JP2669179B2 - Metal corrosion resistant thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a video tape housing which is excellent in corrosion resistance of metal due to corrosive gas, has antistatic properties, and has excellent mechanical properties such as impact resistance.
The present invention relates to a metal-corrosion-resistant thermoplastic resin composition for a magnet.

[0002]

2. Description of the Related Art Synthetic polymer materials have excellent mechanical properties,
Although it is used in a wide range of fields due to its workability, it is an electrical insulator. If these materials are provided with antistatic properties in addition to the mechanical strength of the materials, their applications can be further expanded. That is, it can be applied to housings of electronic and electric machines such as copiers, facsimile machines, televisions, video tapes and the like, and their parts, various dustproof parts, etc., which are to be prevented from being damaged by static electricity.

As a method for improving the antistatic property of a synthetic polymer material, a hydrophilic rubber-like polymer obtained by copolymerizing a conjugated diene and / or an acrylate ester and a vinyl monomer having an alkylene oxide group is known. (Japanese Patent Application Laid-Open No. 55-36237) and a modified vinyl polymer containing a polyetheresteramide, a rubber-reinforced styrene resin, and a carboxyl group There is a composition (Japanese Unexamined Patent Publication No. 62-241945) in which the above is blended, and the practical antistatic property is achieved.

[0004] JP-A-64-62343 describes an antistatic composition containing a styrene resin, a polyamide elastomer, an antistatic agent and an alkali metal salt such as potassium thiocyanate.

[0005]

However, the antistatic resin obtained by graft-polymerizing the hydrophilic rubbery polymer described in JP-A-55-36237 is a special hydrophilic rubbery polymer. Since it is used, there are disadvantages that the production method is complicated and the mechanical properties of the obtained resin are inferior, and the corrosion prevention of metal is not sufficiently satisfactory. Further, the composition described in JP-A-62-241945 has excellent mechanical properties such as impact resistance, but does not have satisfactory metal corrosion prevention properties.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a metal corrosion resistant thermoplastic resin composition having excellent corrosion resistance of metal, permanent antistatic property, and excellent mechanical properties such as impact resistance. And

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present invention efficiently achieves the above object by blending a specific alkali metal salt with a polyamide elastomer and a styrene-based thermoplastic resin. The inventors have found that they have been achieved and have reached the present invention.

That is, the present invention comprises (A) 1 to 40 parts by weight of a polyether ester amide or a polyether amide,
(B) Modification containing 99 to 5 parts by weight of a styrene-based thermoplastic resin and (C) 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. Total amount of vinyl polymer 0 to 50 parts by weight ((A) +
With respect to (B) + (C) = 100 parts by weight), (D) an alkali metal salt of an acid selected from silicic acid, titanic acid, cyanic acid, acetic acid, boric acid, carbonic acid, and phosphoric acid 0.01 to 10 It is a metal-corrosion-resistant thermoplastic resin composition for a housing of a video tape, which is mixed with parts by weight.

Hereinafter, the present invention will be described specifically.

The (A) polyetheresteramide of the present invention is obtained by reacting (a) a polyamide-forming component with (b) a polyetherester-forming component comprising a poly (alkylene oxide) glycol and a dicarboxylic acid, The polyetheramide is obtained by reacting (a) a polyamide-forming component, (b) aminated or carboxylated poly (alkylene oxide) glycol at both ends with a polyether-forming component comprising a dicarboxylic acid or a diamine. It is a block or graft copolymer.

(A) Specific examples of the polyamide-forming component include ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid,
-Aminocapric acid and 11-aminoundecanoic acid,
Aminocarboxylic acids such as 12-aminododecanoic acid or lactams such as caprolactam, enantholactam, capryllactam and laurolactam and hexamethylenediamine-adipate, hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate; Examples thereof include diamine-dicarboxylic acid salts, and in particular, caprolactam, 12-aminododecanoic acid, and hexamethylenediamine-adipate are preferably used.

Examples of (b) poly (alkylene oxide) glycol preferably used in the present invention include poly (ethylene oxide) glycol, poly (1,2-propylene oxide) glycol and poly (1,3-propylene oxide) glycol. , Poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydrofuran, and both ends of which are aminated or carboxyl Those that have been converted are used. Among these, poly (ethylene oxide) glycol and those having both terminals aminated or carboxylated are particularly preferably used because of their excellent antistatic properties. In this case, the number average molecular weight of poly (alkylene oxide) glycol is 2
The range of from 00 to 10,000, particularly from 400 to 6,000 is preferable in that the polymerizability is excellent.

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-sulfo acid 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, aliphatic dicarboxylic acids such as sebacic acid and dodecandioic acid (decanedicarboxylic acid), and especially terephthalic acid, isophthalic acid;
4-Cyclohexanedicarboxylic acid, sebacic acid, adipic acid and dodecanediacid are preferably used from the viewpoint of polymerizability, color tone and physical properties.

Examples of the diamine component include aromatic, alicyclic and aliphatic diamines. Of these, hexamethylenediamine, an aliphatic diamine, is preferably used for economic reasons.

The ratio of (a) the polyamide-forming component / (b) the polyetherester-forming component or the polyether-forming component of (A) the polyetheresteramide or the polyetheramide used in the present invention is from 10/90 to 90. / 1
0% by weight, particularly preferably in the range of 20/80 to 70/30% by weight, is preferred because the resin composition has excellent impact resistance and antistatic properties.

The method for producing the polyetheresteramide or polyetheramide (A) is not particularly limited, and examples thereof include JP-A-56-65026 and JP-A-55-13.
The method disclosed in, for example, Japanese Patent No. 3424 can be used.

The styrene thermoplastic resin (B) in the present invention is a (co) polymer containing 20% by weight or more of styrene units, 1 to 80 parts by weight of a rubbery polymer and 20% by weight of styrene.
A graft (co) polymer obtained by graft polymerization of 99 to 20 parts by weight of the monomer or monomer mixture contained above, and a mixture thereof.

Here, as the rubbery polymer, those having a glass transition temperature of 0 ° C. or lower are preferable. Specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, butyl acrylate -Butadiene copolymers, styrene-butadiene block copolymers, and diene rubbers such as hydrogenated products thereof,
Examples include acrylic rubber such as polybutyl acrylate, polyisoprene, polychloroprene, ethylene-propylene-diene-based monomer terpolymer, and chlorinated polyethylene.

(B) Specific examples of the styrene-based thermoplastic resin include polystyrene, rubber-modified polystyrene, styrene-acrylonitrile copolymer, styrene-rubber polymer-acrylonitrile copolymer (ABS resin, AES resin, AAS resin) , ACS resin) and the like. Two or more of these can be used. Furthermore, some or all of these styrenes and / or some or all of the acrylonitriles are α-methylstyrene, p-methylstyrene, pt
Styrene such as -butylstyrene, ester compounds such as methyl, ethyl, propyl and n-butyl of (meth) acrylic acid; maleimide monomers such as maleimide, N-methylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide And those substituted with a vinyl monomer copolymerizable with the same.

As the styrene-based thermoplastic resin, rubber-modified polystyrene, ABS resin, AES resin,
AAS resin, ACS resin, MBS resin and the like are preferably used. In that case, the content of the rubbery polymer in the resin composition is usually 40% by weight or less, preferably 30% by weight or less.
If the amount exceeds 40% by weight, the resin composition becomes soft, which is not preferable.

(B) The method for producing the styrene-based thermoplastic resin is not limited, and includes a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method,
An ordinary method such as a bulk-suspension polymerization method can be used. A modified vinyl polymer (C) containing at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group, a polyalkylene oxide group or a derivative thereof (hereinafter, referred to as (C)) As a modified vinyl polymer), has a structure obtained by polymerizing or copolymerizing one or more vinyl monomers, and has a carboxyl group, an epoxy group, an amino group, It is a polymer having at least one functional group selected from the group consisting of a hydroxyl group, a polyalkylene oxide group or a derivative thereof. Regarding the content of the compound containing these functional groups,
Although not limited, it is preferably 0.1 to 20% by weight, particularly 0.1 to 10% by weight, per 100 parts by weight of the modified vinyl polymer. Normally, the effect of the present invention is effectively exerted if one molecule of the modified vinyl polymer contains substantially one or more of the above functional groups on average.

(C) The method for introducing a carboxyl group into the modified vinyl polymer is not particularly limited, but a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid and itaconic acid or an anhydride thereof may be used. A method for copolymerizing a vinyl monomer having a carboxyl group with a predetermined vinyl monomer, γ, γ′-azobis (γ
-Cyanovaleic acid), α, α′-azobis (α-cyanoethyl) -polymerization initiator having a carboxyl group such as p-benzoic acid and succinic peroxide and / or thioglycolic acid, α-mercaptopropionic acid, β- Method for (co) polymerizing a predetermined vinyl polymer using a polymerization degree regulator having a carboxyl group such as mercaptopropionic acid, α-mercapto-isobutyric acid and 2,3 or 4-mercaptobenzoic acid, and methacrylic acid A method of saponifying a copolymer of a (meth) acrylate monomer such as methyl or methyl acrylate with an aromatic vinyl monomer and, if necessary, a vinyl cyanide monomer with an alkali. Can be used.

The method of introducing the epoxy group is not particularly limited, but for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylic acid, glycidyl itaconic acid, allyl glycidyl ether, styrene-p.
-A method of copolymerizing glycidyl ether, p-glycidyl styrene and the like with a predetermined vinyl monomer can be used.

The method for introducing the amino group is not particularly limited, but for example, the following formula (I)

[0026]

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(Wherein, R ¹ represents hydrogen, a methyl group or an ethyl group; R ² represents hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, and a carbon atom having 6 carbon atoms) Phenyl group or cycloalkyl group or a derivative thereof), and a vinyl monomer having at least one functional group of an amino group or a substituted amino group represented by the following formula: A method of polymerizing can be used.

Specific examples of the vinyl monomer having at least one functional group of an amino group or a substituted amino group include aminoethyl acrylate, propylaminoethyl acrylate, methylaminoethyl methacrylate, and ethylamino methacrylate. Alkyl ester derivatives of acrylic acid or methacrylic acid such as propyl, phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate, N-vinyldiethylamine and N
-Vinylamine derivatives such as acetylvinylamine, allylamine derivatives such as allylamine, methallylamine and N-methylallylamine, acrylamide, methacrylamide and N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide and the like (meth ) Acrylamide derivatives and aminostyrenes such as p-aminostyrene.

The method for introducing a hydroxyl group is not particularly limited. For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2,2-acrylic acid, 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.

The method of introducing a polyalkylene oxide group is not particularly limited. For example, (1) the following formulas (II) and (III)

[0031]

Embedded image

Wherein R ³ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ⁴ is an alkyl group having 2 to 6 carbon atoms, R ⁵ is hydrogen or an alkyl group having 1 to 6 carbon atoms. Represents a group, and n represents 2 to 500.) A method of copolymerizing a vinyl monomer having a polyalkylene oxide group represented by the following formula with a predetermined vinyl monomer can be used.

Specific examples include polyethylene glycol acrylate, polyethylene glycol methacrylate, poly (propylene oxide) glycol acrylate, poly (propylene oxide) glycol methacrylate, poly (tetramethylene oxide) glycol acrylate, poly (tetramethylene oxide) glycol. Methacrylate, poly (hexamethylene oxide) glycol methacrylate, methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate, methoxy poly (propylene oxide) glycol acrylate, methoxy poly (propylene oxide) glycol methacrylate, methoxy poly (tetramethylene oxide) glycol methacrylate, ethoxy polyethylene Recall acrylate, ethoxy polyethylene glycol methacrylate, Etokishipori (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, methoxy polyethylene glycol acrylamide, methoxy polyethylene glycol methacrylamide, methoxy poly (propylene oxide) glycol acrylamide,
Methoxy poly (propylene oxide) glycol methacrylamide, methoxy poly (tetramethylene oxide)
Examples thereof include glycol methacrylamide.

Further, (2) acrylic acid, methacrylic acid,
An ester of a carboxyl group-containing vinyl polymer obtained by a method of copolymerizing maleic acid, maleic anhydride, phthalic acid, etc. with a desired vinyl monomer and a 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 as used herein includes, for example, methoxypolyethylene glycol, methoxypoly (1,2)
-Propylene oxide) glycol, methoxy poly (1,3-propylene oxide) glycol, methoxy poly (tetramethylene oxide) glycol, methoxy poly (hexamethylene oxide) glycol, methoxy poly (block or random copolymer of ethylene oxide and propylene oxide) and methoxy ( (A block or random copolymer of ethylene oxide and tetrahydrofuran). The number average molecular weight of poly (alkylene oxide) glycol having an alkyl ether at one end is used in the range of 75 to 20,000.

The vinyl monomer used for the polymerization of the modified vinyl polymer (C) is not particularly limited, and examples thereof include aromatic vinyl monomers such as styrene, α-methylstyrene and vinyltoluene, and acrylonitrile. , Vinyl cyanide monomers such as methacrylonitrile, methyl methacrylate, ethyl methacrylate, methyl acrylate,
(Meth) acrylate monomers such as butyl acrylate, maleimide monomers such as maleimide, N-methylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide, and olefin monomers such as ethylene and propylene One or more of vinyl monomers such as vinyl chloride, vinyl acetate, and butadiene can be selected and used according to the purpose. In particular, aromatic vinyl monomers such as styrene, (meth) acrylate monomers such as methyl methacrylate, vinyl cyanide monomers such as acrylonitrile, and maleimide monomers such as N-phenylmaleimide It is preferably used because the mechanical properties of the resin composition that can be used as a body are excellent.

If necessary, polybutadiene, acrylonitrile / butadiene copolymer (NBR), styrene / butadiene copolymer (SBR), polybutyl acrylate and ethylene / propylene / diene rubber (E
A rubbery polymer such as PDM) can also be used in combination with the above vinyl-based monomer.

As the method of introducing the functional group, the above-mentioned various methods can be arbitrarily combined and used.

(C) The method for producing the modified vinyl polymer is also not particularly limited, and includes a bulk polymerization method, a solution polymerization method, a suspension polymerization method,
Conventional methods such as emulsion polymerization method and bulk-suspension polymerization method can be used.

In the present invention, the proportions of (A) polyetheresteramide or polyetheramide, (B) styrene thermoplastic resin and (C) modified vinyl polymer are as follows: component (A), component (B) and component (C). ) Total amount of ingredients 10
1 to 40 parts by weight of component (A), preferably 4 to 30 parts by weight, and 99 to 20 parts by weight of component (B), relative to 0 parts by weight.
Preferably 95 to 45 parts by weight and (C) component 0 to 5
0 parts by weight, preferably 0.1 to 30 parts by weight.

If the amount of the polyetheresteramide or polyetheramide (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 be soft and have poor mechanical properties. It is inferior and not preferable. On the other hand, if the amount of the modified vinyl polymer (C) exceeds 50 parts by weight, the moldability deteriorates and the appearance of the molded product is impaired, so that the molded product cannot be used.

The alkali metal salt (D) in the present invention is
It is an alkali metal salt of an acid selected from silicic acid, titanic acid, cyanic acid, acetic acid, boric acid, carbonic acid and phosphoric acid. Of these, alkali metal salts of silicic acid, titanic acid, acetic acid, and cyanic acid are preferable, and alkali metal salts of silicic acid, titanic acid, and acetic acid are particularly preferable.

Examples of the alkali metal salt include lithium, sodium, potassium and the like. Specific examples include lithium carbonate, sodium carbonate, potassium carbonate, monopotassium phosphate, dipotassium phosphate, potassium phosphate,
Monosodium phosphate, disodium phosphate, lithium silicate, sodium silicate, potassium silicate, lithium acetate, potassium acetate, sodium cyanate, potassium cyanate, sodium borate, sodium titanate, potassium titanate, etc. To be Among them, sodium silicate, potassium silicate, potassium titanate, sodium titanate, sodium acetate, potassium is handling properties, excellent corrosion resistance of the metal, is preferably used.

In the present invention, it is important to use the above-mentioned specific alkali metal salt. When an acid other than the acid used in the present invention is used, it is difficult to obtain a metal having excellent corrosion resistance. .

(D) The particle size of the alkali metal salt is 10 μm
The following is preferable, and 5 μm or less is particularly preferable. When a carbonate is used, it is preferable to use one having a diameter of 2.0 μm or less, particularly 1.0 μm or less.

In the present invention, the added amount of the alkali metal salt (D) is 100% by weight of the total amount of (A) polyetheresteramide or polyetheramide, (B) styrene thermoplastic resin and (C) modified vinyl polymer. Parts by weight, preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight.

If the amount is less than 0.01 part by weight, the corrosion resistance of the metal is poor, and if it exceeds 10 parts by weight, the impact resistance of the composition is remarkably deteriorated.

The method for producing the resin composition of the present invention is not particularly limited, and examples thereof include (A) a polyetheresteramide or polyetheramide, (B) a styrene-based thermoplastic resin, (C) a modified vinyl-based polymer, (D) It is commercialized by melt-kneading a mixture of alkali metal salts with a Banbury mixer, roll, extruder or the like.

The resin composition of the present invention is made of another thermoplastic resin compatible with the resin composition of the present invention, for example, polycarbonate, polyphenylene ether, polyglutarimide,
Improve impact resistance and heat resistance by mixing polycyclohexyl dimethylene terephthalate, etc., improve chemical resistance by mixing polyolefin, polybutylene terephthalate, polyethylene terephthalate, etc. It is possible to improve the corrosion resistance of the metal and the flame retardancy by mixing a vinyl chloride resin or the like.
Further, it is possible to further improve the antistatic property by adding an antistatic agent such as a metal salt of sulfonic acid or an anionic, cationic or nonionic surfactant, and further, if necessary, to prevent oxidation. It is also possible to add various stabilizers such as agents and ultraviolet absorbers, pigments, dyes, lubricants and plasticizers, and flame retardants.

The metal corrosion resistant thermoplastic resin composition of the present invention is excellent in permanent antistatic properties, mechanical properties, and metal corrosion resistance, and is useful for video tape housings .

[0051]

EXAMPLES In order to more specifically describe the present invention, examples and comparative examples will be described below. In addition, after the resin composition finally obtained was molded by an injection molding method, various physical properties were measured by the following test methods.

Izod impact test: ASTM D256-56A Flexural modulus: ASTM D790 Surface resistivity: 2 mm ^t × 40 mm ^φ disk, room temperature 2
The measurement was performed in an atmosphere of 3 ° C. and a humidity of 50% RH. A super insulation resistance meter SM-10 type manufactured by Toa Denpa Kogyo Co., Ltd. was used for the measurement.

Corrosion resistance of metal: A composition for determining the corrosion resistance of a metal having a lid of 20 mm × 20 mm × 15 mm and a hole of 6 mmφ formed on a side and a lid is formed by molding a nickel foil of 8 mm × 18 mm with a lid of 20 mm × 20 mm × 15 mm. After leaving the container in a desiccator containing about 3 ppm of hydrogen chloride at 23 ° C. for 8 hours, the surface of the nickel foil was observed with an optical microscope. The surface of the nickel foil was evaluated as ◎: extremely good, ：: good, Δ: corroded, ×: markedly corroded. In addition, the number of copies and% in the examples
Indicates parts by weight and% by weight, respectively.

Reference Example (1) (A) Preparation of polyamide elastomer A-1: 40.0 parts of caprolactam, number average molecular weight of 1
53.1 parts of polyethylene glycol and 9.2 parts of terephthalic acid together with 0.2 part of "Irganox" 1098 (antioxidant) and 0.1 part of antimony trioxide catalyst in a reaction vessel equipped with a helical ribbon stirring blade. After charging, purging with nitrogen and heating and stirring at 260 ° C. for 60 minutes to obtain a transparent homogeneous solution, polymerization was carried out at 260 ° C. and 0.5 mmHg or less for 4 hours to obtain a viscous and transparent polymer.

The polymer was discharged in a gut shape on a cooling belt and pelletized to prepare a pelletized polyetheresteramide (A-1).

A-2: Acrylonitrile was reacted with polyethylene glycol having a number average molecular weight of 4000, and hydrogenation reaction was carried out to obtain polyethylene glycol diamine having amino groups at both ends. This was subjected to a salt reaction with terephthalic acid by a conventional method to obtain a 40% solution of polyethylene glycol diammonium terephthalate.

120 parts of the 40% aqueous solution of polyethylene glycol diammonium terephthalate in a concentrated canister,
16 parts of a 40% aqueous solution of hexamethylene diammonium adipate are charged, and the pressure is reduced to about 2 ° C. at normal pressure until the internal temperature reaches 110 ° C.
Heated for hours and concentrated to 80% concentration. Subsequently, the concentrated solution was transferred to a polymerization vessel, and heating was started while flowing nitrogen into the polymerization vessel.

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, pelletized polyetheramide (A-2) 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 diameter 0.2
40 parts of a monomer mixture consisting of 72% styrene and 28% acrylonitrile was emulsion-polymerized in the presence of 60 parts (solid content) of 5 μ, gel content 80%.

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% of methyl methacrylate, 24% of styrene, acrylonitrile 4 in the presence of 40 parts (in terms of solid content) of the polybutadiene latex used in B-1
% After the emulsion polymerization of 60 parts of the monomer mixture consisting of
The powdery graft copolymer (B-
2) was prepared.

B-3: Diene NF35A (Asahi Kasei Corporation)
10 parts by weight) was dissolved in 90 parts by weight of styrene, and then bulk polymerization was carried out to prepare a graft polymer (B-3).

(B2) Copolymer b-1: 72 parts of styrene and 28 parts of acrylonitrile were subjected to suspension polymerization to prepare a copolymer (b-1).

B-2: 72 parts of methyl methacrylate, 24 parts of styrene and 4 parts of acrylonitrile were subjected to suspension polymerization to prepare a copolymer (b-2).

B-3: A copolymer (b-3) was prepared by emulsion-polymerizing 50 parts of styrene, 30 parts of N-phenylmaleimide, and 20 parts of acrylonitrile.

(3) Preparation of (C) Modified Vinyl Polymer C-1: 68 parts of styrene, 27 parts of acrylonitrile and 5 parts of methacrylic acid are subjected to suspension polymerization to obtain a modified vinyl polymer (C-1). Prepared.

C-2: 70 parts of methyl methacrylate, 21 parts of styrene, 4 parts of acrylonitrile and 5 parts of methacrylic acid were subjected to suspension polymerization to prepare a modified vinyl polymer (C-2).

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

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

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, methacrylic acid 5
The resulting mixture was subjected to suspension polymerization to prepare a modified vinyl polymer (C-6).

(4) (D) Preparation of alkali metal salt D-1: Sodium acetate (Katayama Chemical Co., Ltd.) was used.

D-2: Potassium silicate (manufactured by Nippon Kagaku Kogyo Co., Ltd.) was used.

D-3: Potassium titanate (Tismo-D
Otsuka Chemical Co., Ltd. was used.

D-4: Potassium thiocyanate (Katayama Chemical Co., Ltd.) was used.

D-5: Sodium thiocyanate (Katayama Chemical Co., Ltd.) was used.

Examples 1 to 16 (A) Polyetheresteramide or polyetheramide prepared in Reference Example, (B) Styrene-based thermoplastic resin; (b-1) graft copolymer, (b-2) copolymer The polymer, (C) the modified vinyl polymer and (D) the alkali metal salt were mixed at the compounding ratio shown in Table 1, and the mixture was vented to 40 mmφ.
A pelletized polymer was produced by melt-kneading and extruding at a resin temperature of 220 ° C. in an extruder.

Then, test pieces were molded at a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C. using an injection molding machine, and each physical property was measured. The surface specific resistance value was measured under the following conditions using an injection molded disc having a thickness of 2 mm.

(1) Immediately after molding, the surface was washed with an aqueous solution of a detergent "Mama Lemon" (manufactured by Lion Oil & Fat Co., Ltd.), and then sufficiently washed with distilled water to remove water on the surface.
H, measured at 23 ° C. for 24 hours.

(2) After molding, 1% in 50% RH and 23 ° C.
After leaving it to stand for 00 days, it was washed with an aqueous solution of a detergent “Mama Lemon”, and then sufficiently washed with distilled water to remove water on the surface. Then, the humidity was adjusted at 50% RH and 23 ° C. for 24 hours.

The container for determining the corrosion resistance of the metal was molded by an injection molding machine under the conditions of a cylinder temperature of 230 ° C. and a mold temperature of 40 ° C. Table 2 shows the measurement results.

Comparative Examples 1 to 8 (A) Polyetheresteramide or polyetheramide prepared in Reference Example, (B) Styrene-based thermoplastic resin; (b-1) graft copolymer, (b-2) copolymer The polymer, (C) the modified vinyl polymer and (D) the alkali metal salt were mixed at the compounding ratio shown in Table 1, and the physical properties were measured in the same manner as in the examples. Table 2 shows the measurement results.

[0084]

[Table 1]

[0085]

[Table 2]

From the results of Table 2, the following is clear.
The resin compositions of the present invention (Examples 1 to 16) all have excellent balance between mechanical properties such as impact strength and flexural modulus and corrosion resistance of metal, and have low surface resistivity. There is. In addition, the resistance value hardly changes even when the surface is washed or changes with 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 property.

On the other hand, when the amount of the alkali metal salt (D) is less than 0.01 part by weight (Comparative Examples 1 and 6), the corrosion resistance of the metal is poor, and when it exceeds 10 parts by weight (Comparative Example 3). The impact strength becomes extremely low, and a desirable resin composition cannot be obtained.

When the amount of polyetheresteramide or polyetheramide was less than 1 part by weight (Comparative Example 3), the resistance was high, the antistatic property was poor, and the corrosion resistance of the metal was extremely poor. Exceeding the weight part (Comparative Example 5) is not preferred because the flexural modulus is inferior. When an alkali metal salt other than the present invention is used (Comparative Examples 7 and 8), the metal corrosion resistance is not improved.

[0089]

The metal corrosion resistant thermoplastic resin composition of the present invention has excellent permanent antistatic properties, mechanical properties such as impact resistance, and metal corrosion resistance. According to the present invention, it is possible to provide a novel permanent antistatic resin suitable for a video tape housing having excellent metal corrosion resistance.

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Claims (2)

(57) [Claims] 1. A polyetheresteramide or polyetheramide (A) in an amount of 1 to 40 parts by weight, (B) a styrene thermoplastic resin in an amount of 99 to 5 parts by weight, and (C) a carboxyl group, an epoxy group, an amino group or a hydroxyl group. Modified vinyl polymer containing at least one functional group selected from polyalkylene oxide groups and their derivatives
５０50 parts by weight total ((A) + (B) + (C) = 10
To 0 parts by weight), (D) silicate, titanate, cyanate, acetate, borate, carbonate, by blending an alkali metal salt 0.01 to 10 parts by weight of acid selected from phosphoric acid video
Metal-corrosion-resistant thermoplastic resin composition for tape housing . 2. The metal-corrosion-resistant thermoplastic resin composition according to claim 1, wherein the alkali metal salt is an alkali metal salt of silicic acid, titanic acid or acetic acid.