used in the present invention is 10/90 to 90/10% by weight, particularly 20/80
A range of 70/30% by weight is preferable since the resin composition has excellent impact resistance and antistatic properties.

(A) There are no particular restrictions on the method for producing the polyamide elastomer;
Methods disclosed in Japanese Patent Laid-Open No. 55-133424, etc. can be used.

In the present invention, (B) styrenic thermoplastic resin is a (co)polymer containing 10% by weight or more of styrene units, 1 to 80 parts by weight of a rubbery polymer and 10% by weight of styrene.
These are graft (co)polymers obtained by graft polymerization of 99 to 20 parts by weight of monomers or monomer mixtures containing the above, and mixtures thereof.

[0017] As the above-mentioned rubbery polymer, those having a glass transition temperature of 0°C or less are suitable, and specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, and styrene-butadiene block are preferred. Copolymers, diene rubbers such as butyl acrylate-butadiene copolymers and their hydrogenated products, acrylic rubbers such as butyl polyacrylate, polyisoprene,
Examples include polychloroprene, ethylene-propylene-diene monomer terpolymer, and chlorinated polyethylene.

The (B) styrenic thermoplastic resin in the present invention specifically includes polystyrene, rubber-modified polystyrene (HI-PS resin), styrene-acrylonitrile copolymer, and styrene-rubber polymer-acrylonitrile copolymer. Combined (ABS resin, AES resin, AAS resin,
ACS resin), etc. Two or more types of these can also be used. Furthermore, part of these styrenes and/or part or all of acrylonitrile can be converted into α-methylstyrene, p-methylstyrene, pt-butylstyrene, methyl, ethyl, propyl, n-butyl (meth)acrylate. ester compounds such as maleimide, N-
Methylmaleimide, N-cyclohexylmaleimide, N
-Also includes those substituted with vinyl monomers copolymerizable with styrene, such as maleimide monomers such as phenylmaleimide.

Here, as the styrenic thermoplastic resin, in particular, HI-PS resin, ABS resin, AES resin, AA
S resin, ACS resin, MBS resin, etc. are preferably used. In that case, the amount of the rubbery polymer in the resin composition is 40% by weight or less, preferably 30% by weight or less. If it exceeds 40% by weight, the resin composition becomes flexible, which is not preferable. (B) There are no restrictions on the manufacturing method of the styrenic thermoplastic resin, including bulk polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization.
Conventional methods such as suspension polymerization can be used.
(C) A modified vinyl polymer (hereinafter referred to as a modified vinyl polymer) containing at least one functional group selected from a carboxyl group, an epoxy group, an amino group, a hydroxyl group, a polyalkylene oxide group, or a derivative thereof used in the present invention. (abbreviated as "polymer") has a structure obtained by polymerizing or copolymerizing one or more vinyl monomers, and has a carboxyl group, epoxy group, amino group, hydroxyl group, A polymer having at least one functional group selected from polyalkylene oxide groups or derivatives thereof. The content of compounds containing these functional groups is not limited, but is particularly 0.1 to 20% by weight per 100 parts by weight of the modified vinyl polymer.
A range of is preferred.

Normally, the effects of the present invention can be effectively exhibited if one or more of the above-mentioned functional groups is substantially contained on average in one molecule of the modified vinyl polymer.

(C) There is no particular restriction on the method of introducing a carboxyl group into the modified vinyl polymer, but the method of introducing a carboxyl group into the modified vinyl polymer is as follows. A method of copolymerizing a vinyl monomer having an anhydride carboxyl group with a specified vinyl monomer, ■γ,γ′-azobis(γ-
Polymerization initiators having a carboxyl group such as cyanovalic acid), α,α′-azobis(α-cyanoethyl)-p-benzoic acid and peroxide succinic acid and/or thioglycolic acid, α-mercaptopropionic acid, β-mercapto A method of (co)polymerizing a predetermined vinyl polymer using a polymerization degree regulator having a carboxyl group such as propionic acid, α-mercapto-isobutyric acid, and 2,3 or 4-mercaptobenzoic acid, and ■ methacrylic acid. A method of saponifying a copolymer of a (meth)acrylic acid ester monomer such as methyl or methyl acrylate with an aromatic vinyl monomer and, if necessary, a vinyl cyanide monomer, with an alkali, etc. can be used.

There is no particular restriction on the method of introducing the epoxy group, but for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether, styrene-p
A method of copolymerizing -glycidyl ether, p-glycidyl styrene, etc. with a predetermined vinyl monomer can be used.

[0023] There is also no particular restriction on the method of introducing the amino group, but for example, the following formula (I)

[0024]

[Chemical formula 1]

(In the formula, R1 represents hydrogen, a methyl group, or an ethyl group, and R2 represents hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, or an alkanoyl group having 6 to 12 carbon atoms. A vinyl monomer having at least one functional group of an amino group or a substituted amino group represented by phenyl group, cycloalkyl group, or derivatives thereof) is copolymerized with a predetermined vinyl monomer. method etc. can be used.

Specific examples of the vinyl monomer having at least one functional group such as an amino group or a substituted amino group include aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, and ethylaminomethacrylate. Alkyl ester derivatives of acrylic acid or methacrylic acid such as propyl, phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate, vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, allylamine, methalylamine and N -Allylamine derivatives such as methylallylamine, (meth)acrylamide derivatives such as acrylamide, methacrylamide and N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, and aminostyrenes such as p-aminostyrene. It will be done.

There are no particular limitations on the method of introducing hydroxyl groups, but examples include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, and 2-hydroxyethyl acrylate. 3,4,5,6-pentahydroxyhexyl, 2,3,4,5,6-pentahydroxyhexyl methacrylate, 2,3,4,5-acrylic acid
Tetrahydroxypentyl, methacrylic acid 2,3,4,
5-tetrahydroxypentyl, 3-hydroxy-1-
Propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2
-butene, 3-hydroxy-2-methyl-1-propene, cis-5-hydroxy-2-pentene, trans-5
-Hydroxy-2-pentene, 4-dihydroxy-2-
A method of copolymerizing butene or the like with a predetermined vinyl monomer can be used.

There is also no particular restriction on the method of introducing the polyalkylene oxide group, but for example, (1) the following formulas (II) and (III)

[0029]

[Case 2]

(In the formula, R3 represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R4 represents an alkyl group having 2 to 6 carbon atoms, and R5 represents hydrogen or an alkyl group having 1 to 6 carbon atoms.) , n is 2 to 500) can be used. A method can be used in which a vinyl monomer containing a polyalkylene oxide group represented by the following formula is copolymerized with a predetermined vinyl monomer.

Specific examples include polyethylene glycol acrylate, polyethylene glycol methacrylate, poly(propylene oxide) glycol acrylate, poly(propylene oxide) methacrylate, poly(tetramethylene oxide) glycol acrylate, poly(tetramethylene oxide) glycol methacrylate. , poly(hexamethylene oxide) glycol methacrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol methacrylate, methoxypoly(propylene oxide) glycol acrylate, methoxypoly(propylene oxide) glycol methacrylate, methoxypoly(tetramethylene oxide) glycol methacrylate, ethoxypolyethylene glycol acrylate, Ethoxypolyethylene glycol methacrylate, ethoxypoly(propylene oxide) glycol acrylate, polyethylene glycol acrylamide, polyethylene glycol methacrylamide, poly(propylene oxide) glycol acrylamide, poly(propylene oxide) glycol methacrylamide, poly(tetramethylene oxide) glycol acrylamide, poly( tetramethylene oxide) glycol methacrylamide, methoxypolyethylene glycol acrylamide, methoxypolyethylene glycol methacrylamide, methoxypoly(propylene oxide) glycol acrylamide, methoxypoly(propylene oxide) glycol acrylamide,
Examples include propylene oxide) glycol methacrylamide and methoxy(tetramethylene oxide) glycol methacrylamide.

[0032] Also, (2) acrylic acid, methacrylic acid,
Ester of a vinyl polymer containing a carboxyl group obtained by copolymerizing maleic acid, maleic anhydride, phthalic acid, etc. with a desired vinyl monomer and polyalkylene oxide glycol having an alkyl ether at one end. A method in which the reaction is carried out at high temperature under normal pressure or reduced pressure can also be used.

The poly(alkylene oxide) glycol having an alkyl ether at one end used here includes, for example, methoxypolyethylene glycol, methoxypoly(1,2
-propylene oxide) glycol, methoxypoly(1
, 3-propylene oxide) glycol, methoxypoly(tetramethylene oxide) glycol, methoxypoly(hexamethylene oxide) glycol, methoxy (block or random copolymer of ethylene oxide and propylene oxide) and methoxy (block or random copolymer of ethylene oxide and tetrahydrofuran) combination), etc. The number average molecular weight of poly(alkylene oxide) glycol having an alkylene ether at one end is in the range of 75 to 20,000.

There are no particular restrictions on the vinyl monomer used in the polymerization of the modified vinyl polymer (C), and examples include aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyltoluene, and acrylonitrile. , vinyl cyanide monomers such as methacrylonitrile, (meth)acrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, methyl acrylate, butyl acrylate, maleimide, N-methylmaleimide, N - One or more of maleimide monomers such as cyclohexylmaleimide and N-phenylmaleimide, oleic monomers such as ethylene and propylene, and vinyl monomers such as vinyl chloride, vinyl acetate, and butadiene. They can be selected and used together. In particular, aromatic vinyl monomers such as styrene, methyl methacrylate, etc.
Preferred are meth)acrylic acid ester monomers, vinyl cyanide monomers such as acrylonitrile, and maleimide monomers such as N-phenylmaleimide.

[0035] If necessary, polybutadiene, acrylonitrile/butadiene copolymer (NBR), styrene/butadiene copolymer (SBR), polybutyl acrylate, and ethylene/propylene/diene rubber (E
Rubbery polymers such as PDM) can also be used in combination with the above vinyl monomers.

[0036] Furthermore, as the method for introducing the functional group, any of the various methods described above can be used in combination.

There is no particular restriction on the method for producing the modified vinyl polymer (C), and bulk polymerization, solution polymerization, suspension polymerization,
Conventional methods such as emulsion polymerization and bulk-suspension polymerization can be used.

The polyamide resin (D) in the present invention includes lactams such as caprolactam, enantlactam, dodecanolactam, and undecanolactam, ω-aminocaproic acid, ω-aminoenantoic acid, ω-aminocaprylic acid, and ω-aminopergone. acids, ω-aminocapric acid and aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid, nylon-6.6, -
6.9, -6.10, -6.12, -11.6, -12
・There are polymers of diamine-dicarboxylic acid salts that are precursors such as caprolactam, 11-aminoundecanoic acid, 12-aminododecanoic acid, and nylon-6.
Polymers of 6-salt, -6.10-salt, -6.12-salt, and -11.6-salt are preferred.

(D) The degree of polymerization of the polyamide resin is not particularly limited, but the relative viscosity measured in sulfuric acid at 25° C. at a concentration of 1.0% is 1.1 to 5.0, particularly 1.5 to 4.0. A range of is preferred.

(D) There are no particular restrictions on the method for producing the polyamide resin, and ordinary polymerization methods can be used. In the present invention, (A) polyamide elastomer, (B) styrene thermoplastic resin, (C) modified vinyl polymer, and (
D) The proportion of polyamide resin is (A) component, (B) component,
Component (A) is 1 to 40 parts by weight, preferably 4 to 30 parts by weight, based on 100 parts by weight of the total amount of components (C) and (D).
parts by weight, component (B) is 98 to 5 parts by weight, preferably 90 parts by weight
-20 parts by weight, component (C) is 0 to 50 parts by weight, preferably 1 to 40 parts by weight, and component (D) is 1 to 90 parts by weight, preferably 5 to 75 parts by weight. However, (A) + (B)
The total of +(C)+(D) is 100 parts by weight.

If the amount of polyamide elastomer (A) is less than 1 part by weight, the antistatic properties of the resin composition will be insufficient, and if it exceeds 40 parts by weight, the resin composition will become flexible and have poor mechanical properties, which is not preferable. (B) If the styrenic thermoplastic resin is less than 5 parts by weight, the impact resistance will be poor, and if it exceeds 98 parts by weight, the antistatic property will be poor, which is not preferable. (C) If the amount of modified vinyl polymer exceeds 50 parts by weight, the appearance of the molded product will deteriorate and it cannot be used.

If the amount of polyamide resin (D) is less than 1 part by weight, the corrosion resistance of the metal will be poor, and if it exceeds 90 parts by weight, the impact resistance will be poor.

[0043] The present invention provides the above resin composition with an alkali metal,
When an inorganic metal salt selected from alkaline earth metals, transition metals, and aluminum metals (hereinafter abbreviated as inorganic metal salt) is blended, the corrosion resistance of the metal is further improved.

The metals of the inorganic metal salt (E) in the present invention include Li, Na, K, Rb, Cs, Be, Mg, C
a, Sr, Ba, Ti, Zr, Mn, Fe, Co, Ni
, Cu, Zn, Al, etc., especially Ca, Mg,
Zn and Al are preferred.

On the other hand, examples of groups that form salts with the above metals include nitric acid, sulfuric acid, chloric acid, carbonic acid, oxalic acid, silicic acid, phosphoric acid, boric acid, cyanic acid, halogen, chloric acid, thiocyanic acid, and water. Examples include acids and oxygen, and among these, hydroxy acid, oxygen, carbonic acid, and silicic acid are preferred.

Specifically, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, zinc hydroxide, calcium oxide, magnesium oxide, aluminum oxide, zinc oxide, calcium carbonate, basic calcium carbonate, magnesium carbonate, basic carbonate Magnesium, aluminum carbonate, zinc carbonate, potassium silicate, sodium silicate, calcium silicate, magnesium silicate and hydrotalcite, among others calcium hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, calcium carbonate, Magnesium carbonate, calcium silicate,
Magnesium silicate and hydrotalcite are particularly preferred since they have excellent corrosion resistance for metals.

[0047] Here, hydrotalcite has the general formula

[
0048

[Chemical formula 3]

This is a compound represented by: Among them, Mg4.5 Al2 (OH)13CO3 .3.
5H2 O, Mg4.5 Al2 (OH)13CO3
It is.

Hydrotalcite-like compounds can be synthesized by various methods such as those described in US Pat. No. 3,539,306.

Generally, synthetic hydrotalcite can be produced by co-precipitation of a solution of a cationic component and a solution of an anionic component. The most readily available hydrotalcite would be magnesium-aluminum hydroxycarbonate hydrate. The preferred hydrotalcite is Mg4.5Al2(O
H) Magnesium aluminum hydroxyhydrate available under the commercial name DHT-40 characterized as 13CO3 .3.5H2O.

[0052] The above inorganic metal salts may be used alone or in combination of two or more.

(E) The particle size of the inorganic metal salt is not particularly limited, but in order to effectively achieve the purpose of the present invention, the average particle size is preferably 10 μm or less, particularly 5 μm or less.

In the present invention, the amount of (E) inorganic metal salt added is the total amount of (A) polyamide elastomer, (B) styrene thermoplastic resin, (C) modified vinyl polymer, and (D) polyamide resin (( A)+(B)+(C)+(D
) = 100 parts by weight), the range is from 0.01 to 10 parts by weight, preferably from 0.05 to 5 parts by weight.

If the amount added is less than 0.01 part by weight, the corrosion resistance of the metal will not be improved, and if it exceeds 10 parts by weight, the impact resistance will deteriorate, which is not preferable.

There are no particular limitations on the method for producing the resin composition of the present invention; for example, (A) a polyamide elastomer, (B) a styrene thermoplastic resin, (C) a modified vinyl polymer, (D) a polyamide resin, and As necessary (E)
It is manufactured by melt-kneading a mixture of inorganic metal salts using a Banbury mixer, rolls, extruder, etc.

The resin composition of the present invention may contain other thermoplastic resins that are compatible with the resin composition of the present invention, such as polycarbonate, polyphenylene ether, polyglutarimide,
Mixing polycyclohexane dimethylene terephthalate, etc. to improve impact resistance and heat resistance, mixing polyolefin, polybutylene terephthalate, polyethylene terephthalate, etc. to improve chemical resistance, and mixing vinyl chloride resin, etc. to improve resistance to chemicals. Flammability can also be improved. It is also possible to further improve antistatic properties by adding antistatic agents such as metal salts of sulfonic acid and anionic, cationic, or nonionic surfactants, and if necessary, oxidation prevention. It is also possible to add various stabilizers such as UV absorbers, pigments, dyes, lubricants and plasticizers, flame retardants, etc.

[0058]

[Examples] In order to explain the present invention more specifically, Examples and Comparative Examples will be given below. In addition, after the finally obtained resin composition was molded by injection molding, various physical properties were measured by the following test methods.

Izod impact strength: ASTM D25
6-56A Flexural modulus: ASTM D790 Surface specific resistance: Using a 2t x 40mmφ disc, at room temperature 2
Measurement was carried out at 3°C under an atmosphere of 50% RH and humidity. A super insulation resistance meter SM-10E manufactured by Toa Denpa Kogyo Co., Ltd. was used for the measurement.

Corrosion resistance of metal: 8 x 18 mm nickel foil with a 20 x 20 x 15 mm lid, and 6 pieces on the sides and lid.
A composition for determining the corrosion resistance of metal with holes of mmφ was placed in a molded container, and after being left in a desiccator adjusted to contain about 3 ppm of hydrogen chloride at 23°C for 8 hours, a nickel foil was placed. The surface was observed using an optical microscope. The judgment criteria were that the surface of the nickel foil was ◎: extremely good, ○: good, △: corroded, and ×: markedly corroded.

[0061] Parts and percentages in the examples indicate parts by weight and percentages by weight, respectively.

Reference Example (1) (A) Preparation of polyamide elastomer A-1: 40.0 parts of caprolactam, 53.1 parts of polyethylene glycol having a number average molecular weight of 1000, and 9 parts of terephthalic acid.
．． 2 parts of “Irganox” 1098 (antioxidant) 0
．． 2 parts of antimony trioxide catalyst and 0.1 part of antimony trioxide catalyst were charged into a reaction vessel equipped with a helical ribbon stirring blade, and the mixture was purged with nitrogen and heated and stirred at 260°C for 60 minutes to obtain a transparent homogeneous solution. Polymerization was carried out for 4 hours under conditions of 5 mmHg or less to obtain a viscous and transparent polymer.

[0063] Pellet-shaped polyether ester amide (A-1) was prepared by discharging the polymer in a gut shape onto a cooling belt and pelletizing it.

A-2: Polyethylene glycol diamine having amino groups at both ends was obtained by reacting polyethylene glycol with a number average molecular weight of 4000 with acrylonitrile and further carrying out a hydrogenation reaction. This and terephthalic acid were subjected to a salt reaction using a conventional method, and 40% of polyethylene glycol diammonium terephthalate was obtained.
A solution was obtained.

120 parts of the above 40% polyethylene glycol diammonium terephthalate aqueous solution in a concentration can;
Add 16 parts of 40% hexamethylene diammonium adipate aqueous solution and heat at normal pressure for about 2 hours until the internal temperature reaches 110°C.
It was heated for an hour and concentrated to 80% concentration. Subsequently, the concentrated solution was transferred to a polymerization can, and heating was started while flowing nitrogen into the polymerization can.

[0066] When the internal temperature reached 120°C, a predetermined amount of sodium dodecylbenzenesulfonate and 1,3,5
10 parts of -trimethyl-2,4,6-tri(3,5-di-t-butylhydroxybenzyl)benzene were added, stirring was started, and the temperature was raised until the internal temperature reached 245°C. 24
The polymerization was completed by heating at 5° C. for 18 hours.

Thereafter, polyetheramide (A-2) in the form of pellets was prepared in the same manner as in A-1.

(2) (B) Preparation of styrenic thermoplastic resin (b1) Graft copolymer B-1: Polybutadiene latex (rubber particle size 0.2
5μ, gel content 80%)) 40 parts of a monomer mixture consisting of 72% styrene and 28% acrylonitrile was emulsion polymerized in the presence of 60 parts (in terms of solid content).

The obtained graft copolymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to prepare a powdery graft copolymer (B-1).

B-2: 72% methyl methacrylate, 24% styrene, 4% acrylonitrile in the presence of 40 parts (solid content) of the polybutadiene latex used in B-1.
After emulsion polymerization of 60 parts of a monomer mixture consisting of B-
Powder-like graft copolymer (B-2) was prepared in the same manner as in 1.
) was prepared.

B-3: Diene NF35A (Asahi Kasei Corporation)
After dissolving 10 parts of styrene in 90 parts of styrene, a graft polymer (B-3) was prepared by bulk polymerization.

(b2) Copolymer b-1: Copolymer (b-1) was prepared by suspension polymerization of 72 parts of styrene and 28 parts of acrylonitrile.

b-2: A copolymer (b-2) was prepared by suspension polymerization of 72 parts of methyl methacrylate, 24 parts of styrene, and 4 parts of acrylonitrile.

b-3: Copolymer (b-3) was prepared by emulsion polymerization of 50 parts of styrene, 30 parts of N-phenylmaleimide, and 20 parts of acrylonitrile.

(3) (C) Preparation of modified vinyl polymer C
-1: Modified vinyl polymer (C-
1) was prepared.

C-2: A modified vinyl polymer (C-2) was prepared by suspension polymerization of 67 parts of methyl methacrylate, 21 parts of styrene, 4 parts of acrylonitrile, and 5 parts of methacrylic acid.

C-3: A modified vinyl polymer (C-3) was prepared by suspension polymerization of 70 parts of styrene, 25 parts of acrylonitrile, and 5 parts of 2-hydroxyethyl methacrylate.

C-4: A modified vinyl polymer (C-4) was prepared by suspension polymerization of 69 parts of styrene, 30 parts of acrylonitrile, and 1 part of glycidyl methacrylate.

C-5: A modified vinyl polymer (C-5) was prepared by emulsion polymerization of 70 parts of styrene, 25 parts of acrylonitrile, and 5 parts of methacrylamide.

C-6: 95 parts of styrene, 5 parts of methacrylic acid
A modified vinyl polymer (C-6) was prepared by suspension polymerization.

(4) (D) Preparation of polyamide resin D-1
: CM-1021 (nylon-6, manufactured by Toray Industries, Inc.) was used.

D-2: CM-3001 (nylon-66
, manufactured by Toray Industries, Inc.) was used.

(5) (E) Preparation of inorganic metal salt E-1: Calcium carbonate (Calfine 200, Maruo calcium (
Co., Ltd.) was used.

E-2: Magnesium hydroxide (Katayama Chemical (
Co., Ltd.) was used.

E-3: Hydrotalcite (DHT-4
A-2, manufactured by Kyowa Kagaku Co., Ltd.) was used.

Examples 1 to 18 (A) polyamide elastomer prepared in Reference Example, (B
) Styrenic thermoplastic resin: (b1) graft copolymer, (b2) copolymer, (C) modified vinyl copolymer, (
D) Polyamide resin and (E) inorganic metal salt were mixed at the compounding ratio shown in Tables 1 and 2, and melt-kneaded and extruded at a resin temperature of 240°C (Example 14, 270°C) using a vented 40mmφ extruder. A pellet-shaped polymer was produced by performing the following steps. Next, a test piece was molded using an injection molding machine at a cylinder temperature of 250°C (Example 14, 280°C) and a mold temperature of 60°C, and each physical property was measured. The surface resistivity value was measured using an injection molded disk with a thickness of 2 mm under the following conditions.

(1) Immediately after molding, it was washed with an aqueous solution of the detergent "Mama Lemon" (manufactured by Lion Corporation), and then thoroughly washed with distilled water to remove surface moisture, and then heated to 50% RH.
The humidity was adjusted at 23° C. for 24 hours and measured.

(2) After molding, 1 at 50% RH and 23°C
After being left for 00 days, it was washed with an aqueous solution of the detergent "Mama Lemon", and then thoroughly washed with distilled water to remove surface moisture, and then conditioned at 50% RH and 23° C. for 24 hours and then measured.

[0089] The container for measuring corrosion resistance of metal was molded using an injection molding machine at a cylinder temperature of 250°C (Examples 14 and 2).
80°C) and a mold temperature of 40°C. The measurement results are shown in Tables 3 and 4.

Comparative Examples 1 to 6 (A) polyamide elastomer prepared in Reference Example, (B
) Styrenic thermoplastic resin: (b1) graft copolymer, (b2) copolymer, (C) modified vinyl polymer, (D
) Polyamide resin and (E) inorganic metal salt were mixed at the compounding ratios shown in Tables 1 and 2, and their physical properties were measured in the same manner as in the examples. The measurement results are shown in Tables 3 and 4.

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

[Table 3]

[0094]

[Table 4]

From the results in Tables 3 and 4, the following is clear. All of the resin compositions of the present invention (Examples 1 to 18) have an excellent balance between mechanical properties represented by impact strength and flexural modulus, and metal corrosion resistance, and have low surface resistivity values. ing. Furthermore, the resistance value hardly changes even after surface cleaning or changes over time, and it exhibits excellent permanent antistatic properties. That is, the resin composition of the present invention has excellent mechanical properties, metal corrosion resistance, and permanent antistatic properties.

On the other hand, when the amount of polyamide elastomer (A) is less than 1 part by weight (Comparative Example 1), the resistance value is high;
The antistatic property is poor and the corrosion resistance of the metal is poor, and when it exceeds 40 parts by weight (Comparative Example 2), the flexural modulus is poor, which is not preferable.

If the amount of the styrene thermoplastic resin is less than 5 parts by weight (Comparative Example 3), the impact resistance will be poor, and if it exceeds 98 parts by weight (Comparative Example 4), the antistatic property will be poor, which is not preferable. Furthermore, if the amount of polyamide resin blended is less than 1 part by weight (Comparative Example 5), the corrosion resistance of the metal will be poor, and if it exceeds 90 parts by weight, the impact resistance and antistatic properties will be poor, which is not preferable.

[0098]

Effects of the Invention The thermoplastic resin composition of the present invention exhibits excellent permanent antistatic properties, mechanical properties such as impact resistance, and corrosion resistance of metals. ADVANTAGE OF THE INVENTION According to the present invention, it was possible to provide a permanently antistatic resin that has excellent corrosion resistance for metals.

Claims (3)

[Claims] Claim 1: (A) 1 to 40 parts by weight of polyamide elastomer, (B) 98 to 5 parts by weight of styrene thermoplastic resin,
(C) 0 to 50 parts by weight of a modified vinyl polymer containing at least one functional group selected from carboxyl groups, epoxy groups, amino groups, hydroxyl groups, polyalkylene oxide groups, or derivatives thereof, and (D) 1 to 90 parts by weight of polyamide resin ((A)+(B)+(C)+(
The total amount of D) is 100 parts by weight. ) A thermoplastic resin composition. 2. (A) 1 to 40 parts by weight of polyamide elastomer, (B) 98 to 5 parts by weight of styrene thermoplastic resin,
(C) 0 to 50 parts by weight of a modified vinyl polymer containing at least one functional group selected from carboxyl groups, epoxy groups, amino groups, hydroxyl groups, polyalkylene oxide groups, or derivatives thereof, and (D) Total amount of polyamide resin 1 to 90 parts by weight ((A) + (B) + (
C) + (D) = 100 parts by weight), and (E) 0.01 to 10 parts by weight of an inorganic metal salt selected from alkali metals, alkaline earth metals, transition metals, and aluminum metals. Plastic resin composition. 3. The thermoplastic resin composition according to claim 2, wherein the inorganic metal salt is an inorganic alkaline earth metal salt and hydrotalcite.