JPH01178549A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which is excellent in all of permanent antistatic property, impact resistance and heat resistance and can give a molding free from delamination, by mixing a polyamide elastomer with an aromatic polyester, a functional modified vinyl polymer and a COOH or epoxy-containing modified ethylene polymer. CONSTITUTION:1-50pts.wt. polyamide elastomer (A) such as a block or graft copolymer obtained by reacting a polyamideforming component with a poly(alkylene oxide) glycol is mixed with 1-98pts.wt. aromatic polyester (B), 0.1-50 pts.wt. modified vinyl polymer (C) having at least one kind of a functional group selected from among COOH, epoxy, (substituted)NH2 and the like groups and 1-30pts.wt. modified ethylene polymer (D) containing COOH or epoxy groups in amounts to give a total of components A-D of 100pts.wt.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention has permanent antistatic properties, has excellent mechanical properties such as impact resistance, and excellent heat resistance in balance, and has a layered structure of molded products. This invention relates to a conductive resin composition that does not peel off (turn over).

[Prior Art] Thermoplastic polyester has excellent mechanical properties, electrical properties, heat resistance, etc., and is therefore widely used in various applications such as mechanical parts and electrical equipment parts. Although thermoplastic polyester has these excellent properties, it has the disadvantages of high volume resistivity and surface resistivity, being easily charged by friction, easily attracting dust, and easily causing electrostatic damage. ing. For this reason, its use is limited to applications that require antistatic properties, such as electronic and electromechanical parts such as copying machines and televisions.

As a method for improving the conductivity of polyester, polyether ester (Japanese Unexamined Patent Publication No. 56-1592
No. 45), polyether ester amide (U.S. Pat. No. 4,309,518, Japanese Patent Application Laid-Open No. 183352/1983)
(Japanese Patent Application Laid-Open No. 57-5748), Polyetheramide
It has been proposed to incorporate polymeric materials such as (Japanese Patent Publication No.

[Problems to be Solved by the Invention] However, the antistatic resin disclosed in JP-A-56-159245 has insufficient antistatic effect. Also, U.S. Pat.
The antistatic resins disclosed in JP-A No. 352 and JP-A-57-5748 have poor affinity with polyester and polyether ester amide or polyether amide, resulting in poor impact resistance and delamination of molded products. Due to these drawbacks, it is not possible to obtain a satisfactory composition.

Therefore, the present invention has permanent antistatic properties, and has excellent mechanical properties such as impact resistance and heat resistance in a well-balanced manner.
It is an object of the present invention to provide an antistatic resin composition that does not cause delamination of molded products.

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, we found that in order to solve the above problems, polyamide elastomer and aromatic polyester should be modified vinyl polymers containing specific functional groups and The present invention was achieved by discovering that it is important to blend a modified ethylene polymer.

That is, the present invention includes (A) 1 to 50 parts by weight of polyamide elastomer, (B) 1 to 98 parts by weight of aromatic polyester, and (C) at least one selected from carboxyl group, epoxy group, amino group, and substituted amino group. (A) + (B) 0.1 to 50 parts by weight of a modified vinyl polymer containing a seed functional group and (D) 1 to 30 parts by weight of a modified ethylene polymer containing a carboxyl group or an epoxy group.
A thermoplastic resin composition containing 100 parts by weight of + (C) + (D) is provided.

The present invention will be explained in detail below.

The polyamide elastomer (A) in the present invention includes:
Examples include block or graft copolymers obtained from the reaction of (a) a polyamide-forming component and (b) poly(alkylene oxide) glycol.

(a) Specifically, the polyamide forming components include ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-amino Aminocarboxylic acids such as dodecanoic acid or lactams such as caprolactam, enantholactam, capryllactam and laurolactam and hexamethylene diamine
Salts of diamine-dicarboxylic acids such as adipate, hexamethylenediamine-sepacate, and hexamethylenediamine-isophthalate are mentioned, and caprolactam, 12-aminododecanoic acid, and hexamethylenediamine-adipate are particularly preferably used. It will be done.

Examples of poly(alkylene oxide) glycol (b) 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, block or random copolymers of ethylene oxide and propylene oxide, block or random copolymers of ethylene oxide and tetrahydrofuran, etc. are used. Among these, poly(ethylene oxide) glycol is particularly preferably used because of its excellent antistatic properties. In this case, the number average molecular weight of the poly(alkylene oxide) glycol is 200 to 6000, particularly 400 to 40.
A range of 00 is preferred.

Furthermore, diol compounds represented by the following formulas (I) to (III) can be used in combination with (b) poly(alkylene oxide) glycol.

I (viscous←O-c?-0 edition←H(I) m n (wherein, R+, R2 represents at least one of an ethylene oxide group and a propylene oxide group, Y is a covalent bond,
C1-6 alkylene group, alkylidene group, cycloalkylidene group, arylalkylidene group, o, 5oS
so2, C05S, CF2, C(CF3)2 or NH
shows. ) Specific examples include ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol S, propylene oxide adduct of bisphenol S, ethylene oxide adduct of brominated bisphenol A, and brominated bisphenol A. Ethylene oxide and/or propylene oxide adducts of bisphenols such as propylene oxide adducts, ethylene oxide adducts of 4,4'-dihydroxybenzofinone, propylene oxide adducts of 4,4'-dihydroxybenzofinone, hydroquinone adducts, Ethylene oxide and/or propylene oxide adducts, ethylene oxide and/or propylene oxide adducts of dihydroxynaphthalene and block (co)polymers thereof, 4.4'-(hydroxy)biphenyl ethylene oxide adducts, 4.4'
- bis(hydroxy)biphenyl propylene oxide adduct, bis(4-hydroxyphenyl) sulfide propylene oxide adduct, bis(4-hydroxyphenyl) sulfide propylene oxide adduct, bis(4-hydroxyphenyl) sulfide propylene oxide adduct, bis(4-hydroxyphenyl) sulfide propylene oxide adduct;
ethylene oxide adduct of bis(4-hydroxyphenyl) sulfoxide, propylene oxide adduct of bis(4-hydroxyphenyl) sulfoxide, ethylene oxide adduct of bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl) sulfoxide
-hydroxyphenyl)methane propylene oxide (
-J adduct, ethylene oxide adduct of bis(4-hydroxyphenyl) ether, propylene oxide adduct of bis(4-hydroxyphenyl) ether, bis(4-
Ethylene oxide adduct of hydroxyphenyl)amine, propylene oxide adduct of bis(4-hydroxyphenyl)amine, ethylene oxide adduct of 2,2-bis(4-hydroxyphenyl)ethane, 2,2-bis(
Propylene oxide adduct of 4-hydroxyphenyl)ethane, nyletine oxide adduct of 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(
Bisphenols such as a propylene oxide adduct of 4-hydroxyphenyl)hexane can be mentioned.

Preferred diol compounds include ethylene oxide adducts of hydroquinone, ethylene oxide adducts of bisphenol A, ethylene oxide adducts of brominated bisphenol A, ethylene oxide adducts of bisphenol S, ethylene oxide adducts of dihydroxynaphthalene, and block polymers thereof. Ethylene oxide adducts of bisphenol A and block polymers thereof are preferred. Further, by using an ethylene oxide adduct of brominated bisphenol A, an ethylene oxide adduct of brominated bisphenol S, etc., the flame retardance of the resin composition can be improved.

These poly(alkylene oxide) glycols and diol compounds represented by general formulas (I) to (III) can be used alone or in combination of two or more as necessary.

Although there is no particular restriction on the amount of diol compounds represented by general N I ) to (III), it is preferably in the range of 0 to 60% by market weight based on polyether ester units obtained by copolymerizing with dicarboxylic acid.

Further, other diol compounds can be copolymerized within a range that does not impair the effects of the present invention.

Specifically, aliphatic diols such as ethylene glycol, 1,4-butanediol and hexanediol, aromatic diols such as p-xylylene glycol and m-xylylene glycol, 1,2-cyclohexanediol, 1
．． 3-cyclohexanediol, 1,4-cyclohexanediol, 1゜4-cyclohexane dimetatool, 1
, 3-cyclohexane dimetatool, and other alicyclic diol compounds can be copolymerized.

As an example of the reaction of the polyamide elastomer of the present invention, (
a) the polyamide-forming component and (b) the poly(alkylene oxide) glycol are (b) the poly(alkylene oxide)
Depending on the end group of the glycol, an ester reaction or an amide reaction is possible.

In addition, depending on the reaction, dicarboxylic acids, diamines, etc.
Component (C) can also be used.

In this case, the dicarboxylic acid component has 4 to 4 carbon atoms.
20 are preferably used, specifically terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2°7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, and dicarboxylic acid. Aromatic dicarboxylic acids such as phenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate, fats such as 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and α◇chlorohexyl-4,4'-dicarboxylic acid. Cyclic dicarboxylic acids and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid and dodecanedioic acid (decanedicarboxylic acid), etc.
In particular, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, adipic acid and domicandic acid are preferably used from the viewpoint of polymerizability, color tone and physical properties.

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

The polyether ester or polyether component is a constituent unit of polyamide elastomer and is used in a range of 90 to 10% by weight. If it exceeds 90% by weight, the mechanical properties of the polyamide elastomer will be poor, and if it is less than 10% by weight, the resin will become statically charged. It is not preferable because the prevention property is poor.

(A) The method for producing the polyamide elastomer is not particularly limited, and methods disclosed in, for example, JP-A-56-65026 and JP-A-60-177022 can be used.

The aromatic polyester (B) used in the present invention is a polyester having an aromatic ring in the chain unit of the polymer, and is composed of an aromatic dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative). It is a polymer or copolymer obtained by a condensation reaction in which the main component is a condensation reaction.

The aromatic dicarboxylic acids mentioned here include terephthalic acid,
Isophthalic acid, orthophthalic acid, 1,5-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6
-naphthalenedicarboxylic acid, 4'-biphenyldicarboxylic biphenyldicarboxylic acid, 4,4'-diphenyl etherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid,
4.4'-diphenylisopropylidene dicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 2.5-anthracene dicarboxylic acid, 2,6
-anthracenedicarboxylic acid, 4,4'-p-terphenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, etc., and terephthalic acid is preferably used.

Two or more of these aromatic dicarboxylic acids may be used in combination. If the amount is small, one or more types of aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecane dicarboxylic acid, and alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid may be used in combination with these aromatic dicarboxylic acids. be able to.

In addition, diol components include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,
Examples include aliphatic diols such as 3-propanediol, diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexane dimetatool, and mixtures thereof. In addition, if it is a small amount, the molecular weight is 400 to 6. One or more long-chain diols of OOCI, such as polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc., may be copolymerized.

Specific aromatic polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate,
In addition to polyethylene naphthalate-1, polybutylene naphthalate, polyethylene-1゜2-bis(phenoxy)ethane-4,4'-dicarboxylate, polyethylene isophthalate/terephthalate, polybutylene terephthalate/isophthalate, polyethylene Examples include copolymerized polyesters such as butylene terephthalate/depolymer dicarboxylate. Among these, polybutylene terephthalate and polyethylene terephthalate, which have well-balanced mechanical properties and moldability, are preferably used. The method for producing the aromatic polyester (B) is not particularly limited, and any known production method can be used.

(C) At least one selected from carboxyl group, epoxy group, amino group, substituted amino group used in the present invention
A modified vinyl polymer containing various functional groups (hereinafter referred to as modified vinyl polymer) has a structure obtained by polymerizing or copolymerizing one or more vinyl monomers. A polymer having at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, and an amino group or a substituted amino group in the molecule. The amount of these functional groups may be very small, or may be contained in a large amount as long as the performance as a resin is not impaired.

Usually, the effects of the present invention can be effectively exhibited if the modified vinyl polymer contains substantially one or more of the above functional groups on average in one molecule. (C) There are no particular restrictions on the method of introducing a carboxyl group into the modified vinyl polymer, but there are two methods: A method of copolymerizing a vinyl monomer having a monomer with a predetermined vinyl monomer,
Polymerization initiators with carboxyl groups such as γ-cyatubaleic acid), α, α′-azobis (α-cyanoethyl-p-benzoic acid) and peroxide succinic acid and/or thioglycolic acid, α-mercaptopropionic acid, β −
A method of (co)polymerizing a predetermined vinyl monomer using a polymerization degree regulator having a carboxyl group such as mercaptopropionic acid, α-mercapto-isoacetic acid, and 2.3- or 4-mercaptobenzoic acid; A method of saponifying a (co)polymer of (meth)acrylic acid ester such as methyl methacrylate or butyl acrylate with an alkali can be used.

There is no particular restriction on the method of introducing the epoxy group, but for example, the following formula (IV) (wherein R3 is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a glycidyl ester group)
Specifically, a method of copolymerizing glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, etc. with a predetermined vinyl monomer can be used.

There are no particular restrictions on the method of introducing an amino group or a substituted amino group, but for example, the zero-order formula (wherein R4 represents hydrogen, a methyl group, or an ethyl group, and R5 represents hydrogen or a carbon atom number of 1 to 12 alkyl groups, 2 to 1 carbon atoms
2 represents an alkanoyl group, a phenyl group having 6 to 12 carbon atoms, a cycloalkyl group, or derivatives thereof. ) A method of copolymerizing a vinyl monomer having at least one functional group of an amino group or a substituted amino group represented by (V) above with a predetermined vinyl monomer; A method of (co)polymerizing a predetermined vinyl monomer using a chain transfer agent and/or initiator having at least one functional group selected from the group consisting of amino groups and mineral acid salts thereof, etc. can be used.

Specific examples of vinyl monomers having at least one functional group such as an amino group or a substituted amino group include aminoethyl acrylate, propylaminoethyl acrylate,
Dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate, alkyl ester derivatives of acrylic acid or methacrylic acid 8, N-vinyldiethylamine, N-acetylvinylamine, etc. vinylamine derivatives such as allylamine, allylamine derivatives such as methalylamine and N-methylallylamine, (meth)acrylamide derivatives such as acrylamide, methacrylamide and N-methylacrylamide, and aminostyrenes such as p-aminostyrene. can be mentioned.

Further, specific examples of chain transfer agents having the above-mentioned functional groups include mercaptomethylamine, β-mercaptoethylamine, γ-mercaptopropylamine, N-(β-mercaptoethyl)-N-methylamine, N-(β-mercaptoethyl)-N-methylamine, and N-(β-mercaptoethyl)-N-methylamine. -mercaptoethyl)-N-phenylamine, N-(β-mercaptoethyl)-N-cyclohexylamine, bis-(4
-aminophenyl)disulfide, bis-(2-aminophenyl)disulfide, bis-(3-aminophenyl)disulfide, p-mercaptoaniline, O-
Examples of initiators include mercaptoaniline, m-mercaptoaniline, and their hydrochlorides, and specific examples of initiators include α,α′-azobis(γ-amino-α,γ-dimethylvaleronitrile), α,α′-azobis( γ-methylamino-α, γ-dimethylvaleronitrile), α, α′ −
Examples include azobis (γ-ethylamino-α, γ-dimethylvaleronitrile), α,α'-azobis (γ-dimethylamino-α, γ-dimethylvaleronitrile), and p-aminobenzoyl peroxide.

(C) There are no particular restrictions on the vinyl monomer used in the polymerization of the modified vinyl polymer, such as styrene,
Aromatic vinyl monomers such as α-methylstyrene and vinyltoluene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, methyl methacrylate, ethyl methacrylate, methyl acrylate, acid, butyl lylate, etc. (meth)acrylic acid ester monomers, maleimide monomers such as maleimide, N-methylmaleimide, and N-phenylmaleimide, olefin monomers such as ethylene and propylene, and vinyl chloride, vinyl acetate, butadiene, etc. One or more vinyl monomers can be selected and used depending on the purpose. especially,
Mechanical properties of resin compositions in which aromatic vinyl monomers such as styrene, (meth)acrylic acid ester monomers such as methyl methacrylate, and cyanide vinyl monomers such as acrylonitrile are used. It is preferably used because of its excellent properties.

In addition, if necessary, rubber-like polymers such as polybutadiene, acrylonitrile/butadiene copolymer (NBR), styrene/butadiene copolymer (SBR), polybutyl acrylate, and ethylene/propylene/diene rubber (EPDM) may be added to the above. It can also be used in combination with vinyl monomers.

Further, as the method for introducing the functional group, any combination of the various methods described in section 2 can be used.

(C) There are no particular restrictions on the method for producing the modified vinyl polymer, and conventional methods such as bulk polymerization, solution polymerization, suspended '/fA polymerization, emulsion polymerization, bulk-suspended r:J polymerization, etc. can be used.

In the present invention, in order to further improve the performance, (abbreviated as (D)) is further used.

The modified ethylene polymer is one type or two type 1-α
- A polymer having a structure obtained by polymerizing or copolymerizing olefins and having at least one functional group such as a carboxyl group or an epoxy group in the molecule. The content of these functional groups is not particularly limited, but is between 0.1 and
50% by weight, especially 1 to 30% by weight is preferred.

(D) Modification process There is no particular restriction on the method of introducing carboxyl groups into the polymer, but examples include carboxyl groups such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, and itaconic acid. Methods such as (1) copolymerizing a vinyl monomer having a group or anhydrous carboxyl group with a predetermined α-olefin, and (2) grafting it onto an ethylene polymer in the presence of a radical-generating catalyst can be used.

There is no particular restriction on the method of introducing the epoxy group, but for example, the following formula (Vl) CH2=C-C-0-CH2-CH-CH2...
...(VI)111 \/ (wherein, R6 is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a glycidyl ester group)
Specifically, a method of copolymerizing vinyl monomers having an epoxy group such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaconate with a predetermined α-olefin; A method such as grafting onto an ethylene polymer in the presence of a generated catalyst can be used.

In addition, the copolymer of the vinyl monomer containing the above functional group and α-olefin may be further copolymerized with other vinyl monomers such as vinyl ethers and vinyl esters such as vinyl acetate. , (meth)acrylic esters such as methyl, ethyl, butyl, acrylonitrile, styrene, carbon oxide, etc. may be copolymerized.

(D) The α-olefin used in the polymerization of the modified ethylene polymer includes ethylene, propylene, butene-1, and mixtures of two or more thereof, and in particular, ethylene,
Mixture of ethylene and propylene, ethylene and butene-1
A mixture of is preferred.

In addition, ethylene polymers include polyethylene, polypropyne, ethylene-propyne copolymer, ethylene-butene-
Examples include a single copolymer and a mixture of two or more thereof.

(D) There are no particular limitations on the method for producing the modified ethylene polymer; for example, (1) an α-olefin and a vinyl monomer containing a carboxyl group or an epoxy group are brought into contact with a Ziegler-Natsuta catalyst in a solvent. , normal temperature to 80℃, 3 to 10 kg
/crI polymerization method.

(2) The vinyl monomer is mixed in the presence of a radical generating catalyst at a rate of 5 to 200 kg/c [l? , a method of grafting onto an ethylene polymer at 50 to 300°C, etc. can be used.

One type or two or more types of these modified ethylene polymers can be used.

Okibe, (B) aromatic polyester 1-98-TTf[,
Preferably 20 to 90 parts by weight, (C) modified vinyl polymer 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, and (D) modified ethylene polymer 1 to 30 parts by weight, preferably (A) + (B) + in the range of 2 to 20 parts by weight
Blend so that (C) + (D) becomes 100 parts by weight.

(A) If the polyamide elastomer is less than 1 part by weight, the antistatic properties of the resin composition will be insufficient, and if it exceeds 50 parts by weight,
This is not preferable because the resin composition becomes flexible and has poor mechanical properties.

If the aromatic polyester (B) is less than 1 part by weight, the heat resistance of the resin composition will be poor, and if it exceeds 98 parts by weight, the antistatic properties of the resin composition will deteriorate, which is not preferred.

If the amount of the modified vinyl polymer (C) is less than 0.1 part by weight, the resin composition will cause delamination and cannot be used, and if it exceeds 50 parts by weight, the surface gloss of the molded product will be significantly deteriorated, which is undesirable.

In addition, if (D) the modified ethylene polymer is less than 1 part by weight, the impact resistance of the resin composition will not be improved, and if it exceeds 30 parts by weight, the resin composition will become flexible and have poor mechanical properties, so it is preferable. do not have.

There are no particular limitations on the method for producing the resin composition of the present invention, and for example, (A) polyamide elastomer, (B) aromatic polyester, (C) modified vinyl polymer, and (D
) A product is produced by melt-kneading a resin mixture of a modified ethylene polymer using a Banbury mixer, roll, extruder, etc.

The resin composition of the present invention may contain other thermoplastic polymers that are compatible with the resin composition of the present invention, such as polyamide, polycarbonate, polyphenylene ether, polyglutarimide, rubber-modified styrene such as ABS resin, MBS resin, and AES resin. polyolefins such as polyethylene, polypropylene, ethylene/propylene copolymers, ethylene/butene-1 copolymers, and elastomers such as hydrogenated and/or non-hydrogenated sfrene-butadiene block copolymers. They can be mixed to improve their performance as molding resins.

In addition, metal salts of sulfonic acid, anionic type, cationic type,
It is also possible to further improve antistatic properties by adding antistatic agents such as nonionic surfactants, and if necessary, compatibilizers such as oligomers, antioxidants, ultraviolet absorbers, etc. Various stabilizers, pigments, dyes, lubricants, plasticizers, glass fibers, flame retardants, etc. can also be added. In addition, when using a modified vinyl polymer containing an epoxy group, by adding a metal salt of sulfonic acid, a tertiary amine, and a phosphorus compound, component (A) and (B) can be combined.
It is also possible to further improve the compatibility of the components.

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

Izot impact strength: ASTM D256-56A Flexural modulus: ASTM D790 Vicat softening temperature: ASTM D2525-58T Volume surface G resistance: Measured using a 2mmt x 40mmφ disk at room temperature of 23° C. and humidity of 50% RH. A super insulation resistance meter 5M-10 model manufactured by Toa Denpa Kogyo ■ was used for the measurement.

The delamination prevention property of the molded article was determined by observing the molded article when it was bent, and the criteria for evaluation were: @;: H is very good, ○: good, and ×: the molded article causes delamination.

In addition, 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=
50 parts of caprolactam, 44.2 parts of polyethylene glycol with a number average molecular weight of 1.000, and 7 parts of terephthalic acid.
．． 6 parts of “Irganox” 1098 (antioxidant,
The mixture was charged into a reaction vessel equipped with a helical ribbon stirring blade together with 2 parts of Ciba-Geigy (manufactured by Ciba Geigy) and 0.1 part of antimony trioxide catalyst, and the mixture was purged with nitrogen and heated and stirred at 260°C for 60 minutes to form a transparent homogeneous solution. After that, 260'C, 0.5m
Polymerization was carried out for 4 hours under conditions of ml or less to obtain a viscous and transparent polymer.

A pellet-shaped polyamide elastomer (A-1) was prepared by discharging the polymer onto a cooling belt and pelletizing it.

A-2 = 40 parts of prolactam, 7.16 parts of ethylene oxide adduct of bisphenol A, Eupol BPE20 (manufactured by Sanyo Chemical Industries, Ltd.), 44.2 parts of polyethylene glycol having a number average molecular weight of 1.000, and 11.0 parts of terephthalic acid. 7 parts of "Irganox" 10980.2 parts and antimony trioxide 0.02 parts were charged into the reaction vessel used in A-1, and the mixture was purged with nitrogen and heated and stirred at 260"C for 60 minutes to form a transparent homogeneous solution. Next, the pressure was reduced to 500 mm/g according to the decompression program to remove moisture in the gas phase of the reaction vessel, and then the pressure was reduced according to the zirconium tetrabutoxide pressure program to 260'C and 0.5 mm.
Polymerization was carried out for 3 hours and 20 minutes under conditions of 11 g or less to obtain a viscous and transparent polymer. Thereafter, pellet-shaped polyamide elastomer (A-2) was prepared in the same manner as A-1.

A-3: Poly(ethylene oxide) glycol diamine having an amino group at both ends is produced by reacting poly(ethylene oxide) glycol with an average molecular weight of 4,000 with acrylonitrile and further performing a hydrogenation reaction. I got it. This was subjected to a salt reaction with terephthalic acid in a conventional manner to obtain a 40% aqueous solution of poly(ethylene oxide) glycol diammonium terephthalate. Add 200 parts of the above 40% poly(ethylene oxide) glycol diammonium terephthalate aqueous solution to a concentrator and add 85% ε-
120 parts of caprolactam aqueous solution was heated to 40% for about 2 hours and concentrated to 80% concentration. Subsequently, the concentrated solution was transferred to a polymerization apparatus, and heating was started while flowing nitrogen into the polymerization apparatus.

When the internal temperature reached 120°C, 5.0 parts of 1,3.5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene was added and stirring was continued. The temperature was raised until the internal temperature reached 245°C. The polymerization was completed by heating at 245°C for 18 hours, and then a pellet-shaped polyamide elastomer (A-3) was prepared in the same manner as A-1.

(2) (B) Preparation of aromatic polyester B-1 = polybutylene terephthalate (B-1) with a relative viscosity of 1.38 measured in orthochlorophenol (OCP) at 25°C and 0.5% concentration was used. .

B-2S Polybutylene terephthalate)-(B-
2) was used.

(3) (C) Preparation of modified vinyl polymer C-1 = A modified vinyl polymer (C-1) was prepared by suspension polymerization of 70 parts of styrene, 25 parts of acrylonitrile, and 5 parts of methacrylic acid.

The intrinsic viscosity ([η]) of the obtained modified vinyl polymer (C-1) measured in methyl ethyl ketone (MEK) at 30° C. at a concentration of 0.4% was 0.61.

C-2 = A modified vinyl polymer (C-2) was prepared by suspension polymerization of 71 parts of styrene, 28 parts of acrylonitrile, and 1 part of glycidyl methacrylate.

The obtained modified vinyl polymer (C-2) was measured in the same manner as C-1 and had a [η] of 0.56.

C-3 = Emulsion polymerization of 73 parts of styrene, 25 parts of acrylonitrile, and 2 parts of acrylamide to obtain a modified vinyl polymer (
C-3) was prepared.

The obtained modified vinyl polymer (C-3) had [η] of 0.51 when measured by the same method as C-1.

(/l) (D) Preparation of modified ethylene polymer D-1
=Ethylene/glycidyl methacrylate copolymer [90/
10 weight ratio, Ml (1906C) 3°2 g/10 min] was used.

D-2 = A copolymer (MI (190 °C) 2.5 g / 10 minutes) in which 2 mol% of methacrylic acid was grafted onto an ethylene/butene-1 copolymer (90/10 market weight ratio) was used. .

Examples 1 to 7 (A) polyamide elastomer, (B) prepared in reference example
Aromatic polyester, (C) modified vinyl polymer, and (D) modified ethylene polymer are mixed at the compounding ratio shown in Table 1, and melt-kneaded and extruded at a resin temperature of 250°C using a vented 40 mmφ extruder. A beret was manufactured by this method.

Then, using an injection molding machine, the cylinder temperature was set to 250°C1.
A test piece was molded at a mold temperature of 80°C, and each physical property was measured.

The volume resistivity value was measured using an injection molded disk with a thickness of 2 mm under the following conditions.

(1) Immediately after molding, wash with detergent “Mama Lemon” (manufactured by Lion Oil) aqueous solution, then thoroughly wash with distilled water to remove surface moisture, and then heat at 50% RH 123°C for 2 hours.
The humidity was controlled for 4 hours and then the temperature was set.

(2) 50% after molding After leaving 200 mouths in RH1239C, washing with detergent "Mama Lemon" aqueous solution, then thoroughly washing with distilled water to remove surface moisture, 50%
Measurements were made after adjusting the humidity at RH and 23°C for 24 hours.

The measurement results are shown in Table 2.

Ratio Examples 1 to 8 (A) Polyamide elastomer prepared in Reference Example, (B)
Aromatic polyester, (C) a modified vinyl polymer, and (D) a modified ethylene polymer were mixed at the blending ratio shown in Table 1, and their physical properties were measured in the same manner as in the examples. The results are shown in Table 2.

The following is clear from the results in Margin Table 2 below. All of the resin compositions of the present invention (Examples 1 to 7) are excellent in mechanical properties represented by impact strength and flexural modulus, and heat resistance in a well-balanced manner, and have low volume resistivity values. Moreover, 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, heat 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 antistatic property (resistance value) is poor, and when the amount of polyamide elastomer (A) exceeds 50 parts by weight (Comparative Example 2) has poor heat resistance and flexural modulus, causing delamination of molded products.

When the blending amount of the aromatic polyester (B) is less than 1 part by weight (Comparative Example 3), the heat resistance is poor, and the aromatic polyester (
When B) exceeds 98 parts by weight (Comparative Example 4), antistatic properties are poor.

When the amount of the modified vinyl polymer (D) is less than 1 part by weight (Comparative Example 5), the improvement in impact resistance is insufficient, and when the amount of the modified ethylene polymer (D) exceeds 30 parts by weight. (Comparative Example 6) is inferior in flexural modulus.

Furthermore, when the amount of the modified vinyl polymer (C) is less than 0.1 parts by weight (Comparative Example 7), delamination occurs in the molded product, and when the amount of the modified vinyl polymer (C) exceeds 50 parts by weight. In this case (Comparative Example 8), the appearance and antistatic properties of the molded product deteriorate, which is not preferable.

That is, the resin composition of the present invention has excellent mechanical properties, heat resistance, and permanent antistatic properties, and is a composition that exhibits extremely good delamination of molded products.

[Effect of the invention] The thermoplastic resin composition of the present invention has specific (A), (B),
Since specific amounts of (C) and (D) are blended, the composition has excellent mechanical properties such as permanent antistatic properties and impact resistance, and heat resistance, and is free from delamination.

Patent applicant: Higashimune Shiki Company

Claims (1)

Scope of Claims: (A) 1 to 50 parts by weight of polyamide elastomer, (B) 1 to 98 parts by weight of aromatic polyester, and (C) at least one selected from carboxyl group, epoxy group, amino group, and substituted amino group. (A)+(B)+ A thermoplastic resin composition containing 100 parts by weight of (C)+(D).