JPH0676547B2 - Thermoplastic resin composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention provides the polyamide resin with excellent hygroscopicity, moldability and impact resistance while maintaining excellent mechanical toughness, durability and solvent resistance. The present invention relates to an improved thermoplastic resin composition and a method for producing the same, and the composition can be used in a wide range of fields such as electric and electromechanical parts and automobile parts.

[Prior Art] Polyamide resins have become increasingly important in the industrial parts field in recent years. Polyamide resin has extremely excellent thermal stability and extremely high hardness, and also has good heat resistance. However, its use is limited because of its low impact strength and high hygroscopicity.

As a technical means for improving the impact strength, it is known to use a reactive group-containing polyolefin elastomer such as a maleic anhydride-modified polyolefin elastomer or an epoxy group-containing polyolefin elastomer as an impact resistance improver.

Further, a method of melting and mixing polystyrene, a styrene-acrylonitrile copolymer (Japanese Patent Publication No. 40-7380), or an α, β-unsaturated dicarboxylic acid anhydride or epoxy for the purpose of improving the hygroscopicity of the polyamide resin. Method of melting and mixing group-containing polystyrene (JP-A-60-86162)
Japanese Patent Publication No. 4), a method of mixing glass fiber and a thermoplastic resin (Japanese Patent Publication No. 48-13944).

[Problems to be Solved by the Invention] However, the reactive group-containing polyolefin elastomer as the impact modifier is essentially a rubber-like polymer for that purpose and has a glass transition temperature of room temperature or lower. Is. Therefore, if the impact resistance is to be increased, the amount of the reactive group-containing polyolefin elastomer may be increased. Therefore, the tensile strength, surface hardness and thermal dimensional stability of the polyamide resin are reduced due to the thermal dimensional stability. There is a problem that important characteristics are deteriorated, such as decrease in

The method of mixing polystyrene and styrene / acrylonitrile copolymer for the purpose of improving the hygroscopicity of the polyamide resin is a method in which these vinyl-based copolymers have low compatibility with the polyamide resin, resulting in delamination of the molded product and mechanical It is known that the strength is remarkably reduced and a good molding material cannot be obtained.

Further, the method of mixing the glass fiber and the thermoplastic resin in the polyamide resin has the effect of lowering the hygroscopicity, but the glass fiber easily wears the molding equipment such as the screw of the extruder and the mold of the extruder, and further Secondary processing such as ion plating, sputtering, and coating becomes difficult, and there is a drawback that the fluidity also decreases.

The method of melting and mixing α, β-unsaturated dicarboxylic acid anhydride or polystyrene containing epoxy group is a method in which the low compatibility of both resins is improved by the reaction between the reactive group and the residual reactive group of the polyamide resin. Along with this, an effect of improving hygroscopicity is confirmed, but it has a drawback that impact resistance is lowered.

[Means for Solving Problems] In order to solve these conventional drawbacks and simultaneously improve impact resistance and hygroscopicity while maintaining mechanical and thermal properties of polyamide resin. As a result of intensive research, a thermoplastic resin composition obtained by blending a polyamide resin with a specific multi-phase structure thermoplastic resin is mechanically
The inventors have found that it is optimal to improve impact resistance and hygroscopicity at the same time while maintaining thermal characteristics, and to melt and knead them at a specific temperature in the production thereof, thereby completing the present invention.

That is, the first invention of the present invention is (I) polyamide resin 50 to 99% by weight, (II) epoxy group-containing olefin copolymer 5 to 95% by weight.
And 95 to 5% by weight of a vinyl-based (co) polymer obtained from at least one vinyl monomer.
50 to 1% by weight of a thermoplastic resin having a multiphase structure in which a polymer forms a dispersed phase having a particle size of 0.001 to 10 μm, and (III) an inorganic filler 0 to 100 parts by weight of the above (I) + (II) The thermoplastic resin composition contains ˜150 parts by weight.

Further, the second invention of the present invention is to provide an aqueous suspension of an epoxy group-containing olefin copolymer with at least one vinyl monomer, at least one radical (co) polymerizable organic peroxide and radical polymerization. An initiator is added and heated under conditions where decomposition of the radical polymerization initiator does not substantially occur, and the vinyl monomer, the radical (co) polymerizable organic peroxide, and the radical polymerization initiator are mixed with an epoxy group-containing olefin. When the copolymer is impregnated and the impregnation rate reaches 50% by weight or more at the beginning, the temperature of this aqueous suspension is raised to remove the vinyl monomer and the radical (co) polymerizable organic peroxide. , 1 to 100% by weight of a grafting precursor (A) copolymerized in an epoxy group-containing olefin copolymer, 0 to 99% by weight of an epoxy group-containing olefin copolymer (B), and at least one vinyl monomer. The quantity The vinyl-based (co) polymer (C) obtained by polymerization is melted and mixed with 0 to 99% by weight of the polyamide-based resin (I), or the (A), (B) and (C) are preliminarily added to 100- It is a method for producing a thermoplastic resin composition, which comprises melting and mixing in the range of 300 ° C. and melting and mixing with the polyamide resin.

The polyamide-based resin used in the present invention is an aliphatic polyamide resin such as nylon 6, nylon 6.6, nylon 6/10, nylon 6/12, nylon 11, nylon 12, nylon 4.6; polyhexamethylene. Examples thereof include aromatic polyamide resins such as diamine terephthalamide, polyhexamethylene diamine isophthalamide, and xylene group-containing polyamide, and modified products or mixtures thereof. Particularly preferred polyamide resins are nylon 6, nylon 6.6 and the like.

The epoxy group-containing olefin copolymer in the multi-phase structure thermoplastic resin used in the present invention is, for example, a binary copolymer of olefin and an unsaturated glycidyl group-containing monomer by high pressure radical polymerization or It is a ternary or multi-component copolymer of olefin with an unsaturated glycidyl group-containing monomer and another unsaturated monomer, and ethylene is particularly preferable as the olefin of the copolymer, and ethylene 60 to 99.5% by weight, A copolymer composed of 0.5 to 40% by weight of a glycidyl group-containing monomer and 0 to 39.5% by weight of another unsaturated monomer is preferable.

As the unsaturated glycidyl group-containing monomer, glycidyl acrylate; glycidyl methacrylate; itaconic acid monoglycidyl ester; butene tricarboxylic acid monoglycidyl ester; butene tricarboxylic acid diglycidyl ester; butene tricarboxylic acid triglycidyl ester; and α- Glycidyl esters such as chloroallyl, maleic acid, crotonic acid, fumaric acid or vinyl glycidyl ether; allyl glycidyl ether; glycidyl oxyethyl vinyl ether; glycidyl ethers such as styrene-p-glycidyl ether; p-glycidyl styrene and the like. And glycidyl methacrylate; acrylic glycidyl ether are particularly preferable.

The other unsaturated monomer is at least one monomer selected from olefins, vinyl esters, α, β-ethylenically unsaturated carboxylic acids or their derivatives, specifically propylene; Butene-1; hexene-1; decene-1; octene-1; olefins such as styrene, vinyl acid acrylate; vinyl propionate; vinyl esters such as vinyl benzoate, acrylic acid; methacrylic acid; acrylic acid or methacrylic acid Esters such as methyl, ethyl, propyl, butyl, 2-ethylhexyl, cyclohexyl, dodecyl and octadecyl; maleic acid;
Maleic anhydride; itaconic acid; fumaric acid; maleic acid monoesters and diesters; vinyl chloride; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether, and acrylic acid amide compounds, but acrylic acid ester is particularly preferable. .

Specific examples of the epoxy group-containing olefin copolymer include ethylene / glycidyl methacrylate copolymer; ethylene / vinyl acetate / glycidyl methacrylate copolymer;
Ethylene / ethyl acrylate / glycidyl methacrylate copolymer; ethylene / carbon monoxide / glycidyl methacrylate copolymer; ethylene / glycidyl acrylate copolymer; ethylene / vinyl acetate / glycidyl acrylate copolymer and the like. . Among them, ethylene / glycidyl methacrylate copolymer is preferable.

These epoxy group-containing olefin copolymers can be used even if mixed.

The method for producing an epoxy group-containing olefin copolymer by high-pressure radical polymerization is 60 to 99.5% by weight of the above-mentioned ethylene, 0.5 to 40% by weight of one or more unsaturated glycidyl group-containing monomers,
At least one other unsaturated monomer, from 0 to 39.5% by weight of the monomer mixture, based on the total weight of all of the monomers.
Polymerization pressure in the presence of 0001 to 1 wt% radical polymerization initiator 500 to 4,000 kg / cm ² , preferably 1,000 to 3,500 kg / cm ² ,
A reaction temperature of 50 to 400 ° C, preferably 100 to 350 ° C,
In this method, the monomers are simultaneously or stepwise contacted and polymerized in a tank or tube reactor in the presence of a chain transfer agent and, if necessary, an auxiliary agent.

Examples of the radical polymerization initiator include conventional initiators such as peroxides, hydroperoxides, azo compounds, amine oxide compounds and oxygen.

Further, as the chain transfer agent, hydrogen, propylene, butene-
1, C ₁ -C ₂₀ or more saturated aliphatic hydrocarbons and halogen-substituted hydrocarbons such as methane, ethane, propane, butane, isobutane, n-hexane, n-heptane, cycloparaffins, chloroform and tetrachloride. Carbon, C ₁ -C ₂₀ or higher saturated aliphatic alcohols such as methanol, ethanol, propanol,
And isopropanol, C ₁ -C ₂₀ or higher saturated aliphatic carbonyl compounds such as carbon dioxide, acetone and methyl ethyl ketone and aromatic compounds such as compounds such as toluene, diethylbenzene and xylene.

Another example of the epoxy group-containing olefin copolymer of the present invention is a modified product obtained by addition-reacting the above-mentioned unsaturated glycidyl group-containing monomer to a conventional olefin homopolymer or copolymer.

The olefin polymers include low density, medium density, high density polyethylene; polypropylene; polybutene-1; poly-
Homopolymer such as 4-methylpentene-1, ethylene-
Propylene copolymer; Ethylene-butene-1 copolymer;
Ethylene-hexene-1 copolymer; ethylene-4-methylpentene-1 copolymer; ethylene-octene-1 copolymer and other ethylene-based copolymers with α-olefin, propylene- Copolymers with other propylene-based α-olefins such as ethylene block copolymers; ethylene-vinyl acetate copolymers; ethylene-acrylic acid copolymers; ethylene-methacrylic acid copolymers; ethylene and Copolymers of acrylic acid or methacrylic acid with esters such as methyl, ethyl, propyl, isopropyl and butyl; ethylene-maleic acid copolymers;
Ethylene-propylene copolymer rubber; ethylene-propylene-diene-copolymer rubber; liquid polybutadiene; ethylene-vinyl acetate-vinyl chloride copolymer and mixtures thereof, or mixtures of these with different synthetic resins or rubbers Included in the present invention.

The vinyl-based (co) polymer in the thermoplastic resin having a multiphase structure used in the present invention includes, specifically, styrene, nucleus-substituted styrene such as methylstyrene and dimethylstyrene.
Ethylstyrene, isopropylstyrene, chlorostyrene, α-substituted styrene such as α-methylstyrene, α-
A vinyl aromatic monomer such as ethylstyrene; an alkyl ester of acrylic acid or methacrylic acid having 1 to 7 carbon atoms, for example, (meth) acrylic acrylic such as methyl (meth) acrylate, ethyl, propyl, isopropyl, butyl ester Acid ester monomers; (meth) acrylonitrile; monomers; vinyl ester monomers such as vinyl acetate and vinyl propionate; (meth) acrylamide monomers; maleic anhydride, maleic acid monoesters, diesters, etc. It is a (co) polymer obtained by polymerizing one or more vinyl monomers. Among them, vinyl aromatic monomers, (meth) acrylic acid ester monomers, (meth) acrylonitrile monomers and vinyl ester monomers are particularly preferably used.

In particular, a vinyl-based (co) polymer containing 50% by weight or more of a vinyl aromatic monomer or a (meth) acrylic acid ester monomer is the most preferable embodiment because it has good dispersibility in a polyamide-based resin.

The term "multiphase thermoplastic resin" as used in the present invention means an epoxy group-containing olefin copolymerization or vinyl (co) polymer matrix in which a vinyl (co) polymer or an epoxy group-containing olefin copolymer which is a different component It means that the coalesced particles are uniformly dispersed in a spherical shape.

The particle size of the dispersed polymer is 0.001 to 10 μm, preferably 0.01 to 5 μm. If the dispersed resin particle size is less than 0.001 μm or exceeds 10 μm, the dispersibility when blended with a polyamide resin is poor, for example, the appearance is deteriorated or the impact resistance improving effect is insufficient, which is not preferable.

The number average degree of polymerization of the vinyl (co) polymer in the multiphase thermoplastic resin of the present invention is in the range of 5 to 10,000, preferably 10 to 5,000.

When the number average degree of polymerization is less than 5, it is possible to improve the impact resistance of the thermoplastic resin composition of the present invention, but the heat resistance is lowered, which is not preferable. The number average degree of polymerization is
If it exceeds 10,000, the melt viscosity is high, the moldability is lowered, and the surface gloss is lowered, which is not preferable.

The multiphase structural thermoplastic resin of the present invention comprises an epoxy group-containing olefin copolymer in an amount of 5 to 95% by weight, preferably 20 to 90% by weight. Therefore, the vinyl (co) polymer content is 95 to 5% by weight, preferably 80 to 10% by weight.

If the epoxy group-containing olefin copolymer is less than 5% by weight, the impact resistance improving effect is insufficient, which is not preferable.
Further, when the epoxy group-containing olefin copolymer exceeds 95% by weight, the impact resistance improving effect is sufficiently obtained, but the heat resistance is deteriorated, which is not preferable.

The grafting method at the time of producing the thermoplastic resin of the multi-phase structure of the present invention may be any radiation such as the well-known chain transfer method and ionizing radiation irradiation, but the most preferable method is shown below. It is due to. The reason is that the grafting efficiency is high and the secondary aggregation due to heat does not occur, so that the performance is more effectively expressed.

Hereinafter, the method for producing the thermoplastic resin composition of the present invention will be specifically described.

That is, water is suspended in 100 parts by weight of an epoxy group-containing olefin copolymer, and 5 to 400 parts by weight of at least one vinyl monomer is added to a radical represented by the following general formula (a) or (b) ( Co) of 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl monomer, and one or a mixture of two or more kinds of polymerizable organic peroxides, and a decomposition temperature of 40 to 40 to obtain a half-life of 10 hours. Radical polymerization was performed by adding a solution in which a radical polymerization initiator at 90 ° C. was dissolved in 0.01 to 5 parts by weight with respect to 100 parts by weight as a total of a vinyl monomer and a radical (co) polymerizable organic peroxide. By heating under conditions that do not cause decomposition of the initiator, the epoxy group-containing olefin copolymer is impregnated with vinyl monomer, radical (co) polymerizable organic peroxide and radical polymerization initiator. When the water content reaches 50% by weight or more, The temperature of Nigoeki raised, and a vinyl monomer and radical (co) polymerizable organic peroxides by copolymerizing an epoxy group-containing olefin copolymer, obtained graft precursor (A). This grafted precursor is also a multiphase thermoplastic resin.

Therefore, the grafting precursor (A) may be directly melted and mixed with the polyamide resin, but the most preferable one is the multi-phase structure thermoplastic resin (II) obtained by kneading the grafting precursor. is there.

That is, the grafted precursor (A) may be kneaded under melting at 100 to 300 ° C. to obtain a multi-phase structure thermoplastic resin which is a graft product of the present invention. At this time, a multi-phase structure thermoplastic resin which is a grafted product even if an epoxy group-containing olefin copolymer (B) or a vinyl (co) polymer (C) is mixed with the grafting precursor and kneaded under melting. Can be obtained.

Also, a mixture of the grafted precursor and the epoxy group-containing olefin copolymer (B) and / or the vinyl (co) polymer (C) may be added to the polyamide resin (I) and melted and mixed. Good.

The radical (co) polymerizable organic peroxides represented by the general formulas (a) and (b) are those represented by the general formula [In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₂ , R ₇ is a hydrogen atom or a methyl group, R ₆ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₃ , R ₄ and R ₈ and R ₉ are each an alkyl group having 1 to 4 carbon atoms, R ₅ and R ₁₀ are each an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group or a cycloalkyl group having 3 to 12 carbon atoms. , M
Is 1 or 2 and n is 0, 1 or 2. ] It is a compound represented by.

As the radical (co) polymerizable organic peroxide represented by the general formula (a), specifically, t-butylperoxyacryloyloxyethyl carbonate; t-amylperoxyacryloyloxyethyl carbonate; t-hexylacryloyl Roxyethyl carbonate; 1,1,3,3-Tetramethylbutylperoxyacryloyloxyethyl carbonate; Cumylperoxyacryloyloxyethyl carbonate; p-Isopropylcumylperoxyacryloyloxyethyl carbonate; t-Butylperoxymethacryloyloxy Ethyl carbonate; t-amyl peroxymethacryloyloxyethyl carbonate; t-hexyl peroxymethacryloyloxyethyl carbonate; 1,1,3,3-
Tetramethylbutylperoxymethacryloyloxyethyl carbonate; cumylperoxymethacryloyloxyethyl carbonate; p-isopropylcumylperoxymethacryloyloxyethyl carbonate; t-butylperoxyacryloyloxyethoxyethyl carbonate; t
-Amylperoxyacryloyloxyethoxyethyl carbonate; t-hexyl peroxyacryloyloxyethoxyethyl carbonate; 1,3,3,3-tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate; cumylperoxyacryloyloxyethoxyethyl carbonate; p-isopropylcumylperoxyacryloyloxyethoxyethyl carbonate; t-butylperoxymethacryloyloxyethoxyethyl carbonate; t-amylperoxymethacryloyloxyethoxyethyl carbonate; t-hexylperoxymethacryloyloxyethoxyethyl carbonate; 1,1,1, 3,3-Tetramethylbutylperoxymethacryloyloxyethoxyethyl carbonate; cumylperoxymethacryloyloxyethoxyethyl carbonate p-isopropyl cumyl peroxymethacryloyloxyethoxyethyl carbonate; t-butyl peroxyacryloyloxy isopropyl carbonate; t-amyl peroxyacryloyloxy isopropyl carbonate; t-hexyl peroxyacryloyloxy isopropyl carbonate; 1,1,3, 3-Tetramethylbutylperoxyacryloyloxyisopropyl carbonate; Cumylperoxyacryloyloxyisopropyl carbonate; p-Isopropylcumylperoxyacryloyloxyisopropyl carbonate; t-Butylperoxymethacryloyloxyisopropyl carbonate; t-Amylperoxymethacryloyloxy Isopropyl carbonate; t-hexyl peroxymethacryloyloxy isopropyl carbonate; 1,1,3,3-tetramethyl And the like can be exemplified p- isopropyl cumyl peroxy methacryloyloxy isopropyl carbonate; chill butylperoxy methacryloyloxy isopropyl carbonate; cumyl peroxy methacryloyloxy isopropyl carbonate.

Further, the compound represented by the general formula (b) includes t
-Butyl peroxyallyl carbonate; t-amyl peroxyallyl carbonate; t-hexyl peroxyallyl carbonate; 1,1,3,3-tetramethylbutyl peroxyallyl carbonate; p-menthane peroxyallyl carbonate; cumyl peroxyallyl carbonate; t-
Butyl peroxy methallyl carbonate; t-amyl peroxy methallyl carbonate; t-hexyl peroxy methallyl carbonate; 1,1,3,3-tetramethyl butyl peroxy methallyl carbonate; p-menthane peroxy methallyl carbonate; cumyl peroxy meta Ryl carbonate; t-butylperoxyallyloxyethyl carbonate; t-amylperoxyallyloxyethyl carbonate; t-hexylperoxyallyloxyethyl carbonate; t-butylperoxymetallyloxyethyl carbonate; t-amylperoxymetallyloxyethyl carbonate; t- Hexyl peroxymetalloxyethyl carbonate; t-butyl peroxyallyloxy isopropyl carbonate; t-amyl peroxyallyloxy isopropyl carbonate; t-hexylpe Oxy allyloxy isopropyl carbonate; t-butyl peroxy meth Lilo carboxylate isopropyl carbonate; t-amyl peroxy meth Lilo carboxylate isopropyl carbonate; and t-hexyl peroxy meth Lilo carboxylate isopropyl carbonate can be exemplified.

Among these, preferred are t-butylperoxyacryloyloxyethyl carbonate; t-butylperoxymethacryloyloxyethyl carbonate; t-butylperoxyallyl carbonate; t-butylperoxymethallyl carbonate.

In the present invention, the polyamide resin is required to be 50 to 99% by weight, preferably 60 to 95% by weight. Therefore, the thermoplastic resin having a multi-phase structure is blended in a proportion of 50 to 1% by weight, preferably 40 to 5% by weight.

When the polyamide resin is less than 50% by weight, mechanical strength and heat resistance are deteriorated, which is not preferable. On the other hand, when the content of the polyamide resin exceeds 99% by weight, the effect of improving the impact resistance and the effect of improving the hygroscopicity which are the objects of the present invention are small, which is not preferable.

In the present invention, a resin component 10 containing the above (I) + (II)
0 to 150 parts by weight of inorganic filler (II
I) can be blended.

Examples of the inorganic filler include powdery, tabular, scaly, acicular, spherical or hollow fibers, and the like. Specifically, calcium sulfate, calcium silicate, clay, diatomaceous earth, talc, alumina, silica sand. , Glass powder, iron oxide, metal powder, graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon black, and other granular fillers; mica, glass plate, sericite, pyrophyllite, aluminum flakes Such as metal foil, flat plate-like or scale-like filler such as graphite; hollow filler such as shirasu balloon, metal balloon, glass balloon, pumice stone; glass fiber, carbon fiber, graphite fiber, whisker, metal fiber, silicon car Examples include bite fibers, asbestos, mineral fibers such as wstonite, and the like.

If the amount of the filler compounded exceeds 150 parts by weight, the impact strength of the molded article decreases, which is not preferable.

The surface of the inorganic filler is stearic acid, oleic acid, palmitic acid or metal salts thereof, paraffin wax, polyethylene wax or modified products thereof,
Surface treatment is preferably performed using an organic silane, an organic borane, an organic titanate or the like.

The thermoplastic composition of the present invention is produced by melting and mixing at a temperature of 150 to 350 ° C, preferably 180 to 320 ° C. When the temperature is less than 150, the melting is incomplete, the melt viscosity is high, the mixing becomes insufficient, and the layered peeling occurs, which is not preferable. If it exceeds 350 ° C, the resin is decomposed or gelled, which is not preferable.

As a method of melting and mixing, a kneading machine which is usually used such as a Banbury mixer, a pressure kneader, a kneading extruder, a twin-screw extruder, and a roll can be used.

In the present invention, other thermoplastic resins such as polyolefin resin, polyvinyl chloride resin, polyvinylidene chloride resin, polycarbonate resin, polyester resin, polyphenylene ether are also included within the scope of the present invention. Resin, polyphenylene sulphide resin, polysulfone resin, natural rubber, synthetic rubber, inorganic flame retardant such as magnesium hydroxide and aluminum hydroxide, halogen-based or phosphorus-based organic flame retardant, antioxidant, ultraviolet ray inhibitor Additives such as a lubricant, a dispersant, a foaming agent, a cross-linking agent, and a coloring agent may be added.

EXAMPLES Next, the present invention will be described in more detail with reference to examples.

Reference Example 1 (Production of thermoplastic resin IIA having a multi-phase layer structure) 2,500 g of pure water was placed in a stainless steel autoclave having a volume of 5 l, and 2.5 g of polyvinyl alcohol was dissolved as a suspending agent. Into this, 700 g of ethylene / glycidyl methacrylate copolymer (glycidyl methacrylate content 15% by weight) "trade name: Lexpearl J-3700" (manufactured by Nippon Petrochemical Co., Ltd.) was added as an epoxy group-containing olefin copolymer. It was stirred and dispersed. Separately, benzoylperoxy as a radical polymerization initiator "Product name: Nyber B" (manufactured by NOF Corporation)
1.5 g, t-butylperoxymethacryloyloxyethyl carbonate as radical (co) polymerizable organic peroxide
6 g was dissolved in 300 g of styrene as a vinyl monomer, and this solution was put into the autoclave and stirred.

Then, the autoclave is heated to 60 to 65 ° C. and stirred for 2 hours to impregnate the epoxy group-containing ethylene copolymer with the vinyl monomer containing the radical polymerization initiator and the radical (co) polymerizable organic peroxide. Let Then, after confirming that the total amount of the impregnated vinyl monomer, the radical (co) polymerizable organic peroxide and the radical polymerization initiator was 50% by weight or more, the temperature was adjusted to 80 to 85%. ℃
The temperature was maintained at that temperature for 7 hours to complete the polymerization, followed by washing with water and drying to obtain a grafted precursor. Extract the styrene polymer in this grafted precursor with ethyl acetate,
It was 900 when the number average degree of polymerization was measured by GPC.

Next, this grafted precursor was extruded at 200 ° C. with a Labo Plastomill uniaxial extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.) and a grafting reaction was carried out to obtain a multiphase thermoplastic resin (IIA).

Scanning electron microscope "JEOL J
When observed with "SM T300" (trade name, manufactured by JEOL Ltd.), it was a multi-phase structure thermoplastic resin in which a spherical resin having a particle diameter of 0.3 to 0.4 µm was uniformly dispersed.

At this time, the graft efficiency of the styrene polymer was 77.1% by weight.

Reference Example 2 (Production of Multiphase Thermoplastic Resin IIB) In Reference Example 1, styrene as a vinyl monomer
A multi-phase structure thermoplastic resin IIB was obtained by repeating Reference Example 1 except that 300 g was changed to a methyl methacrylate monomer and 0.6 g of n-dodecyl mercaptan was used as a molecular weight regulator.

At this time, the number average degree of polymerization of the styrene polymer is 700, and the average particle size of the resin dispersed in this resin composition is 0.
It was 1 to 0.2 μm.

Examples 1 to 6 Caprolactam (η _rel = 3.5 dl / g, 98% concentrated sulfuric acid 1 g / dl, 2
(Measured at 5 ° C.), a predetermined amount of the multiphase structure thermoplastic resin IIA or IIB obtained in Reference Examples 1 and 2 is dry blended,
It was melted and kneaded by a plastomill single-screw extruder [manufactured by Toyo Seiki Seisakusho, Ltd.] set at 280 ° C.

Next, each test piece was prepared with an injection molding machine set at 250 ° C., and the physical properties were evaluated. The results are shown in Table 1.

The test method is as follows.

(1) Tensile strength: ASTM-D638 (2) Izod impact strength (without notch): ASTM-D256 (3) Heat distortion temperature: ASTM-D648 (4) Water absorption rate: Test piece in 23 ° C water for 25 days Soaked, 23
The temperature was allowed to stand for 1 day at 65 ° C and 65% relative humidity, and the weight change was calculated.

(5) Layered peeling state: In the layered peeling state, an adhesive tape was attached to the fractured surface of the molded product, and a peeling test was performed by a method of removing the adhesive tape, and the state after the peeling test was visually observed and ranked as follows.

◎: No peeling ○: Slight peeling ×: Peeling Comparative Examples 1 to 4 Example 1 was repeated except that the unmodified epoxy group-containing olefin copolymer (Et / GMA) used in Reference Example 1 was replaced. The results are shown in Table 2.

Comparative Examples 5 to 6 In Example 1, a test piece was prepared and examined by repeating Example 1 except that the addition amount of the multi-phase structure thermoplastic resin was changed. The results are shown in Table 3.

From the above, when the content of the thermoplastic resin having a multiphase structure exceeds 50% by weight, the composition loses the properties of the polyamide resin at all, and when the amount of the thermoplastic resin having a multiphase structure is less than 1% by weight, It became clear that there was no addition effect.

Examples 7 to 8 and Comparative Examples 10 to 12 Polyhexamethylene adipamide resin (shown as PHMAP in the table) was used as the polyamide resin in Example 1 (η _rel = 2.
9 dl / g, 98% concentrated sulfuric acid 1 g / dl, measured at 25 ° C.) Example 1 was repeated except that the measurement was repeated. The results are shown in Table 4.

Reference Example 3 In Reference Example 1, 300 g of styrene as a vinyl monomer
Was dissolved in 300 g of benzene as a solvent, and 2.5 g of n-dodecyl mercaptan was added as a molecular weight modifier to prepare a graft precursor by repeating Reference Example 1, and the grafting reaction was completed. At this time, the number average degree of polymerization of the styrene polymer was 4.1, which was a liquid substance. As a result of observing this grafted product with an electron microscope, the dispersed particle size could not be confirmed and was estimated to be 0.001 μm or less.

Comparative Example 13 Example 1 was repeated except that the multiphase thermoplastic resin of Example 1 was changed to the graft product of Reference Example 3. As a result, the tensile strength was 620 kg / cm ² , the Izod impact strength was not broken, the heating deformation temperature was 360 ° C., the water absorption rate was 2.2% by weight, and delamination did not exist.

Example 9 The same procedure as in Reference Example 1 was repeated except that the radical (co) polymerizable organic peroxide was not used to obtain a grafted precursor. The dispersed particle size of this grafted precursor is 0.3-
It was 0.4 μm. Example 1 was repeated except that this grafted precursor was a multiphase thermoplastic resin. as a result,
Tensile strength 830kg / cm ² , Izod impact strength 56kg ・ cm / cm,
The heat distortion temperature was 65 ° C, the water absorption rate was 1.9% by weight, and delamination did not exist.

Example 10 10% by weight of grafted precursor obtained in Reference Example 1
(Dispersed particle size 0.3 to 0.5 μm), 5% by weight of the unmodified epoxy group-containing olefin copolymer used in Reference Example 1,
Styrene polymer (trade name "Dialex HF-55", manufactured by Mitsubishi Monsanto Kasei) 5% by weight, polycaprolactam
80% by weight was dry blended and then extruded at 260 ° C. Then, the physical properties were measured according to Example 1, and as a result, the tensile strength was 790 kg / cm, the Izod impact strength was 75 kg · cm / cm, the heat distortion temperature was 67 ° C., the water absorption rate was 1.8% by weight, and the delamination did not exist.

[Effects of the Invention] The thermoplastic resin of the present invention is a resin composition having high impact strength without lowering of heat resistance and improved hygroscopicity, and can be easily produced only by mixing under melting. It has characteristics. From the above points, the thermoplastic resin composition of the present invention can be used in a wide range of applications such as automobile parts, home electric appliance parts, and heat-resistant containers.

Claims (10)

[Claims] 1. (I) Polyamide resin 50 to 99% by weight, (II) Epoxy group-containing olefin copolymer 5 to 95% by weight
And 95 to 5% by weight of a vinyl-based (co) polymer obtained from at least one vinyl monomer.
50 to 1% by weight of a multi-phase layer structure thermoplastic resin in which a polymer forms a dispersed phase having a particle size of 0.001 to 10 μm, and (III) inorganic filler with respect to 100 parts by weight of the above (I) + (II) A thermoplastic resin composition containing 0 to 150 parts by weight. 2. A multiphase thermoplastic resin comprising at least one vinyl monomer and the following general formula (a) or (b): [In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₂ , R ₇ is a hydrogen atom or a methyl group, R ₆ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₃ , R ₄ and R ₈ and R ₉ are each an alkyl group having 1 to 4 carbon atoms, R ₅ and R ₁₀ are each an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group or a cycloalkyl group having 3 to 12 carbon atoms. , M
Is 1 or 2 and n is 0, 1 or 2. ] 1 to 100% by weight of a grafting precursor (A) obtained by copolymerizing at least one radical (co) polymerizable organic peroxide represented by the following in an epoxy group-containing olefin copolymer particle, containing an epoxy group A mixture comprising 0 to 99% by weight of an olefin copolymer (B) and 0 to 99% by weight of a vinyl-based (co) polymer (C) obtained by (co) polymerizing at least one vinyl monomer, and / Alternatively, the thermoplastic resin composition according to claim 1, which is a graft product obtained by melting and mixing them. 3. The vinyl monomer is a vinyl aromatic monomer,
Claim 1 or 2 which is one or more vinyl monomers selected from the group consisting of (meth) acrylic acid ester monomers, (meth) acrylonitrile monomers and vinyl ester monomers. The thermoplastic resin composition according to item 2. 4. An epoxy group-containing olefin copolymer comprising 60 to 99.5% by weight of ethylene, 40 to 0.5% by weight of glycidyl (meth) acrylate, and 0 to 39.5% by weight of another unsaturated monomer.
The thermoplastic resin composition according to any one of claims 1 to 3, which is a copolymer comprising 5. The thermoplastic resin according to claim 2 or 3, wherein the vinyl (co) polymer is such that 50% by weight or more of the vinyl monomer is a vinyl aromatic monomer. Composition. 6. Radical polymerization by adding at least one vinyl monomer, at least one radical (co) polymerizable organic peroxide and a radical polymerization initiator to an aqueous suspension of an epoxy group-containing olefin copolymer, Heating under conditions where decomposition of the initiator does not substantially occur, impregnating the vinyl monomer, the radical (co) polymerizable organic peroxide and the radical polymerization initiator into the epoxy group-containing olefin copolymer,
When the impregnation rate reaches 50% by weight or more at the beginning, the temperature of the aqueous suspension is raised to remove the vinyl monomer and the radical (co) polymerizable organic peroxide from the epoxy group-containing olefin copolymer. Grafted precursor (A) copolymerized in coalescence
1 to 100% by weight, an epoxy group-containing olefin copolymer (B) 0 to 99% by weight, and a vinyl-based (co) polymer (C) 0 to 99% obtained by polymerizing at least one vinyl monomer. % Of the polyamide resin (I) is melted and mixed, or the (A), (B) and (C) are melted and mixed in the range of 100 to 300 ° C. and further melted and mixed with the polyamide resin. A method for producing a thermoplastic resin composition comprising: 7. A radical (co) polymerizable organic peroxide is represented by the following general formula (a) or (b): [In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₂ , R ₇ is a hydrogen atom or a methyl group, R ₆ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₃ , R ₄ and R ₈ and R ₉ are each an alkyl group having 1 to 4 carbon atoms, R ₅ and R ₁₀ are each an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group or a cycloalkyl group having 3 to 12 carbon atoms. , M
Is 1 or 2 and n is 0, 1 or 2. ] The manufacturing method of the thermoplastic resin composition of Claim 6 which is a 1 type or a mixture of 2 or more types of the peroxy carbonate compound represented by these. 8. The vinyl monomer is a vinyl aromatic monomer,
7. The one or more vinyl monomers selected from the group consisting of (meth) acrylic acid ester monomers, (meth) acrylonitrile monomers and vinyl ester monomers, claim 6 or A method for producing the thermoplastic resin composition according to item 7. 9. An epoxy group-containing olefin copolymer comprising 60 to 99.5% by weight of ethylene, 40 to 0.5% by weight of glycidyl (meth) acrylate, and 0 to 39.5% by weight of another unsaturated monomer.
The method for producing a thermoplastic resin composition according to any one of claims 6 to 8, which is a copolymer comprising 10. The thermoplastic resin composition according to claim 6, wherein the vinyl (co) polymer comprises 50% by weight or more of the vinyl monomer and a vinyl aromatic monomer.