JPS63309552A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To make it possible to form an antistatic resin having excellent permanent antistatic property, impact resistance and transparency, by mixing a specified polyether-ester-amide with a graft copolymer obtained by graft-polymerizing a vinyl monomer mixture in the presence of a rubbery polymer and a modified vinyl polymer. CONSTITUTION:This thermoplastic resin composition contains 1-40wt.% polyether-ester-amide [A] obtained by polymerizing a 6C or higher aminocarboxylic acid or lactam (a) with polyethylene glycol and/or polypropylene oxide glycol (b) of a number-average MW of 200-2,000 and an aromatic dicarboxylic acid and/or alicyclic dicarboxylic acid (c) in the presence of a specified catalyst, 99-40wt.% graft polymer [B] obtained by graft- polymerizing a monomer mixture comprising a (meth)acrylic ester, an aromatic vinyl monomer and a vinyl cyanide monomer in the presence of a rubbery polymer and 0-20wt.% carboxylated or epoxidized modified vinyl polymer (c).

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a thermoplastic resin composition having excellent permanent antistatic properties, impact resistance and transparency.

<Prior art> A resin in which the refractive index of a rubbery polymer and the refractive index of a matrix resin are substantially matched, such as methyl methacrylate.
Butadiene-styrene copolymer (MBSVA resin) and methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS resin) are used in a wide range of fields as resins having excellent impact resistance and transparency.

If these resins are provided with antistatic properties in addition to their mechanical strength and optical properties, their uses can be further expanded. In other words, it is possible to expand the application to IC carry cases, OATli device covers, various dustproof parts, etc. that need to prevent damage caused by static electricity.

As a method of imparting antistatic properties to transparent resins, a hydrophilic rubber-like polymer obtained by copolymerizing a conjugated diene and /'& or acrylic acid alkyl ester with a vinyl monomer having an alkylene oxide group is used. There is a method of graft polymerizing a vinyl monomer whose refractive index substantially matches this (Japanese Unexamined Patent Publication No. 55-36237), which achieves practical antistatic properties.

<Problems to be solved by the invention> Conventional antistatic resins use a special hydrophilic rubber-like polymer, so the manufacturing method is complicated, and the resulting resin has poor impact resistance and elasticity. It has the disadvantage of poor mechanical properties such as ratio, and is not fully satisfactory.

An object of the present invention is to provide an antistatic resin having excellent permanent antistatic properties, anti-fever properties, and transparency.

Means for Solving the Problems> As a result of intensive studies to solve the above problems, the present inventors have developed a polyether ester-forming component composed of a polyamide-forming component, a specific poly(alkylene oxide) glycol, and a dicarboxylic acid. A polyether ester amide polymerized in the presence of a specific polymerization catalyst, a (meth)acrylic acid ester monomer, and an aromatic vinyl monomer in the presence of a rubbery polymer that satisfies specific conditions. The inventors have discovered that the above object can be efficiently achieved by mixing a transparent graft copolymer obtained by graft polymerizing a vinyl monomer mixture contained as a component, and have thus arrived at the present invention.

That is, the present invention provides (^) (a) an aminocarboxylic acid or lactam having 6 or more carbon atoms, (b) a number average molecular weight of 200
-2,000 polyethylene glycol and/or polypropylene oxide glycol and (C) aromatic dicarboxylic acid and/or alicyclic dicarboxylic acid selected from organotin compounds and organotitanium compounds in a weight ratio of 10,010 to 40/60. Transparent polyetheresteramide obtained by polymerization in the presence of one or more antimony oxides and containing 40 to 90% by weight of polyetherester units 1 to 40% by weight
Weight BHa) In the presence of 1 to 80 parts by weight of rubbery polymer (b
) A monomer mixture consisting of a total of 100 to 40% by weight of a (meth)acrylic acid ester monomer and an aromatic vinyl monomer and 0 to 60% by weight of a vinyl cyanide monomer, 99 to 99%.
When graft-polymerizing the 20-layered part, the difference between the refractive index of (b) the polymer obtained by polymerizing only the superimposed body temperature metal material and the refractive index of (a) the rubbery polymer is 0.02 or less. fb)
It consists of 99 to 40% by weight of a graft copolymer obtained by selecting the composition of the monomer mixture and (C) 0 to 20% by weight of a modified vinyl polymer containing a carboxyl group or an epoxy group, and (A This is a thermoplastic resin composition characterized in that the difference in refractive index between two or three components of component ), component fB), or component (C) is 0.02 or less.

The present invention will be explained in detail below.

The (a) aminocarboxylic acid or lactam having 6 or more carbon atoms, which is a component of the polyether ester amide (A) in the present invention, is ω-aminocaproic acid, ω-
Aminocarboxylic acids such as aminoenanthic acid, ω-aminocaprylic acid, ω-aminobergonic acid, ω-aminecapric acid and 11-aminoundecanoic acid, 12-aminododecanoic acid, or caprolactam, enantholactam,
Lactams such as capryllactam and laurolactam are used, and caprolactam is particularly preferably used. 'Also, a small amount of a salt of hexamethylenediamine-isophthalic acid may be used as long as it does not impair the effects of the present invention. Component (a), the aminocarboxylic acid or lactam having 6 or more carbon atoms, is 10 to 60% by weight, preferably 20 to 50% by weight of the polyetheresteramide structural unit.
If it is less than 10% by weight, the mechanical properties of the polyetheresteramide will be poor, and if it exceeds 60% by weight, the transparency of the polyetheresteramide will deteriorate, which is not preferred.

(^) It is a constituent component of polyether ester amide (
8) Polyethylene glycol and/or polypropylene oxide glycol include polyethylene glycol, poly(1,2-propylene oxide) glycol, poly(1,3-propylene oxide) glycol, and block or random copolymers of ethylene oxide and propylene oxide. Among polymers, polyethylene glycol is particularly preferably used from the viewpoint of antistatic properties. The number average molecular weight of polyethylene glycol and/or polypropylene oxide glycol is 200 to 2.0
00, especially used in the range of 400 to t, ooo,
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 transparency of the resulting polyether ester amide will deteriorate, which is not preferable.

(A) Constituent component of polyether ester amide
(C) Aromatic dicarboxylic acids and/or alicyclic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2
Aromatic dicarboxylic acids such as , 7-dicarboxylic acid, diphenyl-4,4-dicarboxylic acid, diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate, 1
．． 4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4°
- alicyclic dicarboxylic acids such as dicarboxylic acids are used,
In particular, terephthalic acid, isophthalic acid, and 1,4-cyclohexanedicarboxylic acid are preferably used from the viewpoint of polymerizability, color tone, and transparency.

(b) Polyethylene glycol and/or polypropylene oxide glycol and (C) dicarboxylic acid react in a molar ratio of 1:1, but l@l of the dicarboxylic acid used! ! Depending on I, the preparation ↓ Hi 1 + 1t will be changed and supplied as appropriate.

The polyether ester derived from component [b) and component (C) has 40 to 90 polyether ester amide units.
It is used in a range of 50 to 80% by weight, and if it is less than 40% by weight, the transparency of the polyetheresteramide will be poor, and if it is more than 90% by weight, the mechanical properties of the polyetheresteramide will be poor. do not have.

Examples of the organic tin compound in the present invention include mono-n-butyl monohydroxytin oxide, mono-n-butyltin triacetate, mono-n-butyltin octylate, mono-n-butyltin monoacetate, monophenylhydroxytin oxide, and monotolyl monohydroxytin oxide. , monoalkyl or monoaryl substituted tin compounds such as monophenyltin triacetate, and dialkyl or diaryltin compounds such as dibutyltin oxide, dibutyltin dichloride, dibutyltin dilaurate, dibutyltin distearate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetate, diphenyltin oxide, etc. compounds, trialkyltin compounds such as tributyltin phthalate, tributyltin maleate, and mixtures thereof. These tin compounds include, for example, tricyclic compounds such as mono-n-butylmono-droxytin oxide, as well as compounds in which several tin compounds are condensed together. It is called mono-n-butyl monohydroxy monooxide, and the present invention also includes such derivatives.

Particularly preferred organic tin compounds include mono-n-butyl monohydroxytin oxide, monobutyl monooctylate, dibutyltin oxide, and tributyltin phthalate.

The organic titanium compound in the present invention includes tetraalkyl titanates such as tetrabutyl titanate, tetraisoglobil titanate, and tetrabutyl titanate, and compounds obtained by hydrolyzing these with a water-containing organic solvent. A particularly preferred organic titanium compound is tetrabutyl titanate.

Further, antimony oxide may be in any form of antimony trioxide, antimony tetroxide, antimony pentoxide, or a mixture thereof. Particularly preferred antimony oxide is antimony trioxide.

It is important that the polyether ester amide used in the present invention undergoes a polymerization reaction in the presence of antimony oxide with one or more selected from the above-mentioned specific mixing ratios of organotin compounds and organotitanium compounds. The weight ratio of one or more species returned from virtuous tin and organic titanium compounds to antimony oxide must be in the range of 10,010 to 40/60, preferably 10,010 to 70.
/30, particularly preferably in the range of 9515 to 80/20. Here, polyether ester amide using antimony oxide in the above ratio maintains transparency and greatly improves color tone.

If this mixing ratio becomes excessive, it is not preferable because the transparency of the polyether ester amide deteriorates.

By selecting the above polymerization components, composition, and catalyst system,
A transparent polyetheresteramide with low crystallinity can be obtained.

Polymerization of the polyether ester amide of the present invention is not particularly limited, and known methods can be used.

If the color tone fluctuates due to manufacturing conditions, it can be stabilized by adding a small amount of a phosphorus compound, such as trimethyl phosphate.

Next, the rubbery polymer (a) which is a constituent component of the graft copolymer (B) in the present invention has a glass transition temperature of 0.
℃ or less, specifically polybutadiene, polystyrene-butadiene, polyacrylonitrile-
diene rubbers such as butadiene, polyisoprene,
Examples include acrylic rubbers such as polychloroprene and polybutyl acrylate, and polyethylene-propylene-diene monomer terpolymers. These are selected so that the difference in refractive index from (A) polyetheresteramide is 0.02 or less. Here, the difference in refractive index between the two is 0.
If it exceeds 02, the transparency of the object will decrease, so f
It cannot be used heavily.

(8) The (b) (meth)acrylic acid ester monomer that is a constituent component of the graft copolymer includes ester compounds of acrylic acid and methacrylic acid such as methyl, ethyl, propyl, n-butyl, and i-butyl. Examples include.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene, and pt-butylstyrene.

Examples of vinyl cyanide monomers include acrylonitrile and methacrylonitrile.

Furthermore, vinyl monomers such as maleimide, N-methylmaleimide, N-ethylmaleimide, and N-phenylmaleimide can also be used if necessary.

The ratio of the (meth)acrylic acid ester monomer to the aromatized vinyl monomer is in the range of 100 to 40% by weight based on the total monomers.

These vinyl monomer mixtures may be grafted if the difference in refractive index between the rubbery polymer and the polymer obtained by polymerizing only the vinyl monomer mixture exceeds 0.02. This is not preferred because the transparency of the copolymer decreases.

The refractive index of a matrix resin made only of a monomer mixture can be determined by calculation from a theoretical formula or by measuring the refractive index of a resin obtained by polymerizing a monomer mixture having the same composition in advance.

(B) The graft copolymer is composed of 1 to 80 parts by weight of a rubbery polymer, preferably 10 to 60 parts by weight, and a total of 100 parts of a (meth)acrylic acid ester monomer and an aromatic vinyl monomer.
-40% by weight and 0-60% by weight of vinyl polymer
99 to 20 parts by weight of a monomer mixture consisting of 99 to 20 parts by weight, preferably 9
It can be obtained in an amount of 0 to 40 parts by weight by a known polymerization method, such as a method of carrying out emulsion graft polymerization by continuously supplying a monomer mixture, a polymerization initiator, and an emulsifier in the presence of a rubbery polymer latex.

([3) If the proportion of the rubbery polymer in the graft copolymer is less than 80 parts by weight, a composition with insufficient M wall resistance will be obtained, and if it exceeds 80 parts by weight, the grafting rate will be low, resulting in a rubbery polymer. This is not preferable because the polymer has poor dispersion and reduces transparency and impact resistance.

A part of this graft copolymer (B) is mixed with other vinyl polymers, such as styrene-acrylonitrile-methyl methacrylate copolymer and styrene-methyl methacrylate copolymer, in order to dilute the concentration of the rubbery polymer. It can be replaced with polymers, etc. However, when the vinyl polymer used here is blended, the ratio of rubber to the total thermoplastic resin composition is preferably in the range of 1 to 40% by weight, and the refractive index of the vinyl copolymer is , (B) The difference in refractive index from the graft copolymer is preferably 0.02 or less.

In the present invention, it is important that the difference in refractive index between (A) polyether ester amide and (B) graft polymer is 0.02 or less.

If the difference in refractive index exceeds 0.02, it is not preferable because the transparency of the resin composition decreases.

(C) Modified vinyl polymer containing a carboxyl group or epoxy group (hereinafter referred to as modified vinyl polymer) used in the present invention is a polymerization or copolymerization of one or more vinyl monomers. It is a polymer having a structure obtained by the following methods and having a carboxyl group or an epoxy group in the molecule.

Here, the carboxyl group may be an anhydride carboxyl group.The content of these carboxyl groups or epoxy groups may be very small, or may be contained in large amounts as long as the performance as a resin is not impaired.

Generally, on average, each molecule of the modified vinyl polymer contains substantially 1
The effects of the present invention can be efficiently exhibited if the polymer contains at least 10 carboxyl groups or epoxy groups. (C) There are no particular restrictions on the method of introducing carboxyl groups into the modified vinyl polymer, but ■ carboxyl groups or anhydrous acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, and itaconic acid A method of copolymerizing a vinyl monomer having a carboxyl group with a predetermined vinyl monomer, ■γ, γ-azobis(γ-cyatubaleic acid)
, α, α゛-7zobis(α-thia)ethyl-p-benzoic acid and carboxyl group-containing polymerization initiators such as succinic acid peroxide and/or thioglycolic acid, α-mercaptopropionic acid, β-mercaptopropion acid, α
- A method of (co)polymerizing a predetermined vinyl monomer using a polymerization degree regulator having a carboxyl group such as mercapto-isobutyric acid and 2,3 or 4-mercaptobenzoic acid; A method of saponifying a (co)polymer of (meth)acrylic acid ester such as butyl acrylate with an alkali can be used.

There are no particular restrictions on the method of introducing an epoxy group into the vinyl polymer (C), but examples include the following general formula (wherein R is substituted with a hydrogen atom, a lower alkyl group, or a glycidyl ester group). (It is a lower alkyl group.)
The compound represented by, specifically glycidyl acrylate,
A method of copolymerizing glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, etc. with a predetermined vinyl monomer can also be used.

(C) There are no particular restrictions on the monomers used in the polymerization of the modified vinyl polymer, such as aromatic vinyl monomers such as styrene and α-methylstyrene, and cyanide such as acrylonitrile and methacrylonitrile. Vinyl monomers, (meth)acrylic acid ester monofitK such as methyl methacrylate and butyl acrylate, alpha, beta-unsaturated carboxylic acids (anhydrides) such as maleic acid and maleic anhydride, maleimide, N -Maleimide monomers such as phenylmaleimide, olefins such as ethylene and propylene
One or more types of vinyl monomers such as vinyl monomers and vinyl monomers such as vinyl chloride, vinyl acetate, and butadiene may be selected and used depending on the purpose.

In particular, the mechanical properties of resin compositions that allow the use of aromatic vinyl monomers such as styrene, (meth)acrylic acid ester monomers such as methyl methacrylate, and cyanide vinyl monomers such as acrylonitrile are particularly important. It is preferably used because of its excellent properties. In addition, if necessary, polybutadiene, acrylonitrile/butadiene copolymer (NBR)
Rubber-like polymers such as , styrene/butadiene copolymer (SBR), polybutyl acrylate, and ethylene/propylene/diene rubber (EPDM) can also be used in combination with the above-mentioned vinyl monomer.

(C) The modified vinyl monomer is selected such that the difference in refractive index between the polyether ester amide (A) and the graft copolymer (B) is 0.02 or less. Become.

If the difference in refractive index between the modified vinyl polymer and the polyether ester amide (A) and the graft copolymer (B) exceeds 0.02, this is not preferred because the transparency of the resin composition will decrease.

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

The thus obtained polymer contains (A) 1 to 40% by weight of polyether ester amide and (B) 99 to 40% by weight of graft copolymer.
40% by weight and (C) modified vinyl polymer in a range of 0 to 20% by weight.

(A) If the polyether ester amide content is less than 1% by weight, the antistatic properties of the resin composition will be insufficient, and if it exceeds 40% by weight, the resin composition will become flexible and have poor mechanical properties, which is not preferable.

If the resin composition of the present invention utilizes (C) a modified vinyl-based heavy body, it can maintain transparency and antistatic properties, and also maintain mechanical properties such as impact resistance and both (A) and (B). The compatibility of the components can be further improved.

However, if the blending amount exceeds 20% by weight, the appearance of the molded product will deteriorate, which is not preferable.

There is no particular requirement regarding the method for producing the resin composition of the present invention. For example, using a Banbury mixer, roll extruder, etc., (A) polyether esteramide and (B)
It is manufactured by kneading a graft copolymer or a modified vinyl polymer (C).

In addition, antistatic properties may be further improved by adding antistatic agents such as metal salts of sulfonic acid and anionic, cationic, and nonionic surfactants within a range that does not impair the transparency of the resin composition. Furthermore, various stabilizers such as antioxidants and ultraviolet absorbers, pigments, dyes, lubricants, and plasticizers may be added as necessary.

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

Izot impact strength A S TM [+256-5
64 Tensile Strength A STM 0638
Volume specific resistivity Measured using a 2t×40fflIφ disk at a room temperature of 23° C. and a humidity of 50% R1+ atmosphere. For the measurement, a super insulation resistance meter 314-10E manufactured by Toa Denpa Kogyo Co., Ltd. was used.

Light Transmittance Total light transmittance was measured using a 2t×40++mφ disc.

For measurement, manufactured by Toyo Seiki Co., Ltd. Using a direct reading haze meter Ta.

Color tone The molded product was visually observed.

The appearance of the molded product was determined by visual inspection of the test piece. ◎: Very good appearance, ○: Good, ×: The surface of the molded product was damaged and was judged as defective.

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

Reference example (1) (A) Preparation of polyether ester amide (1)
(A) Preparation of polyether ester amide A-1: ε-
45 parts of caprolactam, 45.21 parts of polyethylene glycol with a number average molecular weight of 600, 13.0 parts of terephthalic acid.
3 parts and 0.0 parts of "Irganox" 1098 (antioxidant).
2 parts and 0.085 parts of mono-n-butyl monohydroxytin oxide catalyst, 0.015 parts of antimony trioxide catalyst
The mixture was charged into a reaction vessel equipped with a helical ribbon stirring blade, and the mixture was replaced with nitrogen and heated and stirred at 260°C for 60 minutes to make a transparent homogeneous solution.
Polymerization was carried out for 4 hours under conditions of Hg or less to obtain a viscous and transparent polymer. Pellet-shaped polyether ester amide (A-1) is prepared by ridge-shaping the polymer on a cooling belt and pelletizing it. This polyether ester amide is crystal-free even after being left at room temperature for 200 days. Remained transparent.

Part A-2 Polyether ester amide (A
-2) was prepared. When the transparency of this polyether ester amide was confirmed in the same manner as A-1, the transparency became poor due to the catalytic effect.

A-3: ε-caprolactam 45 parts, number average molecular weight 1
．． Polyether ester amide (A-3) was prepared in the same manner as A-1 except that 48.67 parts of polyethylene glycol 000 and 8.42 parts of terephthalic acid were used. The transparency of this polyether ester amide was checked in the same manner as A-1, and it remained transparent.

A-4: ε-caprolactam 45 parts, number average molecular weight 60
A polyether ester amide (A-4) was prepared under the same conditions as A-1 except that 46.48 parts of polyethylene glycol and 12.03 parts of adipic acid were used. When the transparency of this polyether ester amide was checked in the same manner as A-1', it was found that crystallization progressed and the transparency deteriorated significantly.

(2) (B) Preparation of graft copolymer B-1 = Polybutadiene latex (rubber particle size 0.2
60 parts of a monomer mixture consisting of 72% methyl methacrylate, 24% styrene, and 4% acrylonitrile were emulsion polymerized in the presence of 40 parts (solid content equivalent) (gel content 80%). The obtained graft copolymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to prepare a powdery graft copolymer (B-1).

B-2 = 60° 4% methyl methacrylate in the presence of 50 parts (solid content equivalent) of styrene-butadiene copolymer latex (styrene copolymer JL 20%, rubber particle size 0.25μ, gel content 78%); After emulsion polymerizing 50 parts of a monomer mixture consisting of 39.6% styrene, a powdery graft copolymer (B-2) was prepared in the same manner as B-1.

B-3: 7 parts of methyl methacrylate in the presence of 90 parts of the polybutadiene latex (calculated as solid content) used in B-1.
After emulsion polymerization of 10 parts of a monomer mixture consisting of 2% styrene, 24% styrene, and 4% acrylonitrile, a powdery graft copolymer (B-3) was prepared in the same manner as B-1.

After emulsion polymerizing a weight-temperature polymer consisting of 60% methyl methacrylate and 34% styrene in the presence of 60 parts of glass (solid content [I), a powdery graft copolymer ( Prepare B-4).

B-5: A powdery graft copolymer (B-5) was prepared in the same manner as B-1 except that the monomers in B-1 were 72 parts of styrene and 28 parts of acrylonitrile.

<3) (C) Preparation of modified vinyl polymer C-1 = 68 parts of methyl methacrylate, 23 parts of styrene, 4 parts of acrylonitrile, and 5 parts of methacrylic acid were suspended to produce a modified vinyl polymer (C-1 ) was prepared.

C-2: 58 parts of methyl methacrylate, 39 parts of styrene,
Glycidino methacrylate and 3 parts L! A modified vinyl polymer (C-2) was prepared by turbidity polymerization.

(4) (D) Preparation of copolymer D-1: 72 parts of methyl methacrylate, 24 parts of styrene,
A copolymer (D-1>) was prepared by copolymerizing 4 parts of acrylonitrile and 4 parts of acrylonitrile.

D-2=60.4 parts of methyl methacrylate, 39 parts of styrene
, 6 parts were copolymerized to prepare a copolymer (D-2).

D-3: A copolymer (D-3) was prepared by copolymerizing 50 parts of methyl methacrylate and 50 parts of styrene.

D-4: A copolymer (D-4) was prepared by copolymerizing 72 parts of styrene and 28 parts of acrylonitrile.

Examples 1 to 7 (A) polyether ester amide prepared in Reference Example,
(B) Graft copolymer, (C) modified vinyl polymer, and (D) copolymer were mixed at the compounding ratio shown in Table 1, and melt-kneaded at a resin temperature of 200°C using a vented 40 mm diameter extruder. ,
A test piece was molded using an injection molding machine that produced a pellet by extrusion at a cylinder temperature of 230°C and a mold temperature of 60°C, and each physical property was measured.

The measurement was carried out under the following conditions.

(1) Immediately after molding, wash with detergent "Mama Lemon" (manufactured by Lion Yushi Co., Ltd.) aqueous solution, then thoroughly wash with distilled water, remove surface moisture, and then store at 50% RH 123℃ for 2 hours.
The humidity was adjusted for 4 hours and then measured.

(2) After molding, 50% R11, left at 23℃ for 200 days, washed with a detergent "Mama Lemon" aqueous solution, and then thoroughly washed with distilled water to remove surface moisture.
%R1+, measured at 23° C. for 24 hours. The measurement results are shown in Table 2.

Comparative Examples 1 to 10 (A) polyether ester amide prepared in Reference Example,
(B) Graft copolymer and (D) copolymer were mixed at the blending ratio shown in Table 1, and each physical property was measured in the same manner as in Example 1. The measurement results are shown in Table 2.

The following is clear from the results in Table 2. The resin compositions of the present invention (Examples 1 to 7) all have excellent mechanical properties such as transparency and impact strength, and low specific volume resistivity. Furthermore, the resistance value hardly changes even after surface cleaning or changes over time, and it exhibits excellent permanent antistatic properties. Moreover, the appearance of the molded product is also extremely good.

That is, the resin composition of the present invention is a composition that has excellent mechanical properties, permanent antistatic properties, transparency, and a color tone close to colorless, and provides an extremely good appearance of molded products.

On the other hand, the blending amount of (A) polyether ester amide is 1
If it is less than % by weight (Comparative Example 1), antistatic property (resistivity)
If it exceeds 40% by weight (Comparative Example 2), the tensile yield stress and flexural modulus are poor.

When the amount of modified vinyl polymer (C) containing caroxyl groups or epoxy groups exceeds 20% by weight (
In Comparative Example 3), the transparency and appearance of the molded product deteriorated.

When the graft copolymer (B) containing more than 80 parts by weight of rubber polymer is used (Comparative Example 4), the dispersion of the graft copolymer is poor and the appearance of the molded product is impaired. When using (A) polyether ester amide (A) copolymerized using an aliphatic dicarboxylic acid as a polyether ester forming component, <A) polyether ester amide and (B)
When the difference in refractive index between the graft copolymer and the (D) copolymer exceeds 0.02, and when antimony oxide is excessive in the ratio of organotin compound or organotitanium compound/antimony oxide (Comparative Example 5) -10) are not preferred because transparency or color tone is significantly impaired.

<Effects of the Invention> The present invention has made it possible to efficiently obtain a thermoplastic resin composition that has transparency and permanent antistatic properties, as well as excellent Wt impact resistance and bending elasticity.

Claims (1)

Scope of Claims: (A) (a) aminocarboxylic acid or lactam having 6 or more carbon atoms, (b) polyethylene glycol and/or polypropylene oxide glycol having a number average molecular weight of 200 to 2,000, and (c) aromatic dicarboxylic acid and/or alicyclic dicarboxylic acid in a weight ratio of 100/
A polyether ester amide obtained by polymerization in the presence of one or more selected from 0 to 40/60 organic tin compounds and organic titanium compounds/antimony oxide, and the polyether ester unit is 40 to 90% by weight. In the presence of 1 to 40% by weight of a transparent polyether ester amide and 1 to 80 parts by weight of (B) (a) rubbery polymer (
b) Monomer mixture 99 to 99% consisting of a total of 100 to 40% by weight of (meth)acrylic acid ester units and aromatic vinyl monomers and 0 to 60% by weight of vinyl cyanide monomers
When graft polymerizing 20 parts by weight, the difference between the refractive index of (b) the polymer obtained by polymerizing only the monomer mixture and the refractive index of (a) the rubbery polymer is 0.02 or less ( b)
99 to 40% by weight of a graft polymer obtained by selecting the composition of the monomer mixture and (c) 0 to 20% by weight of a modified vinyl polymer containing a carboxyl group or an epoxy group, and (A) component , a thermoplastic resin composition characterized in that the difference in refractive index between two or three components of component (B) or component (C) is 0.02 or less.