JPS62241945A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a compsn. having permanent antistatic properties as well as excellent mechanical properties, moldability and resistance to delamination, by blending a polyether ester amide with a graft (co)polymer-contg. material and a modified vinyl polymer. CONSTITUTION:A resin compsn. is obtd. by blending 1-40pts.wt. polyether ester amide (A) composed of a salt of an aminocarboxylic acid, lactam or diamine with a dicarboxylic acid, a poly(alkylene oxide) glycol and a dicarboxylic acid with 55-98pts.wt. material (B) contg. a graft (co)polymer obtd. by graft-copolymerizing a monomer component consisting of an arom. vinyl monomer and/or a (meth)acrylic ester monomer or a mixture thereof, or a monomer component consisting of an arom. vinyl monomer and/or a (meth) acrylic ester monomer and a vinyl cyanide monomer or a mixture thereof onto a rubbery polymer and 0.1-20pts.wt. modified vinyl monomer (C) having carboxyl groups in such a proportion that the amount of the rubbery polymer accounts for 1-40wt% of the whole of the compsn.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention has permanent antistatic properties, excellent mechanical properties such as impact resistance, and excellent moldability, and is free from delamination (delamination). The present invention relates to an electrically conductive resin composition that does not cause sheet peeling.

<Prior Art> Synthetic polymer materials are used in a wide range of fields due to their excellent properties. These materials can be used in a wide range of applications if they are provided with antistatic properties in addition to their mechanical strength. In other words, it is possible to expand the application to copying machines and various dustproof parts where it is desired to prevent failures due to static electricity.

As a method to improve the control properties of synthetic polymer materials,
A method of obtaining a hydrophilic rubber-like polymer obtained by copolymerizing a conjugated diene and/or acrylic acid ester with a vinyl monomer having an alkylene oxide group, and graft polymerizing a vinyl monomer or a vinylidene monomer (Unexamined Japanese Patent Publication No. 5
5-36237), which have achieved practical antistatic properties.

Furthermore, Japanese Patent Application Laid-open No. 60-23435 discloses that polyamide 1
It is disclosed that by mixing 521 to 75 to 80 parts by weight and 95 to 20 parts by weight of a modified vinyl polymer containing a carboxyl group, a resin having semi-permanent electrostatic properties can be obtained.

<Problems to be Solved by the Invention> However, the electrophilic resin obtained by graft polymerizing a monomer to a hydrophilic rubber-like polymer described in JP-A-55-36237 has a special hydrophilic rubber-like structure. Since the method uses ``Machigogai'', the production method is complicated and the resulting resin has poor mechanical properties, so it is not completely satisfactory.

In addition, the antistatic resin disclosed in JP-A-60-23-435 has a reactivity between a modified vinyl polymer containing a carboxyl group (hereinafter referred to as modified vinyl polymer) and polyether ester amide. In addition, due to the large amount of modified vinyl polymer blended, moldability is extremely poor.
There are also problems in that the physical properties cannot be reproduced well.

Means for Solving the Problems> The present inventors have developed an electrostatic resin that has permanent antistatic properties, has excellent mechanical properties such as impact resistance, and moldability, and does not cause delamination. As a result of intensive studies with the aim of providing a polyether ester amide and a graft (co)polymer-containing material, the above purpose was efficiently achieved by mixing a subordinate amount of a modified vinyl polymer with a specific polyether ester amide and graft (co)polymer-containing material. The present invention was achieved based on this discovery.

That is, the present invention provides (^) (a1) an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a salt of a diamine and dicarboxylic acid having 6 or more carbon atoms, (a2) a number average molecular weight of 200 to 6.000 (7 ) poly(
(alkylene oxide) glycol and (a3) dicarboxylic acid having 4 to 20 carbon atoms, 1 to 40 parts by weight of polyether ester amide containing 95 to 10% by weight of polyether ester units; , (B) Graft containing the following graft (co)polymer (
Co) Polymer-containing material 55-98@Danbe, (b1) (bl-
1) 1 to 80 parts by weight of a rubbery polymer, (bl-2) a monomer or monomer mixture consisting of an aromatic vinyl monomer and/or a (meth)acrylic acid ester monomer, and aromatic A monomer mixture consisting of group vinyl monomers and/or (meth)acrylic acid esters, 99 to 40% by weight of vinyl cyanide monomers, and 1 to 60% by weight of vinyl cyanide monomers. A graft (co)polymer obtained by grafting (co)polymerizing 99 to 20 parts by weight of a polymer or a monomer mixture, and (C) a modified vinyl polymer containing a carboxyl group 0
．． 1 to 20 parts by weight are blended so that (A) + (B) + (C) is 100 parts by weight, and the amount of rubbery polymer in the rest is 1
The object of the present invention is to provide a thermoplastic resin composition blended in such a manner that the amount thereof is 40% by weight.

The present invention will be specifically explained below.

The thermoplastic resin composition of the present invention comprises (Δ) polyether ester amide, (B) a material containing a graft (co)polymer, and (C) a modified vinyl polymer.

The (a1) aminocarboxylic acid or lactam having 6 or more carbon atoms or the salt of diamine and dicarboxylic acid having 6 or more carbon atoms, which is a constituent component of the polyether ester amide (A) according to the present invention, includes ω-aminocaproic acid;
Aminocarboxylic acids such as ω-aminoenantoic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid and 11-aminoundecanoic acid, 12-aminododecanoic acid or caprolactam, enantholactam, capryllactam, and lauro lactams such as lactams and hexamethyleneleamine adipate;
Salts of diamine-dicarboxylic acids such as hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate are used, and caprolactam, 12-aminododecanoic acid, and hexamethylenediamine-adipate are particularly preferably used.

(a1) Salts of aminocarboxylic acids or lactams having 6 or more carbon atoms or diamines and dicarboxylic acids having 6 or more carbon atoms are the constituent units of polyether ester amide with 5
If the amount is less than 5% by weight, the mechanical properties of the polyether ester amide will be poor, and if it is less than 90% by weight, the resulting resin will have poor antistatic properties, which is not preferred.

(A>Constituent component of polyether ester amide (
a2) Poly(alkylene oxide) glycol includes polyethylene glycol, poly(1゜2-propylene oxide) glycol, 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 are used. Among these, polyethylene glycol is particularly preferably used because of its excellent antistatic properties. The number average molecular weight of poly(alkylene oxide) glycol is 2
00 to 6,000, preferably 250 to 4,000.

If the number average molecular weight is less than 200, the mechanical properties of the resulting polyether ester amide will be poor;
If it exceeds 000, the antistatic properties will be insufficient, which is not preferable.

(A) Constituent components of polyether ester amide (
a3) Dicarboxylic acids having 4 to 20 carbon atoms include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,
Aromatic dicarboxylic acids such as 6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4-monodicarboxylic acid, diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid , 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4'-dicarboxylic acid, and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid and dodecanedioic acid, etc. In particular, 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.

(a2) Poly(alkylene oxide) glycol and (
a3) Dicarboxylic acids are reacted at a molar ratio of 1:1, but the charging ratio is usually changed depending on the type of dicarboxylic acid used.

The polyether ester component is a structural unit of polyether ester amide and is used in a range of 95 to 10 weight percent,
If it exceeds 5% by weight, the mechanical properties of the polyether ester amide will be poor, and if it is less than 10% by weight, the antistatic properties of the resin will be poor, which is not preferred.

There are no particular limitations on the polymerization method for (A) polyether ester amide. For example, (a) (a) (at) aminocarboxylic acid or lactam is reacted with (a3) dicarboxylic acid to form a polyamide prepolymer having carboxylic acid groups at both ends. A method of producing a poly(alkylene oxide) glycol and reacting it with (a2) poly(alkylene oxide) glycol under vacuum.

(b) each of the compounds (a1), (a2), and (a3) is charged into a reaction layer and reacted at high temperature in the presence or absence of water to produce a carboxylic acid-terminated polyamide prepolymer; A method of proceeding with the polymerization thereafter under normal pressure or reduced pressure, and (c) the above (a1), [a2), (a3)
After simultaneously charging the compounds into the reaction layer and melting and mixing,
Known methods such as a method of proceeding with polymerization all at once under high vacuum can be used.

In the present invention, (B) in the graft (co)polymer containing material (
b1) Graph 1 ~ The (co)polymer is a monomer consisting of (bl-1) a rubbery polymer and (bl-2) an aromatic vinyl monomer and/or a (meth)acrylic acid ester monomer. A monomer or monomer mixture selected from a monomer mixture consisting of an aromatic vinyl monomer, a (meth)acrylic acid ester monomer, and a vinyl cyanide monomer. This is a mixture obtained by graft (co)polymerization.

(t)1-1) Rubbery polymer used in the present invention includes:
Those with a glass transition temperature of 0°C or less are suitable, and specifically, diene rubbers such as polybutadiene, polystyrene-butadiene, polyac 1) ronitrile → butadiene, and acrylic rubbers such as polyisoprene, polychloroprene, polybutyl acrylate, etc. Rubbery polymers such as rubber and ethylene-propylene-diene thread ternary copolymers can be used.

Particularly preferred are butadiene or butadiene copolymers.

Aromatic vinyl monomers include styrene, α-methylstyrene, vinyltoluene, 〇-ethylstyrene, op
-dichlorostyrene, etc., and styrene is particularly preferred.

(Meth)acrylic acid ester monomers include acrylic acid and methacrylic acid methyl, ethyl, propyl, n
-butyl, 1-butyl, etc., but methyl methacrylate is particularly preferred.

Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, ethacrylonitrile, and acrylonitrile is particularly preferred.

Other vinyl monomers, for example maleimide monomers such as maleimide, N-methylmaleimide, and N-phenylmaleimide, acrylamide, and the like can also be used if necessary.

(b1) The blending ratio of the mixture consisting of the aromatic vinyl monomer and/or (meth)acrylic acid ester monomer and vinyl cyanide monomer used in the graft (co)polymer is 99 to 40% by weight of monomers and/or (meth)acrylic acid ester monomers, preferably 90 to 50% by weight, 1 to 10% of vinyl cyanide monomers
The maximum amount is 60% by weight, preferably 10 to 50% by weight.

If the proportion of the vinyl cyanide monomer is less than 1% by weight, the effect of improving impact resistance due to the inclusion of the vinyl cyanide monomer will not be noticeable, which is not preferable. Moreover, if it exceeds 60% by weight, the thermal stability of the graft copolymer will be significantly reduced, resulting in a molded product with poor color tone, which is not preferable.゛(b1) The proportion of the rubbery polymer and monomer or monomer mixture in the graft (co)@coalescence is 1% of the rubbery polymer in 100 parts of the total graft (co)polymer.
-80 parts by weight, preferably 5-70 parts by weight, 99-20 parts by weight of monomer or monomer mixture, preferably 95-20 parts by weight
It is 30 parts by weight.

If the proportion of the rubbery polymer in this (b1) graft (co)polymer is less than 1 part by weight, the resulting resin composition will have poor impact resistance, and if it exceeds 8.0 parts by weight, the rubbery polymer will be This is not preferable because it causes poor dispersion and impairs the appearance of the molded product.

(b1) The graft (co)polymer is produced by a known polymerization method, such as a method in which a monomer or a monomer mixture and a polymerization initiator are continuously supplied in the presence of a rubbery polymer latex and emulsion-compounded. Obtainable.

In the present invention, it is necessary that the graft (co)polymer-containing material (B) contains the above-mentioned graft (co)polymer, and the amount of the rubbery polymer in the resin composition is 1 to 1.
If the amount is 40% by weight, only the graft (co)polymer may be used.

(B) In the graft (co)polymer-containing material, examples of other (co)polymers include styrene-acrylonitrile copolymer, α-methylstyrene-styrene-acrylonitrile copolymer, and α-methylstyrene-acrylonitrile copolymer. Methyl methacrylate-acrylonitrile copolymer, α-methylstyrene-acrylonitrile copolymer, styrene-methyl methacrylate-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, styrene-N-phenylmaleimide-acrylonitrile copolymer Examples include polystyrene, α-methylstyrene-methyl methacrylate copolymer, polystyrene, and polymethyl methacrylate.

Preferred examples include (co)polymers consisting of aromatic vinyl monomers and/or (meth)acrylic acid ester monomers, aromatic vinyl monomers and/or
Or a copolymer consisting of a (meth)acrylic acid ester monomer or a vinyl cyanide monomer.

In particular, aromatic vinyl monomers and/or (meth)acrylic acid ester monomers 100 to 40% by weight, preferably 100 to 50% by weight, and vinyl monomers by weight 0 to 6%
Most preferred are (co)polymers comprising 0% by weight, preferably 0 to 50% by weight.

In this (co)polymer, if the proportion of the aromatic vinyl monomer and/or (meth)acrylic acid ester monomer is too small, the affinity with the polyether ester amide will deteriorate, causing delamination. Therefore, it is preferable to use it in an amount of 40% by weight or more.

(C) Modified vinyl polymer containing a carboxyl group (hereinafter abbreviated as modified vinyl polymer) used in the present invention is a polymer obtained by polymerizing or copolymerizing one or more vinyl monomers. It is a polymer that has a structure obtained by the process and has a carboxyl group in the molecule.

This carboxyl group may be an anhydride carboxyl group. There is no limit to the content of these carboxyl groups, and it may be a very small amount, or it 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 efficiently exhibited if the modified vinyl polymer contains substantially one or more carboxyl groups on average in one molecule.

(C) There are no particular restrictions on the method of introducing carboxyl groups into the modified vinyl polymer, but there are Method of copolymerizing a vinyl monomer having a carboxyl group with a desired vinyl monomer, ■γ, γ゛-azobis(γ-cyatubaleic acid), α, α゛-(α-cyano)ethyl-
Polymerization initiators with carboxyl groups such as p-benzoic acid and succinic acid peroxide and/or thioglycolic acid, α-mercaptopropionic acid, β-mercaptopropionic acid, α-mercapto-imbutyric acid and 2,3 or 4- A method of (co)polymerizing a desired vinyl monomer using a polymerization degree regulator having a carboxyl group such as mercaptobenzoic acid, and (meth)acrylic acid ester such as methyl methacrylate or butyl acrylate. of the system (
A method such as saponifying the co-)@coalescence with an alkali can be used.

(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, vinyl cyanide monomers such as acrylonitrile and tol methacrylate, and (meth)acrylic acid ester monomers such as methyl methacrylate and butyl acrylate. from olefinic monomers such as ethylene, propylene, and vinyl monomers such as vinyl chloride, vinyl acetate, and butadiene. One type or two or more types can be selected and used depending on the purpose.

In particular, aromatic vinyl monomers such as styrene, (meth)acrylic acid ester monomers such as methyl methacrylate, N
- Maleimide monomers such as phenylmaleimide and vinyl cyanide monomers such as acrylonitrile are preferably used because the resulting resin composition has excellent mechanical 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. Vinyl monomers can also be used in combination.

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

The thus obtained polymer contains (A) 1 to 40 parts by weight, preferably 5 to 30 parts by weight of polyether ester amide;
(B) 55 to 98 parts by weight of graft (co)polymer-containing material,
Preferably 60 to 95 parts by weight and (C) modified vinyl polymer 0.1 to 20 parts by weight, preferably 1 to 18 parts by weight, and (A) + (B) + (C) is 100 parts by weight. Mix so that

(A> If the amount of polyether ester amide 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.

If the content of the graft (co)polymer (B) is less than 55 parts by weight, the impact resistance will be insufficient, and if it exceeds 98 parts by weight, the antistatic property will be poor, which is not preferable.

In addition, (C) the modified vinyl polymer is 0.1fffffi
If the amount is less than 20 parts by weight, it cannot be used because it causes delamination of the resin composition, and if it exceeds 20 parts by weight, the molding processability is significantly deteriorated and the surface of the molded product becomes matte, which is not preferable.

What is required in the resin composition of the present invention is that the proportion of rubber in the resin composition is 1 to 40% by weight, preferably 3 to 30% by weight.

If it is less than 1% by weight, the impact resistance of the resin composition will be poor, and if it exceeds 40% by weight, the resin composition will become flexible and have poor mechanical properties, which is not preferable.

There are no particular limitations on the method for producing the resin composition of the present invention; for example, (A) polyetheresteramide and (B)
) The resin mixture of the graft (co) polymer-containing material and (C) the modified vinyl polymer was mixed in a Banbury mixer, a roll,
It is made into a product by melting and kneading it using an extruder or the like. In addition, in (B), if only the graft (co)@copolymer is not used, the graft (co)polymer and (co)
The blending of the polymers may be independent or may be mixed in advance, and is not particularly limited.

The resin compositions of the present invention may also contain other thermoplastic polymers which are compatible with the resin compositions of the present invention, such as polyamide, polybutylene phthalate, polyethylene terephthalate, polycarbonate, hydrogenated and/or unhydrogenated styrene-butadiene. The performance as a molding resin can be improved by mixing an elastomer such as a block copolymer.

It is also possible to further improve antistatic properties by adding antistatic agents such as metal salts of sulfonic acid, anionic or cationic surfactants, and if necessary, compatibilizers such as oligomers can be added to the coating. , various stabilizers such as antioxidants and ultraviolet absorbers, pigments, dyes, lubricants, plasticizers/plasticizers, flame retardants, etc. can also be added.

<Function> In the present invention, the resin obtained by blending a specific amount of a modified vinyl polymer with a material containing polyether ester amide and Gurarad (co)polymer has permanent antistatic properties, and
Exhibits excellent mechanical properties and moldability. Furthermore, a good product without delamination can be obtained. This phenomenon can be achieved by adding a modified vinyl polymer to a graft (co)polymer that has low affinity with polyetheresteramide, which has antistatic properties. It is assumed that the effect is to increase the

<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.

Izot impact strength: ASTM D256-56Δ Tensile strength: ASTM D638 Flexural modulus: ASTM D790 Flammability: Vertical combustion test 1 according to UL94 standard
/16''XI/2''X5°' (7) A combustion test piece was used.

VFR: Measured under the conditions of nozzle 2φX8, temperature 220'C, load 10 and 3.

Volume resistivity value: using 2t×40φ disk, room temperature 23°
Measurement was carried out at a C1 temperature of 50% RH. A super insulation resistance meter 5M-10 model manufactured by Toa Denpa Kogyo Co., Ltd. was used for the measurement.

The delamination prevention property of the molded product was determined by bending the molded product and observing the fracture surface of a tensile test specimen. ◎: Very good, ○: Good, X: The molded product causes delamination.
Regarding the appearance of the molded product, the following criteria were used: ◎: appearance is very good, ○: good, and X: surface of molded product is damaged and defective.

In addition, parts and percentages in the examples indicate parts by weight and percentages by weight, respectively.

Reference example <1) (A) Preparation of polyether ester amide A-1
: 50 parts of cabrolactam, 45 parts of polyethylene glycol with a number average molecular weight of 1000, and 7.0 parts of adipic acid were mixed with 0.2 parts of "Irganox" 1098 (antioxidant).
1 part and 0.1 part of antimony trioxide catalyst into a reaction vessel equipped with a helical ribbon stirring blade, purged with nitrogen, heated and stirred at 240°C for 60 minutes to make a transparent homogeneous solution, and then heated at 260°C with 0.5NI4Hg. Polymerization was carried out for 4 hours under the following conditions to obtain a viscous and transparent polymer.

A pellet-shaped polyether ester amide (A-1>) was prepared by discharging the polymer onto a cooling belt and pelletizing it.

A-2: Except that 60 parts of nylon 6.6 salt (A H salt), 33.8 parts of polyethylene glycol with a number average molecular weight of 600, and 8.7 parts of adipic acid were used, and the polymerization time was 4 hours. Polyether ester amide (A-2) was prepared in exactly the same manner as in Example 1>.

A-3: 30 parts of ω-aminodecanoic acid, 14 parts of dodecanoic acid.
Polyether ester amide l:, A, -3) was prepared in the same manner as (A-1) except that the polymerization time was 3 hours using 2 parts and 58.6 parts of polyethylene glycol with a number average molecular weight of m1ooo. did.

<2) CB) (b1) Preparation of graft (co)polymer B
-1: Polybutadiene latex (rubber particle size 0.25
40 parts of a monomer mixture consisting of 55% styrene and 45% methyl methacrylate was emulsion polymerized in the presence of μ, gel content 80% > 60 parts (in terms of solid content).

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

B-2: Polybutadiene latex 4 used in B-1
Methyl methacrylate in the presence of 0 parts (calculated as solid content) of 7
A powdery graft copolymer (B-2>) was prepared in the same manner as B-1 by emulsion polymerizing 60 parts of a monomer mixture consisting of 5% styrene and 25% styrene.

After dissolving 10 parts of B-3 Nidiene NF, 35A (manufactured by Asahi Kasei Corporation) in 90 parts of styrene, a graft polymer (B-3> was prepared by bulk polymerization).

B-4: Polybutadiene latex 8 used in B-1
After emulsion polymerizing 15 parts of a monomer mixture consisting of 45% styrene and 55% methyl methacrylate in the presence of 5 parts (solid content), a powdery graft copolymer (B -4> was prepared.

B-5: Polybutadiene latex (rubber particle size 0.2
40 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile was emulsion polymerized in the presence of 60 parts (in terms of solid content) (5μ, gel content 80%). The graft copolymer obtained by 1q is lj! Coagulated with f acid, neutralized with caustic soda, washed, filtered, and dried to form a powdery graph 1 ~ copolymer (
B-5> was prepared.

B-6: 7 parts of methyl methacrylate in the presence of 40 parts of the polybutadiene latex (calculated as solid content) used in B-5.
After emulsion polymerization of 60 parts of a monomer mixture consisting of 2% styrene, 24% styrene, and 4% acrylonitrile, a powdery graft copolymer (B-6>) was prepared in the same manner as in 8-5.

B-7: Polybutadiene latex 8 used in B-5
In the presence of 5 parts (solid content), 15 parts of a monomer mixture consisting of 70% styrene and 1 to 30% acryloni was emulsion polymerized. Polymer (B-7>) was prepared.

B-8: Polybutadiene latex 1 used in B-5
After emulsion polymerizing 85 parts of a monomer mixture consisting of 75% styrene and 1 to 25% acrylonitrile in the presence of 5 parts (solid content), a powdery graft copolymer ( B-8> was prepared.

(3) (B) (b2) Preparation of (co)polymer b-1:
A copolymer (b-1>) was prepared by copolymerizing 55 parts of methyl methacrylate and 45 parts of styrene.

b-2: A copolymer (b-2>-) was prepared by copolymerizing 72 parts of styrene and 28 parts of acrylonitrile.

b-3: 72 parts of methyl methacrylate, 24 parts of styrene,
By copolymerizing 4 parts of acrylonitrile, '# copolymer b-3
> was prepared.

b-4: 50 parts of styrene, 30 parts of N-phenylmaleimide
part, and 20 parts of acrylonitrile to form a copolymer (
b-4> was prepared.

<4) (C) Preparation of modified vinyl polymer containing carboxyl group C-1: 45 parts of styrene, 50 parts of methyl methacrylate,
A bead-shaped modified vinyl polymer (C-1>) was prepared by suspension polymerization of 5 parts of methacrylic acid.

C-2: A bead-shaped modified vinyl polymer (C-2>) was prepared by suspension polymerization of 70 parts of styrene, 25 parts of acrylonitrile, and 5 parts of methacrylic acid.

C-3 = 70 parts of methyl methacrylate, 24 parts of styrene,
A bead-shaped modified vinyl polymer (C-3>) was prepared by suspension polymerization of 4 parts of acrylonitrile and 2 parts of acrylic acid.

C-4: A bead-shaped modified vinyl polymer (C-4>) was prepared by suspension polymerization of 90 parts of styrene and 10 parts of methacrylic acid.

C-5: After mixing 90 parts of styrene and 10 parts of anhydrous maleic VI in a solution, the solvent was removed and a modified vinyl polymer (C
-5) was prepared.

C-6: A bead-shaped modified vinyl polymer (C-6) was prepared by suspension polymerization of 72 parts of styrene, 18 parts of acrylonitrile, and 10 parts of acrylic acid.

Examples 1 to 9 Prepared in reference example (A>polyether ester amide,
(B) (b1) graft copolymer, (i) 2) (co)
The polymer and (C) modified vinyl polymer were mixed at the compounding ratio shown in Table 1, and the resin temperature was increased to 2 using a vented 40 mφ extruder.
Pellets were produced by melt mixing and extrusion at 20°C.

Next, a test piece was molded using an injection molding machine at a cylinder temperature of 220°C and a mold temperature of 60°C, and each physical property was measured.

The volume resistivity value was determined using an injection molded disk with a thickness of 2#.
Measurements were made under the following conditions.

(1) Direct molding, detergent “Mama Lemonpa (lion oil)”
Co., Ltd.) aqueous solution, followed by thorough washing with distilled water to remove surface moisture, and then humidity-controlled at 50% RH 123°C for 24 hours and measured. (2) 50% RH1 after molding
After leaving it at 23°C for 200 days, it was washed with an aqueous solution of the detergent "Mama Lemon", then thoroughly washed with distilled water to remove surface moisture, and conditioned at 23°C for 24 hours with 50% R8. Measured wet.

The measurement results are shown in Table 2.

Comparative Examples 1 to 13 Prepared in Reference Example (A>polyether ester amide,
(B) (b1) graft (co)polymer, (b1) (co)
The polymer and ('C) modified vinyl polymer were mixed at the blending ratio shown in Table 1, and each physical property was measured in the same manner as in Example 1. In addition, (A) polyether ester amide, (B)
The physical properties of the graft (co)polymer and (C) modified vinyl polymer alone were also measured in the same manner. The results are shown in Table 2.

From the results in Table 2, it is clear that the 6 resin compositions of the present invention (Examples 1 to 9) all have excellent and low mechanical properties represented by tensile properties, flexural modulus, and impact strength. It has a volume resistivity value. Moreover, the resistance value hardly changes even after surface cleaning or changes over time, and it exhibits excellent permanent antistatic properties. Furthermore, the molded product has no delamination and has an extremely good appearance.

On the other hand, the blending amount of polyether ester amide (A>
If it is less than part by weight (Comparative Example 1), antistatic property (resistance value)
The tensile yield stress and flexural modulus of polyether ester amide (when A> exceeds 40 parts (comparative example 2°11)) are poor.

When the proportion of the rubbery polymer (bi-i) in the resin composition is less than 1% by weight (Comparative Examples 3 and 8), the impact resistance is poor, and when it exceeds 40% by weight (Comparative Example 4) has poor antistatic properties.

When the amount of the modified vinyl polymer containing a carboxyl group is less than 0.1 parts by weight (Comparative Example 5, 9.10), the molded product delaminates, and when it exceeds 20 parts by weight (Comparative Example 6) ) is undesirable as it significantly deteriorates molding processability and impairs the appearance of the molded product.

When a graft copolymer with a rubbery polymer content of more than 80 parts by weight is used (Comparative Example 7), the graft copolymer is poorly dispersed and the appearance of the molded product is impaired.

Resin compositions (Comparative Examples 12 and '13) that do not contain polyether ester amide (A>) have a high electrical resistance value and poor antistatic properties, so they are not preferred.

Examples 10 to 18 (A) polyether ester amide prepared in reference example,
(B) (b1) graft copolymer, (B) (b2) copolymer and (C) modified vinyl copolymer were mixed at the blending ratio shown in Table 3, and the same method as in Example 1 was carried out. Each physical property was measured.

The measurement results are shown in Table 4.

Comparative Examples 14-25 Prepared in Reference Example (A>polyether ester amide,
(B) (b1) graft copolymer, (B) (b2) copolymer and (C) modified vinyl copolymer were mixed at the blending ratio shown in Table 3, and the same method as in Example 1 was carried out. Each physical property was measured. In addition, (A>polyether ester amide, (B
) The physical properties of the graft copolymer (b1) and the modified vinyl copolymer (C) were also measured in the same manner.

The measurement results are shown in Table 4.

The following is clear from the results in Table 4. The resin compositions of the present invention (Examples 10 to 18) all have excellent mechanical properties represented by tensile properties, flexural modulus, and impact strength, 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. Furthermore, the molded product has no delamination and has an extremely good appearance.

On the other hand, the blending amount of polyether ester amide (A) is 1
When the amount is less than 40 parts by weight (Comparative Example 14), the antistatic property (resistance value) is poor, and when the polyether ester amide (A> is more than 40 parts by weight (Comparative Example 15.23), the tensile yield stress and flexural modulus are poor. is inferior.

When the proportion of the rubbery polymer (Bl-1) in the resin composition is less than 1% (Comparative Example 16.21), the impact resistance is poor, and when it exceeds 40WMi% (Comparative Example 7) Poor antistatic properties.

When the amount of modified vinyl polymer (C) containing a carboxyl group is less than 0.1 part by weight (Comparative Example 18.22)
In this case, the molded product peels in layers, and when the number of layers exceeds 20 (Comparative Example 19), the molding processability is significantly deteriorated and the appearance of the molded product is impaired, which is not preferable.

Graph where the proportion of rubbery polymer exceeds 80 @ u parts] - When a copolymer is used (Comparative Example 20), the graft copolymer is poorly dispersed and the appearance of the molded product is poor in IQ.

Resin compositions (Comparative Examples 24 and 25) that do not contain polyether ester amide (A) are not preferred because they have a high resistance value and poor antistatic properties.

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

<Effects of the Invention> The thermoplastic resin composition of the present invention has excellent mechanical properties such as permanent antistatic property and impact resistance, and moldability, and is free from delamination.

Patent application submitted to Shisha Co., Ltd.

Claims (2)

[Claims] (1) (A) (a1) Aminocarboxylic acid or lactam having 6 or more carbon atoms, or salt of diamine and dicarboxylic acid having 6 or more carbon atoms, (a2) Poly(alkylene) having a number average molecular weight of 200 to 6,000 1 to 40 parts by weight of a polyether ester amide composed of glycol (oxide) and (a3) dicarboxylic acid having 4 to 20 carbon atoms, the polyether ester amide having a polyether ester unit content of 95 to 10% by weight; B) 55 to 98 parts by weight of a graft (co)polymer-containing material containing the following (b1) graft (co)polymer, (b1) 1 to 80 parts by weight of (b1-1) rubbery polymer (
b1-2) Monomer or monomer mixture consisting of an aromatic vinyl monomer and/or (meth)acrylic acid ester monomer, and an aromatic vinyl monomer and/or (meth)acrylic monomer 99 to 20 parts by weight of a monomer or monomer mixture selected from a monomer mixture consisting of 99 to 40% by weight of an acid ester monomer and 1 to 60% by weight of a vinyl cyanide monomer is grafted (commonly). ) Graft (co)polymer formed by polymerization and (C) Modified vinyl polymer containing carboxyl group 0
．． 1 to 20 parts by weight are blended so that (A) + (B) + (C) is 100 parts by weight, and the amount of rubbery polymer is 1 to 40 weight% of the total. thermoplastic resin composition. (2) (B) The graft (co)polymer-containing material is the graft (co)polymer described in claim 1 and an aromatic vinyl monomer and/or a (meth)acrylic acid ester monomer. 100-40% by weight, vinyl cyanide monomer 0
The thermoplastic resin composition according to claim 1, which is a mixture with a (co)polymer consisting of ~60% by weight.