JPH0715056B2 - Polyamide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Purpose of the Invention [Field of Industrial Application] The present invention is a polyamio resin composition used for a wide range of purposes such as general consumption and industrial molding materials, synthetic fibers, and adhesives. The present invention relates to a polyamide resin composition using a polymer alloy method, which has recently attracted attention as a method for modifying a resin.

[Conventional technology and its problems]

With the remarkable development of the polymer chemical industry in recent years, a large number of polymer materials are used in large quantities in daily life products, industrial products, vehicles, building materials and the like.

Especially after the oil crisis, the need for higher performance and higher functionality of products has increased, and engineering plastics have shown remarkable growth potential in the field of polymer materials as well. it can. Under these circumstances, even in the field of conventional general-purpose plastics, efforts are being made to improve and reform by various methods in order to meet the diversifying demands of the market.

Polyamide is a typical engineering plastic, and it has excellent toughness, self-lubricating property, wear resistance, chemical resistance, self-extinguishing property, gas barrier property, etc., and is used for automobiles, electricity, mechanical parts, packaging materials, etc. Steady growth continues in a wide range of fields.

On the other hand, there remain problems in dimensional change due to moisture absorption and impact strength at low temperatures, so resin suppliers are making various attempts to improve these points.

Above all, modification of polyamide resin by polymer alloy or blend has been studied for a long time, and mainly by blending with a hydrophobic polymer, it is intended to reduce water absorption to improve dimensional stability and to improve low temperature impact strength. Many patent applications have been made for the main purpose.

As a blending partner, acrylonitrile-butadiene-styrene terpolymer (hereinafter abbreviated as ABS),
Acrylonitrile-styrene copolymer (hereinafter abbreviated as AS), acid-modified polyolefin and polystyrene,
Polyester, other types of polyamide, polyphenylene oxide, various rubber components such as carboxyl-modified butadiene rubber, nitrile rubber, polyester rubber and the like. Above all, blends with polyolefins and polystyrenes, and with polyphenylene oxide, which has shown high growth as an engineering plastic in recent years, have been actively tested and many patents have been patented. In these examples, an unsaturated carboxylic acid or its anhydride is partially copolymerized or grafted in a polymer molecule in order to improve the compatibility in a blend with a polyamide which is essentially incompatible. A general method is to introduce a polar group to enhance the interaction with polyamide.

For example, in Japanese Examined Patent Publication No. 42-12546, an ethylene-methacrylic acid copolymer is used as a polyolefin component and blended with a polyamide to obtain a blend excellent in mechanical strength and water resistance. The publication reports a reactive polymer alloy having excellent impact resistance by grafting ε-caprolatum onto an ethylene-ethyl acrylate copolymer.

Blends with excellent flexibility at low temperature in combination with other saponified ethylene-vinyl acetate copolymers (Japanese Patent Publication No. 48-11
221) or a blend with excellent impact strength in combination with ethylene-hydroxyethyl methacrylate copolymer (Japanese Patent Publication No. Sho 48-17665), unsaturated carboxylic acid anhydride, especially grafted with maleic anhydride. Blends with improved impact properties in combination with the modified polyethylene
52-151348), a tough blend obtained by combination with an ethylene-acrylamide-alkyl acrylate copolymer, and the like. In all of these, a monomer unit having a carboxylic acid or a hydroxyl group, an ester bond or the like is incorporated in the skeleton of polyethylene.

There is an example in which ethylene-acrylic acid copolymer metal salt (ionomer resin) was added as a third component to a blend of polyamide and polypropylene to obtain a blend excellent in impact resistance, water resistance and heat resistance. (JP-A-56-16774
(0,167751), in which the ionomer resin is interesting because it acts as a so-called compatibilizer that binds different polymers together.

On the other hand, in the case of blending with a polystyrene resin, many examples of using a copolymer of styrene and an unsaturated carboxylic acid such as maleic acid or maleic anhydride have been reported (Japanese Patent Laid-Open Publication No. Sho.
56-50931, -53134, -62844 and -167750) A graft copolymer obtained by melt-kneading a copolymer containing about 10% of unsaturated carboxylic acids with a polyamide has water resistance and dimensional stability. It is said that the polyamide has been improved and the drawbacks of polyamide have been improved. When the same styrene-methacrylic acid copolymer was used as a compatibilizer for a polyamide / polystyrene blend, it was reported that the dispersibility was improved but the strength was not improved (J. Appl. Ply
m.Sci. 18 963 '74).

It has been reported that a similar copolymer is also effective in a blend of polyamide and polyphenylene oxide (Japanese Patent Laid-Open No. Sho 61-96).
57-36150, 59-27942 and -27943). In these patent examples, a styrene-maleic anhydride copolymer or a styrene-maleimide copolymer is used as a compatibilizing agent for both resins to obtain a blend excellent in oil resistance, acid resistance and impact resistance.

As described above, in a polyamide-based blend, in order to obtain an interaction with a polyamide molecular skeleton having a strong polarity, a method of introducing a polar group into the polymer molecule to be blended by a certain means is common. The blends obtained according to these known methods certainly have some improved performance. However, the method of obtaining compatibility by forming a chemical bond at the time of blending inevitably leads to an increase in molecular weight and causes a drastic decrease in moldability, so that the addition amount is limited. When the above copolymer is used as the compatibilizer, the polar group is introduced to improve the affinity with the polyamide, but the compatibility with the other blend resin is decreased, resulting in the compatibilizing effect. Does not climb as expected. In other words, it can be said that the performance as a compatibilizer is limited in the conventional method in which polar groups are randomly added to the polymer molecular chain. Generally, in the case of blends of resins that are not compatible with each other, at least one of the polymers that make up the blend is modified to improve compatibility, or the interface between both components is strengthened.
Addition of a third component to adhere is required. It is said that a block polymer or a graft polymer having different polymer segments in the same molecule is effective as a third component for achieving such compatibilization, that is, a compatibilizing agent. Therefore, if a block polymer or graft polymer having both a polar group-containing segment for obtaining affinity with polyamide and a segment compatible with the other blended polymer species in the molecule at the same time is used as a compatibilizer, It will have an excellent effect.

Block polymers can usually be synthesized by anionic polymerization,
It is difficult to maintain proper reaction conditions, and the kinds of polymers that can be synthesized are extremely limited. Also, the graft polymer is usually a chain transfer method using a peroxide, a radiation grafting method,
Although polymer initiator methods and the like have been carried out, these methods generally have a low graft ratio and it is difficult to control the molecular weight and composition, and the kinds of polymers that can be synthesized are also limited.

Therefore, if a block polymer or graft polymer that can be used as a compatibilizing agent when blending polyamide and other polymers can be synthesized inexpensively and easily and with the desired control of the molecular structure, etc. The technical and economic value is enormous.

(2) Configuration of the Invention [Means for Solving Problems] The inventors of the present invention have made earnest studies in order to obtain a polyamide resin composition having excellent performance in consideration of the problems of the conventional techniques as described above. As a result, the graft polymer having a specific molecular structure obtained by a specific production method can improve the miscibility of polyamide / a thermoplastic resin-based composition other than polyamide,
The inventors have found that a resin composition having excellent performance can be obtained, and completed the present invention.

That is, the present invention is a polyamide resin composition comprising a thermoplastic resin other than polyamide, polyamide and polyphenylene oxide (hereinafter simply referred to as a thermoplastic resin) and a graft polymer, wherein the graft polymer is compatible with the thermoplastic resin. A polyamide resin composition characterized by being obtained by copolymerization of a macromonomer obtained by using a monomer that gives a good polymer segment and a monomer containing an unsaturated carboxylic acid or an anhydride thereof. .

Next, each configuration of the present invention will be sequentially described.

[Macromonomer]

The macromonomer in the present invention means a high molecular weight monomer having a polymerizable functional group at one end of the molecular chain.

Examples of the terminal polymerizable functional group of the macromonomer in the present invention include (meth) acroyloxy group, allyloxy group, styryl group and the like. Of these, a metacroyloxy group is preferable.

The molecular weight of the macromonomer in the present invention may be in a range that does not impair the polymerizability of the produced macromonomer, and is a number average molecular weight of 1,000 to 20,000, preferably 200.
It is 0-15,000. When the number average molecular weight is less than 1000, the molecular weight as a polymer unit is too low, and the physical properties of the macromonomer are not reflected in the graft polymer, which is not preferable, and when the number average molecular weight exceeds 20,000, the polymerizability of the macromonomer decreases or the reaction This is not preferable because phase separation of the system often occurs and causes problems in the production of the graft polymer.

The number average molecular weight of the macromonomer is a polystyrene equivalent molecular weight by gel permeation chromatography (hereinafter referred to as GPC), and the measurement conditions are as follows.

Equipment: High Performance Liquid Chromatography (eg Toyo Soda Industry Co., Ltd. product name HLC-802UR) Column: Polystyrene gel (eg Toyo Soda Industry Co., Ltd.)
Product name G4000H8 and G3000H8) Elution solvent: Tetrahydrofuran (abbreviated as "THF" hereinafter) Outflow rate: 1.0 ml / min Column temperature: 40 ° C Detector: RI detector The skeleton structure of the macromonomer in the present invention is a vinyl polymerizable monomer. It is a skeleton obtained by polymerizing, and is selected from polymer skeletons having good compatibility with the thermoplastic resin. Examples of the monomer that provides a polymer segment that has good compatibility with the thermoplastic resin include vinyl esters of organic acids such as vinyl acetate, styrene, styrene substitution products, vinyl aromatic compounds such as vinyl pyridine and vinyl naphthalene,
(Meth) acrylic acid ester, (meth) acrylonitrile, acrylene, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, unsaturated acid anhydrides such as maleic anhydride, N-substitution such as N-phenylmaleimide Maleimide, etc. may be mentioned. Preferably, styrene, styrene substitution product, (meth) acrylic acid ester,
One or more monomers selected from (meth) acrylonitrile are used, and more preferably, one or more monomers selected from styrene, alkyl (meth) acrylate, and acrylonitrile are used. A polymer chain having excellent compatibility with the thermoplastic resin may be formed by properly selecting from these monomers and homopolymerizing or copolymerizing them.

The macromonomer production method in the present invention includes the anionic polymerization method established by Milkovich et al.
The radical chain transfer method proposed by Company I can be used.

For example, when a macromonomer is produced by an anionic polymerization method, a hydrocarbon-based monomer such as styrene, butadiene or isoprene may be polymerized using an initiator such as alkyllithium in an inert solvent such as benzene or toluene. . According to this method, the polymerization proceeds to the living room, alkylene oxide is added to this, and the mixture is reacted, and then methacrylic acid chloride is reacted, whereby a high-performance macromonomer having a narrow molecular weight distribution can be produced.

On the other hand, when a macromonomer is produced by the radical chain transfer method, a vinyl-polymerizable monomer is radically polymerized in the presence of a chain transfer agent having a carboxy group in the molecule to obtain a polymer having a carboxyl group at one end (hereinafter referred to as "polymer"). A prepolymer) is synthesized and then reacted with a vinyl polymerizable monomer having a glycidyl group in the molecule.

As a chain transfer agent having a carboxyl group in the molecule used at this time, a mercaptan compound having an appropriate chain transfer constant,
For example mercaptoacetic acid, 3-mercaptopropionic acid, 2-
Mercaptopropionic acid and the like are preferably used.

As the vinyl-polymerizable monomer having a glycidyl group in its molecule, glycidyl meccrylate (hereinafter abbreviated as GMA), glycidyl acrylate, allyl glycidyl ether, etc. are used, and of these, GMA is particularly preferable.

According to this method, various kinds of macromonomers such as polar monomers that cannot be synthesized by anionic polymerization can be easily obtained, and therefore, they have recently received industrial attention.

[Graft polymer]

The graft polymer in the present invention is a macromonomer method,
That is, it is produced by a method using a macromonomer as a raw material for producing a graft polymer. Specifically, the graft polymer can be easily obtained by copolymerizing the above-mentioned macromonomer with another polymerizable monomer. As a polymerization method, any one of a conventionally known solution polymerization method in the presence of a radical polymerization initiator, a bulk polymerization method, an emulsion polymerization method and a dispersion polymerization method may be used. The solution polymerization method is usually preferably used because of the problem of phase separation of the polymerization reaction solution.

A method for producing a graft polymer using such a macromonomer, i) The content of the homopolymer of the branch and trunk components is extremely low. ii) The molecular weight of the trunk component, the molecular weight of the entire graft polymer, and the weight ratio of the branches and the trunk can be easily controlled. iii) The combination of the branch component and the stem component can be freely selected according to the purpose. With such features, it is possible to easily obtain a high-performance graft polymer that cannot be obtained with conventional graft polymers.

The molecular structure of the graft polymer in the present invention comprises a monomer unit derived from an unsaturated carboxylic acid or an anhydride thereof as a main component, and a polymer segment derived from a macromonomer having good compatibility with a thermoplastic resin as a branch component. It has.

Examples of unsaturated carboxylic acids or anhydrides thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and fumaric acid, and unsaturated carboxylic acid anhydrides such as maleic anhydride. Of these, unsaturated carboxylic acid anhydrides are preferable, and maleic anhydride is particularly preferable, from the viewpoint of reactivity with the terminal amino group of polyamide.

The above monomers, alone or by copolymerization with other comonomers, form the backbone component of the graft polymer. In this case, the comonomer is selected from those copolymerizable with the unsaturated carboxylic acid or its anhydride, and usually styrene, (meth) acrylic acid ester, (meth) acrylonitrile, etc. are used. The copolymerization composition of unsaturated carboxylic acid or its anhydride and comonomer is 70/30 to 1/99 by weight.
And preferably 50/50 to 5 to 95, more preferably 30/7
It is from 0 to 10/90. Unsaturated carboxylic acid or its anhydride is 70
If it exceeds 1% by weight, the reaction system tends to undergo phase separation during the production of the graft polymer, which is not preferable. If it is less than 1% by weight, the compatibilizing effect of this graft polymer when melt-kneaded as a compatibilizing agent for polyamide and thermoplastic resin is not preferable. It is not preferable because it is insufficient.

The branch component of the graft polymer is a polymer segment derived from the above-mentioned macromonomer, and a polymer segment having good compatibility with the thermoplastic resin used for blending with the polyamide is selected. The following combinations can be used as an example of the combination of the thermoplastic resin and the corresponding branch segment.

Polystyrene, high-impact polystyrene → polystyrene segment Acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, polycarbonate → acrylonitrile-styrene copolymer segment Methacrylic resin, polyvinyl chloride → polymethyl methacrylate segment The graft polymer in the present invention is Although the above-described trunk and branch components are contained in the molecule, the weight composition of these trunk / branch components is preferably 90/10 to 10/90, preferably 80/20 to 20/90. More preferably, it is / 80. When the content of the trunk or branch component is less than 10% by weight, the compatibilizing effect when melt-kneading the graft polymer as a compatibilizing agent for the polyamide and the thermoplastic resin is insufficient, which is not preferable.

The molecular weight of the graft polymer is 5000 in terms of number average molecular weight.
〜200,000 is preferred, and more preferably 10,000-100,000. When the number average molecular weight is less than 5,000, the polymer segment is too short and a large compatibilizing effect cannot be expected, which is not preferable, and when it exceeds 200,000, the dissolution rate in the resin to be blended is low, which is not preferable.

〔polyamide〕

The polyamide used in the present invention means a polymer formed by a condensation reaction of a diamine and a dibasic acid, a self-condensation reaction of an amino acid, or a ring-opening polymerization reaction of a lactam, and is generally known as "nylon".

Polyamides useful in the present invention have amide bonds or --CO--NH.
-Has a bond in the main chain. Specifically, polyhexamethylene adipamide (nylon-6,6), polycaprolactam (nylon-6), polyundecanolactam (nylon-11), polydodecanolactam (nylon-12),
Polyhexamethylene sebacamide (Natron-6,10), polypyrrolidone (nylon-4), polyheptolactam (nylon-7), polycaprylactam (nylon-)
8), polynonanolactam (nylon-9), polyhexamethylene azelainamide (nylon-6,9), polyhexamethylene isophthalamide, polymethaxylylene adipamide, polyamide of hexamethylenediamine and n-dodecanedioic acid ( Nylon-6,12), polyamide of dodecamethylenediamine and n-dodecanedioic acid (nylon 12,1
2) and their copolymers can be used.

Of these, polycaprolactam (nylon-6),
Polyhexamethylene adipamide (nylon-6,6) is preferably used, and polycaprolactam (nylon-6) is more preferably used.

As the above-mentioned polyamide, one produced by a known production method is used. Usually, it can be produced by equimolar polycondensation reaction of diamine and dicarboxylic acid, self-polycondensation reaction of aminocarboxylic acid, or ring-opening polymerization of lactam.

〔Thermoplastic resin〕

The thermoplastic resin in the present invention is a series of resins known as engineering plastics among the styrene-based, acrylic-based, and vinyl-based resins used as usual molding materials, and engineering plastics that have been growing in demand in recent years. ,
Of these, non-crystalline thermoplastic resins are preferred.

Specifically, polystyrene, rubber modified polystyrene known as high impact polystyrene, acrylonitrile-
Styrene copolymer, acrylonitrile-butadiene-styrene terpolymer generally known as ABS resin, rubber component of ABS resin, acrylic rubber, chlorinated polyethylene, ethylene-propylene-diene monomer copolymer rubber respectively Substituted graft copolymers generally called AAS resin, ACS resin, AES resin, polymethylmethacrylate, polyvinyl chloride, polycarbonate, polysulfone and the like can be mentioned. These resins can be used alone or as a blend of two or more components.
Polystyrene is preferably used.

[Polyamide resin composition]

The polyamide resin composition of the present invention is a resin composition comprising a polyamide, a thermoplastic resin and a graft polymer, and a composition containing these three as the main components is preferable. However, as explained in the section of the graft polymer, the branch component of the graft polymer must be a polymer segment that has good compatibility with the thermoplastic resin, so the structure of the graft polymer depends on the type of thermoplastic resin. To be done.

The mixing ratio of the polyamide and the thermoplastic resin is selected from the range of polyamide / thermoplastic resin = 5/95 to 95/5 by weight ratio. It is preferably used in the range of 20/80 to 80/20. When the proportion of the minor component is less than 5% by weight, the physical properties of the minor component are not sufficiently reflected in the resin composition, which is not preferable.

The amount of the graft polymer to be added is preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total of polyamide and thermoplastic resin. If the addition amount of the graft polymer is less than 1 part by weight, the compatibilizing effect is insufficient, so that it is not preferable, and if it exceeds 30 parts by weight, kneading and melt viscosity increase to cause deterioration of moldability and physical properties of the final molded product. It is not preferable because it may cause deterioration.

The polyamide resin composition of the present invention may be obtained by melt-kneading a polyamide, a thermoplastic resin, and a graft polymer using an ordinary blending method such as an extruder, a kneader, or an open roll. A preferred method is a method of mixing using a Henschel mixer or the like, heating and melting this using an extruder, extruding, and cutting into pellets.

In addition, the resin composition of the present invention contains various commonly used additives such as plasticizers, antioxidants, stabilizers, inorganic fillers, reinforcing agents such as glass fibers, pigments, dyes, impact modifiers, Etc. can be selected and used.

[Action]

According to the present invention, the compatibility of the polyamide / thermoplastic resin composition can be improved by adding a small amount of a graft polymer having a specific structure and manufactured by a specific manufacturing method. A resin composition having both characteristics of resin can be obtained. This is because the above graft polymer has a graft structure containing a trunk component containing an acid anhydride group chemically bonded to a terminal amino group of polyamide and a branch component having excellent compatibility with a thermoplastic resin in the same molecule. Is. That is, it is considered that the interfacial migration characteristic of the graft polymer improves the miscibility of both resins which are originally incompatible with each other and improves the interfacial adhesion.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to Reference Examples, Comparative Reference Examples, Examples, and Comparative Examples.

In the examples,% means% by weight and part means part by weight.

Reference Example 1 (Production of Styrene Macromonomer by Anionic Polymerization Method) 1200 benzene dried with calcium hydride was added to a reactor.
Parts were charged, the reactor was heated to 40 ° C. and 0.1 part of diphenylethylene was added. Furthermore, sec-butyl lithium 11.4
% Hexane solution until the reaction mixture becomes light reddish brown,
Then 15.3 parts were charged. Thereafter, the purified styrene monomer was continuously fed into the reaction solution over 1.5 hours. During this period, the reaction solution was kept at 40 ° C. After further aging for 30 minutes, the mixture was cooled to 20 ° C., 2 parts of ethylene oxide was added for capping treatment, and then 5 parts of methacrylic acid chloride was added to carry out terminal methacrylation. This was precipitated in excess amount of methanol and then dried under reduced pressure at 80 ° C to obtain a solid styrene macromonomer. The polystyrene reduced molecular weight by GPC is
It was 12000 (number average) and 13000 (weight average).

Reference Example 2 (Production of Radical Chain Transfer Method Styrene Macromonomer) A glass flask equipped with a stirrer, a reflux condenser, two dropping funnels, a thermometer and a gas blowing port was charged with styrene 50.
0 parts and 300 parts of toluene were charged, styrene 500 parts in one dropping funnel (referred to as dropping funnel A), and azobisisobutyronitrile (hereinafter abbreviated as AIBN) in the other funnel (referred to as dropping funnel B). A mixed solution of 7.06 parts, 10.6 parts of 3-mercaptopropionic acid and 200 parts of toluene was added. After introducing the nitrogen gas, the reaction solution was heated and kept at 90 ° C., and then the dropping funnel A was dropped for 4 hours and the dropping funnel B was dropped for 14 hours. When further heated for 2 hours, the polymerization conversion rate of styrene is 93.5.
It became%.

After converting from nitrogen bubbling to air bubbling, add 0.3 parts of hydroquinone monomethyl ether, 14.2 parts of glycidyl methacrylate and 15 parts of triethylamine, and add 1 at 110 ° C.
The reaction was carried out for 2 hours. The reaction conversion obtained from the acid value was 96.3%.
Met.

The reaction solution was precipitated in 10 volumes of methanol and dried under reduced pressure at 80 ° C to obtain 912 parts of solid styrene macromonomer. G
The polystyrene reduced molecular weights by PC were 11,000 (number average) and 27,000 (weight average).

Reference Example 3 (Production of Styrene-Maleic Anhydride Graft Polymer I) Stirrer, reflux condenser, two dropping funnels, a thermometer and a glass flask equipped with a gas inlet, and styrene 12
5 parts, 1.0 part of maleic anhydride, 100 parts of styrene macromonomer produced in Reference Example 1 and 125 parts of butyl acetate were charged, and 5 parts of AIBN was added to one dropping funnel (referred to as dropping funnel A).
A mixture of 45 parts of butyl acetate was added, and another mixture of 24 parts of maleic anhydride and 76 parts of butyl acetate was placed in the dropping funnel (referred to as dropping funnel B). After introducing the nitrogen gas, the reaction solution was heated and maintained at 90 ° C., and then the dropping funnels A and B were added dropwise over 8 hours. At this time, the dropping funnel A was set at a constant feed rate, and the dropping funnel B was adjusted to a dropping speed corresponding to the polymerization rate of styrene. When heating was continued for 2 hours after the completion of dropping, the polymerization conversion rate of styrene was 98.1%. This was dried under reduced pressure to obtain 254 parts of a solid graft polymer. The polystyrene reduced molecular weights by GPC were 16000 (number average) and 96000 (weight average).

Reference Example 4 (Production of Styrene-Maleic Anhydride Graft Polymer II) The procedure of Reference Example 3 was repeated except that the styrene macromonomer produced in Reference Example 2 was used. The final polymerization conversion rate of styrene was 98.5%. The molecular weight by GPC was 12000 (number average) and 130000 (weight average).

Reference Example 5 (Production of Styrene-Maleic Anhydride-Methyl Methacrylate Graft Polymer) In a glass flask equipped with a stirrer, a reflux condenser, a thermometer and a gas inlet, 10 parts of styrene, 10 parts of maleic anhydride and methacrylic acid were added. Methyl 40 parts, styrene macromonomer 40 parts produced in Reference Example 1, methyl ethyl ketone 100
Section, AIBN 1 section. After introducing the nitrogen gas, the reaction solution was heated and heated to react at 70 ° C. for 10 hours, and then 1 part of AIBN was touched and aged for 5 hours. The polymerization conversion rate of each monomer was styrene: 100%, maleic anhydride: 96.1%, and methyl methacrylate: 95.6%. The polystyrene reduced molecular weights by GPC were 12,000 (number average) and 37,000 (weight average).

Comparative Reference Example 1 (Production of Styrene-Maleic Anhydride Random Copolymer) Styrene 22 was added to a glass flask equipped with a stirrer, a reflux condenser, two dropping funnels, a thermometer and a gas inlet.
5 parts, maleic anhydride 2.0 parts, and butyl acetate 125 parts were charged, and one part of the dropping funnel (referred to as dropping funnel A) was charged with a mixed solution of 5 parts of AIBN and 45 parts of butyl acetate, and the other dropping funnel (dropping). Rohto B) 23 parts maleic anhydride,
A mixed solution of 76 parts of butyl acetate was added. After introducing the nitrogen gas, the reaction solution was heated and kept at 90 ° C, and then the dropping funnels A and B were added.
Was added dropwise over 8 hours. At this time, the dropping funnel A was set at a constant feed rate, and the dropping funnel B was adjusted to a dropping speed corresponding to the polymerization rate of styrene. When heating was continued for 2 hours after the completion of dropping, the polymerization conversion rate of styrene was 97.9%. This was dried under reduced pressure to obtain 252 parts of a solid copolymer. G
The polystyrene reduced molecular weights measured by PC were 21,000 (number average) and 73,000 (weight average).

Examples 1 to 7 (effect of adding graft polymer to nylon-6 / polystyrene resin composition) 40 parts of commercially available polyamide resin (Ube Industries, Ltd., trade name Ube 6 nylon 1022), polystyrene resin for general use ( Topolex GPPS 525-51) 6 manufactured by Mitsui Toatsu Chemicals, Inc. 6
The amount of the graft polymer produced in Reference Examples 3 to 5 was added to 0 part and melt-blended with a twin-screw extruder. The extruder jacket temperature was 230 ° C. A test piece prepared from this blend was subjected to a tensile test and a Charpy impact test. However, tensile test: According to JIS K7113, the tensile speed was 5 mm / min.

Charpy impact test: In accordance with JIS K7111, it was performed without a notch.

Comparative Example 1 Examples 1 to 7 except that no graft polymer was added.
I went in the same way.

Comparative Example 2 Examples 1 to 7 except that 10 parts of the random copolymer prepared in Comparative Reference Example was added instead of the graft polymer.
The same method was used.

The results of the physical property tests of the polyamide resin composition in each of the above examples are summarized in Table 1.

(3) Effects of the Invention The polyamide resin composition of the present invention has a very good compatibility between the polyamide and the thermoplastic resin, and the physical properties of the polyamide and the thermoplastic resin to be used are sufficiently exhibited, and the molding material,
It is used as a synthetic fiber, adhesive, etc. and has a great practical value.

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Claims (1)

[Claims] 1. A polyamide resin composition comprising a thermoplastic resin other than polyamide, polyamide and polyphenylene oxide, and a graft polymer, wherein the graft polymer has good compatibility with a thermoplastic resin other than polyamide and polyphenylene oxide. A polyamide resin composition, which is obtained by copolymerization of a macromonomer obtained by using a segment-providing monomer and a monomer containing an unsaturated carboxylic acid or an anhydride thereof.