JP2773806B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic resin composition having permanent antistatic properties, excellent mechanical properties such as impact resistance, and excellent moldability.

[0002]

2. Description of the Related Art Thermoplastic resins represented by polyolefin resins such as polyethylene and polypropylene, polyamide resins, polyester resins, styrene resins, polyoxymethylene resins and the like are used in copiers, televisions and the like. It is widely used for electronic and electromechanical parts. Conventionally, the resin used for these components has a problem in products because static electricity is easily generated.

Accordingly, as a resin having improved antistatic properties, a hydrophilic rubber-like polymer obtained by copolymerizing a conjugated diene and / or an acrylic acid ester with a vinyl monomer having an alkylene oxide group, There is a resin composition obtained by graft polymerization of a vinyl monomer or a vinylidene monomer (JP-A-55-36237) and the like, which has reached a practical antistatic property.

Japanese Patent Application Laid-Open No. 1-163234 discloses that a modified olefin polymer containing 1 to 40 parts by weight of a polyetheresteramide, 20 to 98 parts by weight of a polyolefin, and a functional group containing a functional group such as a carboxyl group. It is disclosed that by mixing parts by weight, a resin composition having permanent antistatic properties can be obtained.

Japanese Patent Application Laid-Open No. 2-58566 discloses a modified polyamide obtained by polyaddition of ethylene oxide to 1 to 99% by weight of a thermoplastic resin and aliphatic polyamide.
It discloses that a resin composition having a permanent antistatic property can be obtained by mixing up to 1% by weight.

However, the above-mentioned Japanese Patent Application Laid-Open No. 55-362 discloses
No. 37, the antistatic resin obtained by graft-polymerizing a monomer to a hydrophilic rubber-like polymer uses a special hydrophilic rubber-like polymer. There are drawbacks such as complexity and poor mechanical properties of the obtained resin, which are not satisfactory.

Further, the antistatic resin composition disclosed in Japanese Patent Application Laid-Open No. 1-163234 has a problem that the melt viscosity of the constituent polyetheresteramide is low, so that the compatibility with the polyolefin is not sufficient. is there.

Further, the antistatic resin composition disclosed in Japanese Patent Application Laid-Open No. 2-58566 has a problem that when poly (ethylene oxide) is added to polyamide, the melt viscosity of the resulting modified polyamide becomes abnormally high. . When the modification rate is increased, this is particularly remarkable, so that there is a disadvantage that the compatibility and fluidity of the resin composition are poor, and the resin composition is not sufficiently satisfactory in terms of moldability.

The present invention provides a resin composition having permanent antistatic properties, excellent mechanical properties typified by impact resistance, excellent color tone, and excellent moldability irrespective of a complicated production method. The purpose is to provide.

The present inventor has previously found that a resin composition of a styrene resin and a specific modified polyetheramide solves the above problems, and has already filed an application (Japanese Patent Application No. 3-1).
No. 2399).

As a result of further study on this point, it was found that a resin composition comprising a thermoplastic resin excluding a styrene resin and the above-mentioned specific modified polyetheramide and a new specific modified polyamide elastomer were used. The present inventors have found that the resin composition also solves the above problems, and have reached the present invention.

[0012]

[Means for solving the problems]

[Constitution of the Invention] The present invention relates to (A) a thermoplastic resin excluding a styrene resin , and (B) a polyamide elastomer selected from polyetheramide, polyetheresteramide, and polyesteramide, and 1,2-alkylene. It is a thermoplastic resin composition comprising a modified polyamide elastomer obtained by graft polymerization of an oxide.

[0014]

Hereinafter, the present invention will be described specifically. The thermoplastic resin (A) in the present invention is not particularly limited, but includes a polyamide resin, a polyester resin, a polycarbonate resin, a polyphenylene ether resin,
Examples include polyolefin-based resins, halogenated (mono) olefin-based resins, polyglutarimide-based resins, polyoxymethylene-based resins, polyphenylene sulfide-based resins, acrylic resins, and the like, and resin blends thereof.

Specifically, as the polyamide resin,
Nylon 6, nylon 6.6, nylon 6.6, nylon 11, nylon 12, nylon 612 and the like.

As the polyester resin, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene-1,2-bis (phenoxy) ethane-4,4'- Copolyesters such as dicarboxylate, polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / decanedicarboxylate, and the like can be mentioned.

Examples of the polycarbonate resin include an aromatic polycarbonate, an aliphatic polycarbonate, and an aliphatic resin.
Aromatic polycarbonate and the like can be mentioned. In general, polymers comprising bisphenols such as 2,2-bis (4-oxyphenyl) alkane, bis (4-oxyphenyl) ether, bis (4-oxyphenyl) sulfone, sulfide and sulfoxide, or copolymers thereof It is a polymer using bisphenols substituted with halogen depending on the purpose. The polyphenylene ether-based resin includes a homopolymer or a copolymer having a unit represented by the following formula [I].

[0019]

Embedded image (Where Q ₁ , Q ₂ , Q ₃ and Q ₄ are each independently selected from the group consisting of hydrogen, halogen, hydrocarbon, halohydrocarbon, hydrocarbonoxy and halohydrocarbonoxy, and n is It represents the total number of monomer units and is an integer of 20 or more.)

The polyphenylene ether resin is
Also included are those modified with unsaturated dicarboxylic acids and unsaturated dicarboxylic anhydrides.

Examples of the polyolefin resin include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-1-butene copolymer, and polyisobutylene.

Examples of the halogenated (mono) olefin resin include polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polychlorotrifluoroethylene and the like.

The polyglutarimide resin is represented by the following formula [I
A polymer or copolymer containing a cyclic imide unit represented by formula (I) and a blend thereof.

[0024]

Embedded image (However, R ¹ , R ² and R ³ in the formula each represent hydrogen, a substituted or unsubstituted alkyl or aryl group having 1 to 20 carbon atoms.) Any polyglutaryl unit containing the above cyclic imide unit Although an imide can be applied to the present invention, usually, R ¹ and R ² in the above cyclic imide unit are hydrogen or a methyl group, and R ³ is a hydrogen, a methyl group, an ethyl group, a propyl group, What is a butyl group or a phenyl group is generally used.

The polyoxymethylene resin is an oxymethylene homopolymer or an oxymethylene resin mainly containing oxymethylene units and containing not more than 15% by weight of oxyalkylene units having 2 to 8 adjacent carbon atoms in the main chain. It means a methylene copolymer.

The polyphenylene sulfide resin is a polymer containing a repeating unit represented by the following formula [III] in an amount of 70 mol% or more, a blend thereof, a glass-reinforced material, and the like.

[0027]

Embedded image The acrylic resin is a (co) polymer of an alkyl ester compound such as methyl, ethyl, propyl and butyl of (meth) acrylic acid. Specifically, polymethyl methacrylate, polyethyl methacrylate, polymethacrylic acid Propyl, polymethyl acrylate, polyethyl acrylate,
Methyl methacrylate-ethyl methacrylate copolymer, methyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-methyl acrylate copolymer, methyl methacrylate-ethyl acrylate copolymer, methyl methacrylate-acrylic acid Butyl copolymer and the like.
One or two or more of these acrylic resins can be used.

The method for producing the thermoplastic resin (A) in the present invention is not particularly limited, and a known production method can be used. For example, polyphenylene ether is disclosed in U.S. Pat.
Nos. 06874 and 3306875 and U.S. Pat. Nos. 3,257,357 and 32.
It can be produced by the reaction of phenols according to the procedure described in US Pat.

The modified polyamide elastomer (B) in the present invention is obtained by graft-polymerizing (B ₂ ) 1,2-alkylene oxide onto a polyamide elastomer selected from (B ₁ ) polyetheramide, polyetheresteramide and polyesteramide. Alkylene oxide-grafted polyetheramides, polyetheresteramides, and polyesteramides.

(B ₁ ) Polyetheramide, polyetheresteramide and polyesteramide are produced by a known method. The method for producing polyether amide is described, for example, in JP-B-45-7559 and JP-A-55-11892.
4, JP-B-62-50495, JP-A-59-13162
8, JP-A-59-133224, JP-B-63-5553
5, JP-B-63-456 and JP-B-63-20254. That is, basically, (a) a polyamide-forming monomer, and (b) a polyether having an amino terminal group and / or a carboxyl terminal group (b ₁ ,
b ₂ to), (aliphatic substantially equal amounts in the end groups of c) (b), and dicarboxylic acids (c ₁ selected from alicyclic and aromatic dicarboxylic acids and / or diamines) and / or diamine (and c ₂₎ are prepared by polycondensation as a starting material.

The method for producing polyetheresteramide is described, for example, in JP-B-56-45419 and JP-B-57-2.
4808, JP-B-63-30090, JP-B-63-45
6, which is disclosed in JP-B-63-20254. That is, basically, (a) a polyamide-forming monomer,
(B ') a polyether having a hydroxy end group, (c
₁ ) It is produced by polycondensation using a dicarboxylic acid selected from aliphatic, alicyclic and aromatic dicarboxylic acids as a starting material in substantially the same amount as the terminal group of (b ').

(A) Examples of the polyamide-forming monomer include ω-lactams, ω-aminocarboxylic acids, and salts of diamines with dicarboxylic acids. Specific examples of ω-lactam include caprolactam, enantholactam, decoloractam, undecalactam and dodecalactam. Specific examples of the ω-aminocarboxylic acid include 6
-Aminocaproic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid. Specific examples of the salt of diamine and dicarboxylic acid include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,2
4- / 2,4,4-trimethylhexamethylenediamine, 1,3- / 1,4-bis (aminomethyl) cyclohexane, bis (4,4'-aminocyclohexyl) methane, m- / p-xylylenediamine And diamines such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, and isophthalic acid And salts with such dicarboxylic acids.

(B) The polyether having an amino terminal group or a carboxyl terminal group includes ethylene oxide,
A polyether formed from a polyether-forming monomer such as propylene oxide or tetrahydrofuran into which an amino group or a carboxyl group has been introduced into a terminal by a known method is used. As a specific example, polyoxyethylene aminopropyl ether

[0034]

Embedded image (N in the above formulas is 2 to 60).

(B ') Specific examples of the polyether having a hydroxy terminal group include polyethers formed from polyether-forming monomers such as ethylene oxide, propylene oxide and tetrahydrofuran (the chain length of the polyether structural unit is 2 to 2). 60).

(C ₁ ) Specific examples of dicarboxylic acids selected from aliphatic, alicyclic and aromatic dicarboxylic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Dodecane diacid, 1,4
-Dimerized fatty acids (dimer acids) obtained by coupling cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, oleic acid, linoleic acid, linolenic acid or the like, followed by hydrogenation.

Specific examples of (c ₂ ) diamines selected from aliphatic, alicyclic and aromatic diamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylene. Diamines and dimer diamines (aminated dimers of unsaturated fatty acids such as oleic acid, linoleic acid and linolenic acid ) include the following production examples.

HOOCCH ₂ (C ₃₂ Hx) CH ₂ CO
OH (dimer acid) + NH ₃ → NCCH ₂ (C ₃₂ H
x) CH ₂ CN + H ₂ → H ₂ NCH ₂ CH ₂ (C ₃₂ H
_x) -CH 2 _CH 2 NH ₂ (dimer diamine), 2,
Aliphatic diamines such as 2,4- / 2,4,4-trimethylhexamethylenediamine; 1,3- / 1,4-bis (aminomethyl) cyclohexane, bis (4,4'-aminocyclohexyl A) cycloaliphatic diamines such as methane;
and aromatic diamines such as m- / p-xylylenediamine.

The polycondensation using each of the above-mentioned raw materials is carried out by a conventional method (for example, disclosed in the above cited publication). In the case of polyether amide, components (a), (b) and (c) may be charged together (each terminal group concentration of (b) and (c) is equivalent) for melt polycondensation, The polycondensation of components (a) and (c) first yields a polyamide having a carboxyl end group or a polyamide having an amino end group, and then these and component (b) are brought to substantially equal end group concentrations. And melt polycondensation.

[0040] Further, in the case of the polyether ester amide is similarly, component (a), (b ') and _(c 1)
May be charged together (the concentration of each terminal group of (b ') and (c ₁ ) is equivalent) and the polycondensation of the components (a) and (c ₁ ) may be used first to form a carboxyl end group. Then, a polyamide having the following formula (1) may be obtained, and then this and component (b ') may be charged so that the concentration of each terminal group becomes substantially equivalent, followed by melt polycondensation. The polycondensation is performed under reduced pressure in the presence of a known catalyst if necessary.

The proportion of the polyether segment in these polyetheramides or polyetheresteramides is preferably 5 to 85% by weight, more preferably 10 to 80% by weight.

Further, the method for producing the polyesteramide is as follows:
For example, JP-A-51-151798 and JP-B-61-368.
58. That is, (a) the polyamide-forming monomer, (c ₁ ) a hydrogenated dimerized fatty acid (dimer acid) or a liquid polybutadiene having a carboxyl terminal group, and (c ₂ ) (c ₁ ) a substantially equivalent terminal group. It is produced by a conventional polycondensation using a diamine selected from the above-mentioned aliphatic, alicyclic and aromatic diamines as a starting material.

Examples of (B ₂ ) 1,2-alkylene oxide include ethylene oxide, 1,2-propylene oxide, and 1,2-butylene oxide. And 1,2-propylene oxide are preferred.

In the present invention, (B₁For)
(B₂) Graft polymerization on nylon 6
(B₂)) Is known as a graft polymerization (for example,
H. C. Haas et al. Polym. Sci. ,1
5, 427 (1955); Ger. 956400; US
2835653; Berg. 665018; Ikemura, Taka
,18, 71 (1961); Yamaguchi et al.30, 3
31 (1973)). For example, (B₁)When
(B₂) As required under no or alkaline catalyst
Easily achieved by heating to 60-150 ° C.
You. If necessary, (B₂) 1,2-alkylene oxo
Sid is a hydrocarbon solvent such as hexane, heptane, and toluene
It is used after being dissolved in. (B₁) Is powder, pellet, etc.
Any form may be used. According to our research,
(B₁) To (B₂) Is mainly used for the graft polymerization.
(B₁The following occurs for the amide bond of ()).

[0045]

Embedded image Depending on the reaction conditions, homopolymerization of (B ₂ ) may occur. In such a case, the polymer (B ₂ ) after the reaction is washed with a solvent (for example, hot water, hot alcohol, or chloroform) of the homopolymer. Of course, this operation is unnecessary if the coexistence of the homopolymer of (B ₂ ) does not substantially hinder the operation.
Graft ratio of _{(B 1)} with respect to _{(B 2) ((B 1} ) 10
0 The grafted to the parts per weight of _{(B 2)),} but preferably 1 to 300%, particularly preferably 5 to
200%. When the graft ratio is less than 1%, the antistatic property of the final resin composition is poor. On the other hand, if the content is 300% or more, it is difficult to perform grafting, which is not practical.

The polymer thus obtained is used in an amount of 1 to 99% by weight, preferably 20 to 95% by weight of a thermoplastic resin.
% By weight of the modified polyamide elastomer (B)
It is blended so as to be in the range of 9 to 1% by weight, preferably 80 to 5% by weight.

The resin composition of the present invention comprises (A) a modified vinyl polymer containing at least one functional group selected from a carboxyl group, an epoxy group, an amino group and a substituted amino group, depending on the type of thermoplastic resin. (B) by incorporating the compound (hereinafter abbreviated as a modified vinyl polymer).
The affinity of the component with the modified polyamide elastomer is further improved, and mechanical properties such as impact resistance, and laminar peeling (thousand-turned-up) can be improved.

The modified vinyl polymer containing at least one functional group selected from a carboxyl group, an epoxy group, an amino group and a substituted amino group refers to one or more vinyl monomers. And a polymer having at least one functional group selected from the group consisting of a carboxyl group, an epoxy group and an amino group or a substituted amino group in the molecule. Regarding the content of these functional groups, it may be a very small amount,
Also, a large amount can be contained as long as the performance as a resin is not impaired.

Examples of the modified vinyl polymer containing a carboxyl group, an epoxy group, an amino group or a substituted amino group include unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, and maleic anhydride; ) At least one unsaturated amide such as acrylamide, unsaturated glycidyl such as glycidyl methacrylic acid and / or γ. Using a polymerization initiator having a carboxyl group such as γ′-azobis (γ-cyanopaleic acid), thioglycolic acid, α-mercaptopropionic acid, and a polymerization degree regulator, a predetermined vinyl monomer, for example, acrylonitrile;
Vinyl cyanide monomers such as methacrylonitrile,
(Meth) acrylate monomers such as methyl (meth) acrylate, maleimide monomers such as maleimide and N-phenylmaleimide, α-olefin monomers such as ethylene and propylene, and vinyl chloride. (Co) polymerized (co) polymers and the like.

[0050]

[0051]

When a polyolefin polymer is used, ethylene- (meth) acrylic acid copolymer, propylene- (meth) acrylic acid copolymer, ethylene-glycidyl methacrylate copolymer, propylene-glycidyl methacrylate copolymer For example, a modified vinyl polymer such as a modified vinyl polymer can be used. When a polyamide-based resin or a polyester-based resin is used, a modified vinyl-based polymer may not be particularly used.

The resin composition of the present invention can be further improved in antistatic properties by adding an antistatic agent such as a metal salt of sulfonic acid or an anionic, cationic or nonionic surfactant. In addition, if necessary, a compatibilizer such as an oligomer, an antioxidant, various stabilizers such as an ultraviolet absorber, a pigment, a dye, a lubricant, a plasticizer, a glass fiber, an inorganic filler, and a flame retardant are added. You can also.

[0054]

The thermoplastic resin composition of the present invention comprises a specific modified polyamide elastomer which imparts permanent antistatic properties to a previously applied styrenic resin (Japanese Patent Application No. 3-12399) and a new specific polyamide elastomer. Modified polyamide elastomers have been found to impart permanent antistatic properties to various thermoplastic resins, and are also excellent in mechanical properties such as impact resistance, and "unevenness" of the surface generated during injection molding,
It has excellent performance without the problem of poor appearance such as “undulation”. Therefore, the antistatic resin composition of the present invention is extremely useful as a material for electronic and electromechanical parts such as copying machines.

[0055]

EXAMPLES In order to specifically explain the present invention, reference examples, examples and comparative examples will be described below. In addition, after the resin composition finally obtained was molded by an injection molding method, various physical properties were measured by the following test methods. Izod impact strength (kg-cm / cm): ASTM
D256 Surface specific resistance (Ω): 3.2 mm ^t × 100 mm × 1
Room temperature 23 ° C, humidity 65% RH using a 00mm molded product
It measured under the atmosphere of. Half-life of charged voltage (sec): 3.2 mm ^t × 100 mm
Room temperature 23 ° C, humidity 65% RH on a × 100mm molded product
The initial voltage of 8000 V was charged in the atmosphere described above, and the time until this voltage became 1/2 was measured by a synchroscope waveform of a static honest meter. The surface condition of the molded product was determined by molding a molded product of 30 mm × 100 mm × 3 mm by injection molding and visually observing the presence or absence of a rough surface condition such as “unevenness” or “undulation” on the surface.

Reference Example (A-1): Preparation of Polyester Resin UBE PBT 1000 (manufactured by Ube Industries, Ltd.) was used. (A-2): Preparation of polycarbonate resin Panlite L1250 (manufactured by Teijin Chemicals Ltd.) was used. (A-3): Preparation of modified polyphenylene ether resin Noril 731J (GE Plastics Japan) was used. (A-4): Preparation of nylon 6 resin UBE nylon 6 1013B (manufactured by Ube Industries, Ltd.) was used. (A-5): Preparation of polypropylene resin UBE Polypro J115G (manufactured by Ube Industries, Ltd.) was used.

(A-6): Preparation of polyacetal resin Di-n-formaldehyde gas was introduced into a polymerization reactor filled with n-hexane at a rate of 2 kg / h to perform polymerization. The polymer was separated by filtration, washed with water, and then acetylated with acetic anhydride. Next, the polymer was separated by filtration, washed with acetone, and dried to prepare a polyacetal resin. (A-7): Preparation of polyphenylene sulfide resin UBE PPS NR-04 (manufactured by Ube Industries, Ltd.) was used.

(A-8): Preparation of maleic anhydride-grafted polypropylene resin UBE Polypro J605H ( manufactured by Ube Industries, Ltd.) was used in an extruder (cylinder temperature: 220 ° C.) in an extruder (cylinder temperature: 220 ° C.) with alkyl peroxide to 100 parts by weight of polypropylene. (Perhexin 25B, manufactured by NOF Corporation) 0.3 parts by weight and 0.2 parts by weight of maleic anhydride were melt-kneaded, and the strand extruded from the nozzle was cooled in a water bath, and then cut with a pelletizer to obtain anhydrous maleic anhydride. An acid-grafted polypropylene resin pellet was obtained. (A-9): Preparation of polyglutarimide resin Paraloid EXL4151 (Rohm & Haas Co., Ltd.)
Was used. (A-10): Preparation of polyethylene resin UBE polyethylene F022 (manufactured by Ube Industries, Ltd.) was used.

[0059]

B. Synthesis of Ethylene Oxide Grafted Polyamide Elastomer (B-1): 70 parts by weight of caprolactam, polypropylene glycol diamine having a number average molecular weight of 2,000, and a dimer acid having an approximately equivalent amount to 30 parts by weight were charged into an autoclave, replaced with nitrogen, and replaced with 240 parts by weight. After heating at 3 ° C. for 3 hours, the temperature was raised to 270 ° C. over 1 hour, and the mixture was further heated for 3 hours to complete the polycondensation. The molten resin was extruded into strands from the lower part of the autoclave, and cut into pellets with a pelletizer. The obtained pellet was washed with hot water to remove a monomer component, and then dried.
Thus, a polyetheramide having a melting point of 200 ° C. and η _{r of} 1.67 was obtained. 100 parts by weight of this pellet-form polyetheramide was dispersed in n-hexane at 80 ° C., and 50% by weight of ethylene oxide was further charged and reacted for 8 hours. After the reaction, filtration, washing and drying were performed to obtain an ethylene oxide-grafted polyetheramide. From the weight increase of the obtained polymer, the graft ratio of ethylene oxide was 49%.

(B-2): The same polyether amide as in B-1 was used, and the same operation was carried out to obtain an ethylene oxide-grafted polyether amide having an ethylene oxide graft ratio of 89%. (B-3): 50 parts by weight of ε-caprolactam and 9.35 parts by weight of dodecanedioic acid were charged into an autoclave, substituted with N ₂ and heated at 240 ° C. for 3 hours to obtain a polyamide 6 prepolymer having carboxyl groups at both ends. Then number average molecular weight 1
Then, the polycondensation was completed by charging 40.65 parts by weight of 000 polybutylene glycol and 0.1 part by weight of antimony trioxide as an esterification catalyst, heating to 270 ° C. over about 1 hour, and further heating for 5 hours. The molten resin was extruded into strands from the lower part of the autoclave, and cut into pellets with a pelletizer. This gives η _r 1.92
Of polyetheresteramide was obtained. 100 parts by weight of the pellet-like polyetheresteramide was dispersed in n-hexane at 80 ° C., and 50% by weight of ethylene oxide was further charged and reacted for 8 hours under pressure. After the reaction, the resultant was filtered, washed and dried to obtain an ethylene oxide-grafted polyetheresteramide. From the weight increase of the obtained polymer, the graft ratio of ethylene oxide was 47
%Met.

(C): Synthesis of Ethylene Oxide Grafted Nylon 6 Using nylon 6 pellets (1013B, manufactured by Ube Industries), a graft nylon 6 having a graft ratio of ethylene oxide of 89% was obtained in the same manner as in the operation of B-1. . The melt flow rate (235 ° C., load 2160 g,
JIS D1238R) was 0.

(D): Synthesis of polyether amide Polymerization of polyether amide B-1 using 50 parts by weight of caprolactam, 50 parts by weight of polyethylene glycol diamine having a number average molecular weight of 1000 and a dimer acid having an equivalent amount thereof. Polyetheramide was obtained by the same operation as described above.

(E): Preparation of polyetherester amide 50 parts by weight of ε-caprolactam and 9.3 of dodecanedioic acid
5 parts by weight were charged into an autoclave and replaced with N ₂ to 240
At 3 ° C. for 3 hours.
A prepolymer was obtained. Next, 40.65 parts by weight of polyethylene glycol having a number average molecular weight of 1,000 and 0.1 part by weight of antimony trioxide as an esterification catalyst were added, and the temperature was raised to 270 ° C. over about 1 hour, and further heated for 5 hours to complete the polycondensation. did. The molten resin was extruded into strands from the lower part of the autoclave, and cut into pellets with a pelletizer. Thus, a polyetheresteramide having η _{r of} 1.80 was obtained.

Examples 1 to 11 (A) The thermoplastic resin and (B) the EO-grafted polyamide elastomer prepared in the reference example were mixed at the compounding ratio shown in Table 1, and the resin temperature was 210 to 3 with a vented 30 mmφ extruder.
Pellets were produced by melt-kneading and extrusion at 20 ° C.

[0066]

[Table 1]

[Table 2] Next, the cylinder temperature is 210 to 320 by an injection molding machine.
A test piece was molded at a temperature of 20 ° C. and a mold temperature of 20 to 150 ° C., and each physical property was measured. The results are shown in Table 2.

[0067]

[Table 3]

[Table 4]

Comparative Examples 1 to 7 The same processing as in Example 1 was carried out to mix and melt-knead pellets at the compounding ratios shown in Table 1, and the respective physical properties were measured. Table 2 shows the measurement results.
It was shown to.

Comparative Examples 8 to 11 The thermoplastic resin (A) prepared in the reference example and having the contents shown in Table 1 was injection-molded by an injection molding machine under the same conditions as in the example, and each physical property was measured. Table 2 shows the measurement results.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-14232 (JP, A) JP-A-2-133457 (JP, A) JP-A-62-241945 (JP, A) JP-A-51- 88722 (JP, A) JP 48-2948 (JP, B1) JP 48-10380 (JP, B1) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 101/00-101 / 14 C08L 77/00-77/12

Claims (1)

(57) [Claims] 1. A graft polymerization of 1,2-alkylene oxide on (A) a thermoplastic resin excluding a styrene resin , and (B) a polyamide elastomer selected from polyetheramide, polyetheresteramide, and polyesteramide. A thermoplastic resin composition comprising a modified polyamide elastomer.