JPH072885B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention has excellent antistatic properties, mechanical properties represented by impact resistance, excellent surface gloss of molded articles, and prevention of delamination. The present invention relates to a thermoplastic resin composition having excellent properties.

[Conventional technology]

Synthetic polymeric materials are used in a wide range of fields because of their excellent properties. If these materials are provided with antistatic properties in addition to the mechanical strength of the materials, their applications can be further expanded. In other words, it is possible to expand the application to copying machines, electronic / electromechanical parts such as televisions, various dustproof parts, etc., in which it is desired to prevent failures due to static electricity.

As a method for improving the antistatic property of a synthetic polymer material, a hydrophilic rubber-like polymer obtained by copolymerizing a conjugated diene or / and an acrylic ester and a vinyl monomer having an alkylene oxide group is used as a vinyl polymer. A method obtained by graft-polymerizing a monomer or vinylidene monomer (JP-A-55-36)
237), etc., and has achieved practical antistatic property.

Further, as a component similar to the component of the present invention, there is disclosed in
A composition obtained by blending a polyamide elastomer with a styrene resin disclosed in JP-A 60-170646 is mentioned, which improves the abrasion resistance of the styrene resin.

[Problems to be solved by the invention]

However, since the antistatic resin obtained by graft-polymerizing the hydrophilic rubber-like polymer described in JP-A-55-36237 mentioned above uses a special hydrophilic rubber-like polymer, its production method However, there is a drawback that the obtained resin is inferior in mechanical properties and it is not sufficiently satisfactory. Further, the composition described in JP-A-60-170646 is intended to improve wear resistance, and as an antistatic resin, layered peeling prevention property is insufficient.

An object of the present invention is to provide an antistatic resin having excellent permanent antistatic properties, and particularly excellent mechanical properties represented by impact resistance and delamination prevention properties.

[Means for solving problems]

As a result of intensive studies to solve the above-mentioned object, the present inventors melt kneaded an elastomer containing a specific amount of an alkylene oxide group unit and a rubber-modified styrenic resin, and specified a specific particle size of the elastomer in the composition. It was found that not only the above object can be efficiently achieved but also the antistatic property and the delamination preventive property can be improved remarkably by uniformly dispersing them in the present invention.

That is, the thermoplastic resin composition of the present invention comprises (A) an alkylene oxide group unit having 2 to 4 carbon atoms.
A composition comprising 10 to 90% by weight of polyether amide, 1 to 60% by weight of a polyetherester or polyetheresteramide (B) 40 to 99% by weight of a rubber-modified styrenic resin, wherein the component (A) is Are uniformly dispersed in the composition as particles, and the major axis of the particles is 0.01 to 10 µ, and the major axis / minor axis ratio is 1 to 20.

Hereinafter, the present invention will be specifically described.

Examples of the (A) polyether amide, polyether ester, or polyether ester amide containing an alkylene oxide group unit having 2 to 4 carbon atoms in the present invention include (a) a polyamide-forming component or a polyester-forming component and (b) Examples thereof include block or graft copolymers obtained by reaction with a compound having an alkylene oxide group having 2 to 4 carbon atoms.

Specifically as the (a) -1 polyamide forming component, ω
-Aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid and 11-aminoundecanoic acid, aminocarboxylic acids such as 12-aminododecanoic acid or caprolactam, enantolactam, capryl Lactams such as lactams and laurolactams and salts of diamine-dicarboxylic acids such as hexamethylenediamine-adipate, hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate and the like and mixtures thereof, especially caprolactam. , 12-aminododecanoic acid and hexamethylenediamine-adipate are preferably used.

Specific examples of the polyester-forming component (a) -2 include isophthalic acid, terephthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid and diphenyl-4,4 as dicarboxylic acids. An aromatic dicarboxylic acid such as ′ -dicarboxylic acid, diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate,
1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,3
A cycloaliphatic dicarboxylic acid and succinic acid such as cyclopentanedicarboxylic acid, 1,3-dicarboxymethylcyclohexane, 1,4-dicarboxymethylcyclohexyl and dicyclohexyl-4,4'-dicarboxylic acid, oxalic acid,
Aliphatic dicarboxylic acids such as adipic acid, sebacic acid and dodecanedioic acid (decanedicarboxylic acid) and mixtures thereof and ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2-, as an aliphatic diol.
Examples thereof include 1,3-, 2,3-, or 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, and the like, and a mixture thereof, particularly terephthalic acid, isophthalic acid, 1,4 as dicarboxylic acid. -Cyclohexanedicarboxylic acid, sebacic acid and dodecanedioic acid, and ethylene glycol, 1,2- or 1,3-propylene glycol, 1,4-butanediol as an aliphatic diol are preferably used from the viewpoints of polymerizability, color tone and physical properties.

Examples of the compound (b) having an alkylene oxide group having 2 to 4 carbon atoms used in the present invention include poly (ethylene oxide) glycol, poly (1,2-propylene oxide) glycol and poly (1,3-propylene oxide). )
Glycols, poly (tetramethylene oxide) glycols, block or random copolymers of ethylene oxide and propylene oxide or ethylene oxide and tetramethylene oxide and block or random copolymers of ethylene oxide and tetrahydrofuran and their diamines or dicarboxylic acids. Are used alone or in combination of two or more.

Among these, poly (ethylene oxide) glycol is particularly preferably used because of its excellent antistatic property. In this case, the compound having an alkylene oxide group having 2 to 4 carbon atoms has a number average molecular weight of 200 to 6000, particularly 250 to 40.
A range of 00 is preferred.

Examples of the reaction of the elastomer (A) of the present invention include:
Examples of the reaction include (a) a polyamide-forming component or a polyester-forming component and (b) a compound having an alkylene oxide group having 2 to 4 carbon atoms, and (b) having 2 carbon atoms.
Ester reaction or amide reaction is conceivable depending on the terminal group of the compound having an alkylene oxide group of ˜4.

In addition, depending on the reaction, a third compound such as dicarboxylic acid or diamine may be used.
Ingredients can also be used.

In this case, the dicarboxylic acid component has 4 to 4 carbon atoms.
Those of 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, diphenyl Aromatic dicarboxylic acids such as phenoxyethane dicarboxylic 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 dodecanedicarboxylic acid (decanedicarboxylic acid) and mixtures thereof, in particular terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, Sebacic acid, adipic acid and dodecanedioic acid are Preferably used from the viewpoint of physical properties.

Examples of the diamine component include aromatic, alicyclic and aliphatic diamines. These are used alone or in combination of two or more. Among them, the aliphatic diamine hexamethylenediamine is preferably used for economic reasons.

(B) The alkyl oxide group unit having 2 to 4 carbon atoms is a constituent unit of polyether amide, polyether ester or polyether ester amide and is used in an amount of 10 to 90% by weight, preferably 40 to 80% by weight, If it is less than 10% by weight, the antistatic property of the resin composition is inferior, and if it exceeds 90% by weight, the affinity for the rubber-modified styrenic resin is deteriorated and layer peeling occurs, which is not preferable.

Further, when a polyether amide, a polyether ester or a polyether ester amide containing an alkylene oxide group unit having more than 4 carbon atoms is used, the antistatic property is remarkably deteriorated, which is not preferable.

The relative viscosity of the component (A) polyether amide, polyether ester, or polyether ester amide is not particularly specified, but preferably 1.6 to 7.0 (0.5% o-chlorophenol solution) at 25 ° C., particularly preferably 1.7 to 2.5. Is. When the relative viscosity is 1.6 or more, the elastomer of the component (A) is likely to be uniformly dispersed in the resin composition, and the antistatic property and the delamination preventive property are further excellent. Also, the relative viscosity
In the case of 7.0 or less, the production time of the elastomer of the component (A) is short and economical.

There are no particular restrictions on the method of polymerizing the component (A) polyether amide, polyether ester, or polyether ester amide. For example, a mixture of (a) polyethylene glycol diamine, dicarboxylic acid, and aliphatic diamine may be ε.
− 220-270 ℃ under nitrogen atmosphere in the presence of caprolactam
A method of copolymerizing by heating to a temperature.

(B) The methods disclosed in JP-A-56-65026 and JP-A-52-27497 can be used.

Examples of the (B) rubber-modified styrene resin in the present invention include rubber-modified polystyrene and styrene-rubber polymer-
Examples thereof include acrylonitrile copolymer (ABS resin, AES resin, AAS resin), styrene-rubbery polymer-methyl (meth) acrylate (MBS resin), and the like. The modification by the rubber material is one part modification, and the component (B) of the present invention is precisely a mixture of the rubber polymer and another styrene polymer. Therefore, a so-called diluted product obtained by further mixing the component (B) with a styrene resin can also be used as the component (B). Two or more of these may be used. Furthermore, some of these styrene and / or acrylonitrile residues may be replaced with α-methylstyrene, p-methylstyrene, pt-butylstyrene, (meth) acrylic acid or their methyl, ethyl, propyl, n-butyl, etc. Substituted with ester compounds, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, maleimide-based monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide, and vinyl-based monomers that are copolymerizable with styrene such as acrylamide. It includes those that have been done.

Further, by substituting a part of the rubber-modified styrene resin with a modified vinyl polymer containing a carboxyl group, an amide group, an epoxy group, etc., the affinity with the elastomer of the component (A) is further improved. It is also possible to improve the mechanical properties such as impact strength and the delamination prevention property.

Examples of the modified vinyl polymer containing a carboxyl group, an amide group, an epoxy group and the like include unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid and maleic anhydride, and unsaturated compounds such as (meth) acrylamide. Initiation of polymerization having a saturated amide, at least one kind of unsaturated glycidyl such as glycidylmethacrylic acid and / or a carboxyl group such as γ, γ′-azobis (γ-cyanovaleic acid), thioglycolic acid, and α-mercaptopropionic acid Agent, a polymerization degree regulator, a predetermined vinyl monomer, for example, styrene, aromatic vinyl monomer such as α-methylstyrene, acrylonitrile, vinyl cyanide monomer such as methacrylonitrile, (Meth) acrylic acid ester-based monomers such as methyl (meth) acrylate, maleimide, N-phenyl Examples thereof include (co) polymers (co) polymerized with a maleimide-based monomer such as maleimide.

The proportion of (A) polyether amide, polyether ester, polyether ester amide and (B) rubber-modified styrenic resin in the present invention is such that (A) component is 1 to 60% by weight, preferably 5 to 40% by weight. is there.

If the amount of component (A) is less than 1% by weight, the antistatic property of the resin composition will be insufficient, and if it exceeds 60% by weight, the resin composition will be flexible and the mechanical properties will be poor, such being undesirable.

The resin composition in the present invention is manufactured by melt-kneading the mixture of the component (A) and the component (B) with a Banbury mixer, a roll, an extruder or the like.
By giving a shear rate of 10 sec ^-1 or more in the temperature range of 280 ° C to 280 ° C, the component (A) is easily dispersed in the resin composition as uniform particles, and the antistatic property and the delamination preventive property are further improved. It can be improved. The component (A) is a particle having a major axis of 0.01 to 10 µ, preferably 0.05 to 5 µ, and a major axis / minor axis ratio of 1 to 20 times, preferably 1 to 10 times.
It is necessary that they are evenly dispersed in a double form.

To control the major axis of dispersed particles to less than 0.01μ,
Since the production of the resin composition is complicated and requires a long time, the cost is high, and when it exceeds 10 μ, delamination is unfavorable.

When the major axis / minor axis ratio of the dispersed particles of the component (A) exceeds 20 times, delamination occurs, which is not preferable.

In addition, the dispersed state of the dispersed particles of the component (A) depends on the resin composition.
It can be visually determined by staining with an O ₅ O ₄ staining method and taking a transmission electron micrograph of an ultrathin section.

Other thermoplastic polymers having good compatibility with the rubber-modified styrene resin (B) of the present invention, for example, vinyl chloride resin, polyolefin resin, polyamide, polybutylene terephthalate, polyethylene terephthalate, polycarbonate, polyphenylene ether, polyglutarimide. , A styrene-butadiene block copolymer, a polyolefin elastomer modified with a carboxyl group or the like can be optionally substituted to improve the performance as a molding resin. In this case, the mixture of these polymers is referred to as component (B) in the present invention. Further, the resin composition in the present invention, 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin composition, by mixing an inorganic salt such as hydrotalcite represented by the following general formula, improvement of delamination prevention, It is also possible to improve the corrosion prevention of the molding die.

General formula [▲ M 2 ⁺ _1-x ▼ ▲ M ³⁺ _x ▼ (OH) ₂ ] x ⁺ [▲ A ^n- _{x / n} ▼
· MH ₂ O] x ^{- (wherein, M 2+: Mg 2+, Mn} 2+, Fe 2+, Co 2+, Ni 2+, Cu 2+, 2 -valent metals such as Zn ^2+.

Trivalent metals such as M ³⁺ : Al ³⁺ , Cr ³⁺ , Co ³⁺ , In ³⁺ .

^{An -: OH -, F -} , Cl -, Br -, N ▲ O - 3 ▼, C ▲ O 2- 3 ▼, S ▲ O
_{^{2- 4 ▼, Fe (CN ▲}} ) 3- 6 ▼, CH 3 COO -1, oxalate ion, n-valent anion such as Sarichin ion.

m is the number of moles of water of hydration, n is the charge on the anion A, and x is a number less than 1).

Among them, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ 3.5H ₂ O, M is preferable.
g _4.5 Al ₂ (OH) ₁₃ CO ₃ .

Furthermore, the resin composition of the present invention can be mixed with a flame retardant such as an organic halogen compound and a conductive filler to obtain a flame retardant or electromagnetic wave shielding resin composition.

The organic halogen compound has a halogen atom in the molecule and means a chlorinated or brominated organic compound which is known per se as a flame retardant. Specifically, hexapromobenzene, pentapromotoluene, hexapromobiphenyl, decapromobiphenyl, hexapromocyclodecane, decapromodiphenyl ether, hexapromodiphenyl ether, bis (pentapromophenoxy) ethane, ethylene bis- (tetrabromophthalimide), Low molecular weight organic bromine compound such as tetrabromobisphenol A, brominated polycarbonate (eg, polycarbonate oligomer produced from brominated bisphenol A as a raw material), brominated epoxy compound (eg produced by reaction of brominated bisphenol A with epichlorohydrin) Compounds obtained by reacting diepoxy compounds or brominated phenols with epichlorohydrin), poly (brominated benzyl acrylate) bromine Examples include polyphenylene ether, brominated bisphenol A, condensates of cyanuric chloride and brominated phenol, halogenated polymers and oligomers such as brominated polystyrene, and mixtures thereof. Among them, decabromodiphenyl ether, tetrabromobisphenol A, bromine. Compounded polycarbonate can be preferably used.

1 to 60 parts by weight of these flame retardants can be mixed with 100 parts by weight of the resin composition. The organohalogen compound is optionally used in combination with an antimony compound, such as antimony trioxide. Further, zirconium oxide, zinc sulfide, barium sulfate or the like may be used in combination with antimony trioxide.

Examples of the conductive filler include conductive carbon black, graphite, silver. Copper / nickel / stainless powder, tin oxide, copper-silver / nickel-silver composite powder, silver-coated glass beads, carbon balloon, aluminum flakes, stainless flakes, nickel flakes, copper flakes, stainless steel. copper. aluminum. Fibers and mixtures thereof.

These conductive fillers can be mixed in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the resin composition.

Further, the resin composition of the present invention can further improve the antistatic property by adding an antistatic agent such as a metal salt of sulfonic acid, an anionic surfactant, or a cationic surfactant, and further, if necessary. It is also possible to add various stabilizers such as antioxidants and ultraviolet absorbers, pigments, dyes, lubricants and plasticizers.

Regarding the method for producing the resin composition of the present invention, the dispersed particles of the component (A) are uniformly dispersed in the resin composition in the range of 0.01 to 10 μ in the major axis and 1 to 20 times in the major axis / minor axis ratio. There is no particular limitation as long as it is, for example, (A) polyether amide,
It is made into a product by melt-kneading a mixture of one or more of a polyether ester or a polyether ester amide and (B) a rubber-modified styrene resin with a Banbury mixer, a roll, an extruder or the like.

[Action]

In the present invention, a resin composition containing a specific alkylene oxide group unit, and melt-kneading an elastomer having a specific relative viscosity and a rubber-modified styrenic resin, and defining the dispersed particles of the elastomer in the resin composition, It has excellent permanent antistatic properties, high mechanical properties and delamination resistance. This phenomenon is presumed to be due to controlling the dispersed particles of the elastomer.

〔Example〕

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

Izod impact strength: ASTM D256-56A Tensile strength: ASTM D638 Flexural modulus: ASTM D790 Volume specific resistance value: 2t × 40 ^φ disk, room temperature 23 ℃, humidity 5
It was measured in a 0% RH atmosphere. A super insulation resistance meter SM-10 type manufactured by Toa Denpa Kogyo Co., Ltd. was used for the measurement.

Flame retardance: Vertical combustion test according to UL94 standard 1/16 ″ × 1 /
2 ″ × 5 ″ combustion test pieces were used.

Dispersibility of component (A) component elastomer: The central part of a molded product was cut out and measured with an ultrathin section transmission electron microscope photograph by an O ₅ O ₄ staining method.

Mold Corrosion: Chromium-molybdenum steel of the mold material is # 400
Put the polished material and polymer in a test tube, seal the tube under vacuum, and heat-treat at 260 ° C for 4 hours. The surface of the steel material is ◎: extremely good, ○: good, ×: markedly discolored. And

Delamination prevention property: The molded product was bent and observed by observing the fracture surface of the test piece subjected to a tensile test, and ⊚: extremely good, ◯: good, ×: the molded product causes delamination as a criterion.

Moreover, the number of parts and% in an Example show a weight part and weight%, respectively.

[Reference example]

(1) (A) Preparation of Elastomer A-1: 45 parts of caprolactam, 48.6 parts of polyethylene glycol having a number average molecular weight of 1000 and 8.4 parts of terephthalic acid, 0.2 part of "Irganox" 1098 (antioxidant) and antimony trioxide catalyst Charge into a reaction vessel equipped with a helical ribbon stirring blade together with 0.1 part, replace with nitrogen, heat and stir at 260 ° C for 60 minutes to obtain a transparent homogeneous solution, and then at 260 ° C, 0.5 mmHg
Polymerization was carried out for 4 hours under the following conditions to obtain a viscous and transparent polymer.

The polymer was discharged onto a cooling belt in a gut form and pelletized to obtain a pelletized polyether ester amide. 25 of this polyetheresteramide
Relative viscosity ηr of 0.5% o-chlorophenol solution at
It was 1.98.

A-2: Polyethylene glycol having a number average molecular weight of 4,000 was reacted with acrylonitrile and further hydrogenated to obtain polyethylene glycol diamine having amino groups at both ends. This was subjected to a salt reaction with terephthalic acid by a conventional method to obtain a 40% aqueous solution of polyethylene glycol diammonium terephthalate.

Add 200 parts of the above 40% polyethylene glycol diammonium terephthalate aqueous solution, 120 parts of 85% caprolactam aqueous solution, 16 parts of 40% hexamethylene diammonium adipate aqueous solution into a concentrated can until the internal temperature reaches 110 ° C under normal pressure. It was heated for about 2 hours and concentrated to 80% concentration. Subsequently, the above concentrated solution was transferred to the polymerization vessel, and heating was started while flowing nitrogen into the polymerization vessel.

When the internal temperature reached 120 ° C, a predetermined amount of sodium dodecylbenzenesulfonate and 1,3,5trimethyl-2,4,6-
10 parts of tri (3,5-di-t-butyl-hydroxybenzyl) benzene was added, stirring was started, and the internal temperature was raised to 245 ° C. The polymerization was completed by heating at 245 ° C for 10 hours. After completion of the polymerization, pelletized polyetheramide was obtained in the same manner as in A-1. The relative viscosity ηr of this polyetheramide was 2.1 as measured by the same method as for A-1.

A-3: dimethyl terephthalate 42.3 parts, ethylene glycol 38.8 parts, molecular weight 1000 polyethylene glycol 61.9
Parts, 0.15 parts of tetrabutyl titanate and 0.2 parts of "Irganox" 1010 (antioxidant) were charged into an esterification reaction vessel and reacted at 220 ° C for 2 hours under a nitrogen atmosphere to distill off methanol by the esterification reaction, The reaction solution was transferred to a polymerization vessel and polymerized at 250 ° C. for 4 hours under the condition of 0.5 mmHg or less. After completion of the polymerization, pelletized polyether ester was obtained in the same manner as in A-1. The relative viscosity ηr of this polyether ester was 2.05 as measured by the same method as A-1.

A-4: Polymerized in the same manner as in (A-1) except that 40 parts of lauryl lactam, 54.1 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of 1000, and 8.2 parts of adipic acid were used to give a polyether ester amide. Obtained. Relative viscosity ηr
Was 1.95.

A-5: Polyester ester amide was obtained by polymerizing by the same method as A-1 except that polyethylene glycol of A-5: A-1 was changed to poly (hexamethylene oxide) glycol. The relative viscosity of this polyetheresteramide is ηr
= 2.01.

A-6: Polymerization was carried out in the same manner as in (A-1) except that 95 parts of ω-aminodecanoic acid, 4.2 parts of polyethylene glycol having a number average molecular weight of 1000 and 1.0 part of dodecanedioic acid were used to obtain a polyether ester amide. . The relative viscosity ηr was 1.83.

(2) (B) Preparation of rubber-modified styrene resin (i) Master resin (b) b-1: Polybutadiene latex (rubber particle diameter 0.25 μ,
Styrene in the presence of 60 parts (gel content 80%) (solid content conversion)
40 parts of a monomer mixture consisting of 70% and 30% acrylonitrile was emulsion polymerized.

The obtained graft copolymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, dried and dried to prepare a powdery graft copolymer.

b-2: 60 parts of a monomer mixture consisting of 72% of methyl methacrylate, 24% of styrene and 4% of acrylonitrile was emulsion polymerized in the presence of 40 parts of the polybutadiene latex used in b-1 (in terms of solid content), A powdery graft copolymer was prepared in the same manner as in b-1.

b-3: 10 parts of diene NF35A (manufactured by Asahi Kasei Co., Ltd.) with 9 parts of styrene
After dissolving in 0 part, bulk polymerization was performed to prepare a graft polymer.

(Ii) Blend resin (b ') b'-1: 72 parts of styrene and 28 parts of acrylonitrile were copolymerized to prepare a copolymer.

b'-2: 72 parts of methyl methacrylate, 24 parts of styrene, and 4 parts of acrylonitrile were copolymerized to prepare a copolymer.

b'-3: 50 parts of styrene, 30 parts of N-phenylmaleimide,
A copolymer was prepared by copolymerizing 20 parts of acrylonitrile.

b′-4: 70 parts of styrene, 25 parts of acrylonitrile, and 5 parts of methacrylic acid were suspension-polymerized to prepare a bead-shaped modified vinyl polymer.

b′-5: 70 parts of methyl methacrylate, 24 parts of styrene, 4 parts of acrylonitrile, and 2 parts of acrylic acid were subjected to suspension polymerization to prepare a bead-shaped modified vinyl polymer.

b'-6: 95 parts of styrene and 5 parts of methacrylic acid were subjected to suspension polymerization to prepare a bead-shaped modified vinyl polymer.

b'-7: Lexan 121-111 (polycarbonate manufactured by EPL) was used.

b'-8: CPX-100L (polyphenylene ether manufactured by Mitsubishi Gas Chemical Co., Inc.) was used.

Examples 1 to 11 (A) Polyether amide, polyether ester, polyether ester amide prepared in Reference Example, (B) rubber-modified styrenic resin as master resin (b) and blend resin (b ') are shown. Pellets were produced by mixing in the compounding ratio shown in No. 1 and melt-kneading and extruding with a vented 40 mmφ extruder at the extrusion temperature shown in Table 1.

Then, a test piece was molded with an injection molding machine at a linder temperature of 220 ° C and a mold temperature of 60 ° C, and each physical property was measured. The volume resistivity value was measured under the following conditions using a 2 mm thick disk injection-molded.

(1) Immediately after molding, wash with an aqueous solution of the detergent "Mama Lemon" (manufactured by Lion Oil and Fats Co., Ltd.), then thoroughly wash with distilled water to remove surface water, and then at 24% at 50% RH and 23 ° C. The humidity was measured with time.

(2) After molding, leave it in 50% RH, 23 ° C for 200 days, then wash with an aqueous solution of "Mama Lemon" detergent, then thoroughly wash with distilled water to remove surface moisture, then 50% RH,
The humidity was measured at 23 ° C. for 24 hours for measurement.

The measurement results are shown in Table 2. In addition, a micrograph (10,000 times) of Example 2 is shown in FIG. In FIG. 1, what is seen as an ellipse (black or white) is an elastomer of component A, what is seen as a circle is a rubbery polymer, and the continuous layer is a styrene / acrylonitrile polymer.

Comparative Examples 1 to 8 (A) Polyetheramides, polyetheresters, polyetheresteramides, and (B) rubber-modified styrenic resins prepared in Reference Examples are shown as master resins (b) and blend resins (b '). Mixing was carried out at the compounding ratio shown in 1 and each physical property was measured in the same manner as in the examples.

The measurement results are shown in Table 2.

A micrograph (10,000 times) of Example 5 is shown in FIG. In Figure 2, what looks like an amorphous band is A
It is an elastomer of the component.

From the results of Table 2 and FIGS. 1 and 2, the following is clear. The resin compositions of the present invention (Examples 1 to 11) are representative of impact strength, tensile properties, and flexural modulus by defining dispersed particles of the component (A) elastomer within a certain range in the resin composition. The mechanical properties and the delamination preventive property are well balanced and have a low volume resistivity value. Moreover, the resistance value hardly changes due to surface cleaning or aging, and excellent permanent antistatic property is exhibited.

That is, the resin composition of the present invention has excellent mechanical strength,
Combines layered peeling prevention and permanent antistatic properties.

On the other hand, when the amount of the elastomer as the component (A) is less than 1 part by weight (Comparative Example-1), the antistatic property (resistance value) is poor,
When it exceeds 60 parts by weight (Comparative Examples-2 and 6), the tensile yield stress and flexural modulus are poor.

When the major axis of the dispersed particles of the elastomer of the component (A) exceeds 10 μ and the major axis / minor axis ratio exceeds 20 (Comparative Example-5), the delamination prevention property is deteriorated, which is not preferable.

When the elastomer of component (A) containing alkylene oxide group units having more than 4 carbon atoms or the elastomer of component (A) having less than 10% by weight of alkylene oxide group units having 2 to 4 carbon atoms is used (Comparative Example- 3,4) is inferior in antistatic property. The resin compositions (Comparative Examples-7 and 8) containing no component (A) elastomer are not preferable because they have high resistance and poor antistatic properties.

〔The invention's effect〕

The thermoplastic resin composition of the present invention is excellent in both permanent antistatic properties, mechanical properties such as impact resistance, and delamination prevention properties.

[Brief description of drawings]

FIG. 1 is an electron micrograph of the particle structure of the composition obtained in Example 2 of the present invention, and FIG. 2 is an electron micrograph of the particle structure of the composition obtained in Comparative Example 5.

Claims (2)

[Claims] 1. (A) 1 to 60% by weight of a polyether amide, polyether ester or polyether ester amide containing 10 to 90% by weight of an alkylene oxide group unit having 2 to 4 carbon atoms, and (B) a rubber substance. A composition comprising 40 to 99% by weight of a modified styrenic resin, wherein the component (A) is uniformly dispersed in the composition as particles, and the major axis of the particles is 0.01 to 10 μm.
A thermoplastic resin composition having a ratio of major axis / minor axis of 1 to 20. 2. The relative viscosity ηr of the component (A) resin is 1.6 to 7.0.
The thermoplastic resin composition according to claim 1, which is (0.5%, o-chlorophenol solution, 25 ° C).