JPH01118561A - Thermoplastic resin composition and its production - Google Patents

Abstract

PURPOSE:To obtain the present composition excellent in heat resistance and impact resistance, by mixing a polyamide resin with an ABS resin, a specified multiphase-structure thermoplastic resin and an inorganic filler. CONSTITUTION:A grafted precursor is prepared by adding a solution of a radical-(co)polymerizable organic peroxide (iii) of formula I or II (wherein R1 is a 1-2C alkyl, R2 and R7 are each H or CH3, R3-4 and R8-9 are each a 1-4C alkyl, R6 is H or R3, R5 and R10 are each a 1-12C alkyl, a phenyl or the like, m is 1-2, and n is 0-2) and a radical polymerization initiator (iv) of a 10hr half-life decomposition temperature of 40-90 deg.C in a vinyl monomer (ii) to an aqueous suspension (i) of an epoxy olefin copolymer and reacting them. The obtained precursor is melt-kneaded to obtain a multiphase-structure thermoplastic resin (c) which comprises 5-95wt.% component (i) and 95-5wt.% vinyl (co)polymer obtained from component (ii) and in which either (co)polymer forms a dispersed phase of a particle diameter of 0.001-10mum. 100pts.wt. mixture of 99-1wt.% polyamide resin (a) with 1-99wt.% ABS resin (b) is mixed with 0.1-100pts.wt. component (c) and 0-150pts.wt., per 100pts.wt. in total of components (a)-(c), inorganic filler (d).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a thermoplastic resin composition with excellent heat resistance and impact resistance, and is applicable in a wide range of fields such as automobile parts, electrical and electromechanical parts, etc. It is used.

[Conventional technology] Polyamide resin has excellent moldability, thermal stability, abrasion resistance,
It has excellent properties such as solvent resistance and is widely used in various molded products. However, due to its high hygroscopicity, there were problems with dimensional stability, and its use was limited by υ1 in some cases.

On the other hand, although ABS resin has excellent impact resistance, it has the disadvantage of poor solvent resistance.

If thermoplastic resins with even more excellent characteristics can be obtained by compensating for the disadvantages of polyamide resins and ABS resins with other advantages, it is expected that new applications will open up.

[Problems to be Solved by the Invention] However, since polyamide resins and ABS resins have different chemical structures, their compatibility is extremely poor, and it has been almost impossible to take advantage of their respective strengths.

[Means for solving the problems] As a result of intensive research to solve the above problems, the present invention has been made based on the following:
By blending a specific multiphase thermoplastic resin with polyamide resin and ABS resin as a compatibilizer, the compatibility between polyamide resin and ABS resin is improved, and the polyamide resin has excellent moldability and thermal stability. We have now completed a thermoplastic resin composition that has the excellent impact resistance of ABS resin as well as the excellent impact resistance and abrasion resistance of ABS resin.

That is, the first invention of the present invention is (I>95 to 5% by weight of polyamide resin, (II) AB
S resin 1 to 99% by weight and the above (I) + (I[)
(III) epoxy group-containing olefin copolymer 5 to 95 parts per 100 fliffi parts
% by weight and 95-5% by weight of a vinyl-based (co)polymer obtained from at least one type of vinyl monomer, one of the (co)polymers having a dispersed phase with a particle size of 0.001-10 μm. 0.1 to 100 parts by weight of the forming multiphase structured thermoplastic resin and 100 parts by weight of the above (I) + ('II) + (III), and 0 to 150 parts by weight of the (IV) embodiment filler. It is a thermoplastic resin composition made by blending.

Furthermore, the second invention comprises adding at least one type of vinyl monomer, at least one type of radical (co)' polymerizable organic peroxide, and a radical polymerization initiator to an aqueous suspension of an epoxy group-containing olefin copolymer. is added and heated under conditions that do not substantially cause decomposition of the radical polymerization initiator, and the vinyl monomer and radical (co-)
Impregnating an epoxy group-containing olefin copolymer with a polymerizable organic peroxide and a radical polymerization initiator, and when the impregnation rate reaches the initial 50% by weight or more, increasing the temperature of this aqueous suspension, Grafting precursor (A) 1 to 100 in which a vinyl monomer and a radical (co)polymerizable organic peroxide are copolymerized in an epoxy group-containing olefin copolymer
Weight %, epoxy group-containing olefin copolymer (B) 0~
99% by weight and 0 to 99% by weight of a vinyl (co)polymer (C) obtained by polymerizing at least one vinyl monomer is melt-mixed with a polyamide resin (I) and an ABS resin (II). Alternatively, the (A), (B) and (C) are melt-mixed in advance at a temperature of 200 to 300°C to form a multiphase thermoplastic resin (I[[), and then melted with the (I) and (II). A method for producing a thermoplastic resin composition comprising mixing.

The polyamide resin (I) used in the present invention includes nylon 6, nylon 6.6, nylon 6.10, nylon 6.
12, aliphatic polyamide resins such as nylon 11, nylon 12, nylon 4 and 6; aromatic polyamide resins such as polyhexamethylene diamine terephthalamide, polyhexamethylene diamine isophthalamide, xylene group-containing polyamide; Examples include modified products thereof and mixtures thereof. Particularly preferred polyamide resins include nylon 6 and nylon 6-6.

The ABS resin (II) used in the present invention is obtained by polymerizing two or more compounds selected from vinyl cyanide compounds, aromatic vinyl compounds, and unsaturated carboxylic acid alkyl ester compounds in the presence of a conjugated diene rubber. This is a graft copolymer (C) obtained by Further, if necessary, it may contain a copolymer (d) obtained by polymerizing two or more compounds selected from vinyl cyanide compounds, aromatic vinyl compounds, and unsaturated carboxylic acid alkyl ester compounds.

The composition ratio of the conjugated diene rubber and the above-mentioned compound in the graft copolymer (C) is not particularly limited;
A weight ratio of 0 is preferred. The composition ratio of the above-mentioned compounds is preferably 0 to 30% by weight of the vinyl cyanide compound, 30 to 80% by weight of the aromatic vinyl compound, and 0 to 70% by weight of the unsaturated carboxylic acid alkyl ester compound. Note that the particle size of the conjugated diene rubber is not particularly limited, but is 0.05
~1μ is preferred. The composition ratio of the above-mentioned compounds in the copolymer (d) is 0 to 30% by weight of vinyl cyanide compound,
Preferably, the aromatic vinyl compound is 50 to 90% by weight, and the unsaturated carboxylic acid alkyl ester compound is 0 to 40% by weight. The intrinsic viscosity of the copolymer (d) [30°C, dimethylformamide (DMF)] is also not particularly limited, but is 0.
25 to 1.0 is preferable.

Examples of the conjugated diene rubber include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, and the like.

Examples of vinyl cyanide compounds include acrylonitrile and methacrylatetrile; aromatic vinyl compounds include styrene, α-methylstyrene, vinyltoluene, dimethylstyrene, and chlorostyrene; and examples of unsaturated carboxylic acid alkyl ester compounds include methyl acrylate and ethyl. Acrylate, butyl acrylate, methyl methacrylate, hydroxyethyl acrylate, etc. can be mentioned.

ABS resin (II)! Examples of the IJ manufacturing method include emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, and emulsion-suspension polymerization.

The epoxy group-containing olefin copolymer in the multiphase thermoplastic resin used in the present invention is, in part, a binary copolymer of an olefin and an unsaturated glycidyl group-containing monomer produced by high-pressure radical polymerization, or It is a ternary or multi-component copolymer of an olefin, an unsaturated glycidyl group-containing monomer, and other unsaturated monomers, and the olefin in the copolymer is particularly preferably ethylene, with ethylene having 60 to 99
．． A copolymer comprising 5% by weight of monomer, 0.5 to 40% by weight of mono-R monomer containing a glycidyl group, and 0 to 39.5% by weight of other unsaturated monomers is preferred.

The unsaturated glycidyl group-containing monomers include glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, butenetricarboxylic acid monoglycidyl ester, carboxylic acid diglycidyl ester, butenetricarboxylic acid triglycidyl ester, and α-chloroallyl,
Examples include glycidyl esters such as maleic acid, crotonic acid, and fumaric acid, glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, glycidyloxyethyl vinyl ether, styrene-p-glycidyl ether, and p-glycidyl styrene. Preferred examples include glycidyl methacrylate and acrylic glycidyl ether.

Other unsaturated base materials include at least one monomer selected from olefins, vinyl esters, α, β-ethylenically unsaturated carboxylic acids and their derivatives, and specifically propylene , butene-1, hexene-1,
Olefins such as decene-1, octene-1, and styrene, vinyl esters such as RR vinyl, vinyl propionate, and vinyl benzoate, acrylic acid, methacrylic acid, methyl and ethyl acrylic acid or methacrylate,
Esters such as propyl, butyl, 2-ethylhexyl, cyclohexyl, dodecyl, octadecyl, maleic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid monoesters and diesters, vinyl chloride,
Examples include vinyl ethers such as vinyl methyl ether and vinyl ethyl ether, and acrylic acid amide compounds, with acrylic esters being particularly preferred.

Specific examples of the epoxy group-containing olefin copolymer include ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer,
Examples include ethylene/ethyl acrylate/glycidyl methacrylate copolymer, ethylene/carbon oxide/glycidyl methacrylate copolymer, ethylene/glycidyl acrylate copolymer, ethylene/vinyl acetate/glycidyl acrylate copolymer, etc. . Among these, preferred are ethylene/glycidyl methacrylate copolymer, ethylene/ethyl acrylate/glycidyl methacrylate copolymer, or ethylene/vinyl acetate/glycidyl methacrylate copolymer.

These epoxy group-containing olefin copolymers can be used as a mixture.

The method for producing an epoxy group-containing olefin copolymer by high-pressure radical polymerization includes the above-mentioned 60 to 99.5% by weight of ethylene,
One or more unsaturated glycidyl group-containing monomers 0.5-40
% by weight of at least one other unsaturated monomer 0-39.
The presence of a radical polymerization initiator of o, oooi ~ 1 wt % TFa combined pressure 500 ~ 4, OOO kg /
aA, preferably from 1.000 to 3.500! j／
Ca1l, reaction temperature 50-400°C, preferably 100°C
The polymer is simultaneously reacted in a seed or tube reactor under conditions of ~350° C. in the presence of a chain transfer agent and optionally auxiliary agents.
Alternatively, it is a method of contacting and polymerizing in stages.

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

In addition, as a chain transfer agent, hydrogen, propylene, butene-1
,01-C2o or higher saturated aliphatic and halogen-substituted hydrocarbons such as methane, ethane, propane, butane, isobutane, n-hexane, n-heptane, cycloparaffins, chloroform and carbon tetrachloride, 01- C2o or higher saturated aliphatic alcohols such as methanol, ethanol, propatool,
and isopropanol, C1-C2o or higher saturated aliphatic carbonyl compounds such as carbon dioxide, acetone and methyl ethyl ketone, and aromatic compounds such as toluene, diethylbenzene and xylene.

The epoxy group-containing olefin copolymers of the present invention include homopolymers such as low density, medium density, and high density polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, ethylene-propylene copolymers, Ethylene-
With other α-olefins whose main component is ethylene, such as butene-1 copolymer, ethylene-hexene-1 copolymer, ethylene-4-methylpentene-1 copolymer, and ethylene-octene-1 copolymer. copolymers with other α-olefins mainly composed of propylene such as propylene-ethylene block copolymers, engineered ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-methacrylate Acid copolymers, copolymers of ethylene and esters of acrylic acid or methacrylic acid such as methyl, ethyl, propyl, isopropyl, butyl, ethylene-
Maleic acid copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, liquid polybutadiene, ethylene-vinyl acetate-vinyl chloride copolymer and mixtures thereof, or synthetic resins different from these, or Mixtures with rubber are also included in the invention.

Specifically, the vinyl-based (co)polymer in the multiphase thermoplastic resin used in the present invention includes styrene, nuclear-substituted styrene, such as methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, and chlorstyrene. , α-n-substituted styrene, such as α-methylstyrene,
It is a (co)polymer obtained by mixing one or more of vinyl aromatic type suspensions such as α-ethylstyrene and (meth)acrylonitrile monomers.

In the present invention, the multiphase thermoplastic resin (I It refers to a group-containing olefin copolymer that is uniformly dispersed in a spherical shape.

The particle size of the dispersed polymer is o, ooi ~ 10 μm1
Preferably it is 0.01 to 5 μm.

When the dispersed resin particle size is less than 0.001 μm or 1
If it exceeds 0 μm, the polyamide resin and ABS resin will not be sufficiently compatible, resulting in a decrease in impact resistance and delamination.

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

If 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 it is not preferable because the heat resistance decreases.

Moreover, if the number average degree of polymerization exceeds 10.000, the melt viscosity will increase, moldability will decrease, and surface gloss will decrease, which is not preferable.

The thermoplastic resin having a multiphase structure according to the present invention contains an olefin copolymer containing an epoxy group in an amount of 5 to 95% by weight, or preferably 20 to 9% by weight.
01m%.

Therefore, the vinyl (co)polymer is 95 to 5%,
Preferably it is 80 to 10% by weight.

If the epoxy group-containing olefin copolymer is less than 5% by weight, the compatibility effect with the polyamide resin cannot be sufficiently exhibited, and if the epoxy group-containing olefin copolymer exceeds 95% by weight, the present invention This is not preferable because it impairs the heat resistance and dimensional stability of the thermoplastic resin composition.

The grafting method for producing the multiphase thermoplastic resin of the present invention may be any generally well-known method such as chain transfer method or ionizing radiation irradiation method, but the most preferred method is as shown below. It depends on the method. The reason for this is that the grafting efficiency is high and secondary aggregation due to heat does not occur, so performance is more effectively expressed.

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

That is, 100 parts by weight of an epoxy group-containing olefin copolymer is suspended in water, and 5 to 400 parts by weight of at least one vinyl monomer are mixed with the following formula (a) or (b).
One type or a mixture of two or more types of radical (co)polymerizable organic peroxides represented by
A radical polymerization initiator with a decomposition temperature of 40 to 90°C to obtain a half-life of 10 hours and a radical (co)polymerizable organic polymer in an amount of 0.1 to 10 parts by weight per part of ffi is added to the vinyl monomer. 0.01 to 100 parts of total with oxide
5 parts by weight of the vinyl monomer, the radical (co)polymerizable organic peroxide, and the radical polymerization initiator. is impregnated into an epoxy group-containing olefin copolymer, and when the impregnation rate reaches the initial 50% by weight or more, the temperature of this aqueous suspension is increased, and the vinyl monomer and the radical (co)polymerizable organic The grafted precursor (A) is obtained by copolymerizing the peroxide in an epoxy group-containing olefin copolymer. This grafted precursor is also a multiphase thermoplastic. Therefore, this grafting precursor (A) may be melt-mixed directly with the polyamide resin and ABS resin.

The multiphase thermoplastic resin of the present invention can also be obtained by kneading the grafted precursor (A) while melting at 100 to 300°C. At this time, the grafted precursor (A)
A multiphase thermoplastic resin can also be obtained by separately mixing an epoxy group-containing olefin copolymer or a vinyl (co)polymer and kneading the mixture while melting. Most preferred is a thermoplastic resin with a multiphase structure obtained by kneading a grafted precursor.

The radical (co)polymerizable organic peroxide represented by the above-mentioned formula (a) is - formula % formula %) [wherein, R1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R2 is a hydrogen atom] or a methyl group, R3 and R4 are each an alkyl group having 1 to 4 carbon atoms, and R5 is a methyl group having 1 to 4 carbon atoms;
12 alkyl group, phenyl group, alkyl-substituted phenyl group or cycloalkyl group having 3 to 12 carbon atoms, m
is 1 or 2. ] This is a compound represented by

Further, the radical (co)polymerizable organic peroxide represented by formula (b) is - formula% formula% [wherein, R6 is a hydrogen atom or a furkyl group having 1 to 4 carbon atoms, and R is a hydrogen atom or Methyl group, R8 and R9 are each an alkyl group having 1 to 4 carbon atoms, R is 1 to 12 carbon atoms
represents an alkyl group, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms, and n is 0.
, 1 or 2. ] This is a compound represented by

Examples of the radical (co)polymerizable organic peroxide represented by general formula (a) include t-butylperoxyacryloyloxyethyl carbonate, t-amylperoxyacryloyloxyethyl carbonate, t-hexyl Peroxyacryloyloxyethyl carbonate, 1.1
．． 3.3-Tetramethylbutylperoxyacryloyloxyethyl carbonate, cumylperoxyacryloyloxyethyl carbonate, p-isopropylcumylperoxyacryloyloxyethyl carbonate, t-butylberoxymethacryloyloxyethyl carbonate, t-amylperoxy Acryloyloxyethyl carbonate, t-hexylberoxymethacryloyloxyethyl carbonate, 1.1.3.3-tetramethylbutylberoxymethacryloyloxyl carbonate, cumylperoxymethacryloyloxyethyl carbonate, p- Isopropylcumylperoxyacryloyloxyethyl carbonate, t-butylperoxyacryloyloxyethoxyethyl carbonateoxyethoxyethyl carbonate, t-hexylperoxyacryloyloxyethoxyethyl carbonate, 1
．． 1.3.3-Tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate, cumylperoxyacryloyloxyethoxyethyl carbonate, p-
Isopropylcumylperoxyacryloyloxyethoxyethyl carbonate, t-butylperoxymethacryloyloxyethoxyethyl carbonate, t-amylperoxyacryloyloxyethoxyethyl carbonate, t-hexylperoxymethacryloyloxyethoxyethyl carbonate, 1,1゜3.3-Tetramethylbutylperoxymethacryloyloxyethoxyethoxyethyl carbonate, cumylberoxymethacryloyloxyethoxyethyl carbonate, p-isobrobylcumylperoxymethacryloyloxyethoxyethoxyethyl carbonate, t-butylberoxyacryloyloxyisopropyl carbonate, t-amylperoxyacryloyloxyisopropyl carbonate, sylperoxyacryloyloxyisopropyl carbonate, 1.1,3.3-tetramethylbutylperoxyacryloyloxyisopropyl carbonate, cumylperoxyacryloyloxyisopropyl carbonate,
p-isobrobylcumylberoxyacryloyloxyisopropylene carbonate, t-butylberoxymethacryloyloxyisopropyl carbonate, t-amylperoxyacryloyloxyisopropyl carbonate,
t-hexylperoxyacryloyloxyisopropyl carbonate, 1.1,3.3-tetramethylbutylperoxyacryloyloxyisopropyl carbonate,
Examples include cumylperoxymethacryloyloxyimbrobyl carbonate, p-isopropylene cumylperoxymethacryloyloxyisobrovyl carbonate, and the like.

Furthermore, as a compound represented by formula (b), t
-butylperoxyallyl carbonate t-amylperoxyallyl carbonate, -hexylperoxyallyl carbonate 3,3-tetramethylbutylperoxyallyl carbonate, p-menthane peroxyallyl carbonate t-butylperoxymethallyl carbonate, t-amylperoxyallyl carbonate carbonate, 1-hexylperoxymethallyl carbonate, 1.

1,3.3-Tetramethylbutylperoxymethallyl carbonate, p-menthane peroxymethallyl carbonate, cumylperoxymethallyl carbonate, t-butylperoxyallyloxyethyl carbonate, t-amylberoxyallyloxyethyl carbonate, t- Hexylperoxyallyloxyethyl carbonate, 1-amylperoxymethacryloyloxyethyl carbonate, t
-Hexylperoxymethacryloyloxyethyl carbonate, t-butylperoxyacryloyloxyisopropyl carbonate, t-amylperoxyallyloxyisopropyl carbonate, t-hexylperoxyacryloyloxyisopropyl carbonate, t-butylperoxymethacryloyloxy Examples include isobrobyl carbonate, t-amylperoxyacryloyloxyisopropyl carbonate, and t-hexylperoxymethacryloyloxyisopropyl carbonate.

Among them, preferred are t-butylperoxyacryloyloxyethyl carbonate, t-butylberoxymethacryloyloxyethyl carbonate, t-butylperoxyallyl carbonate, and t-butylperoxymethallyl carbonate.

In the present invention, the above (I) + (II) + (I[
0 to 150 parts by weight of the inorganic filler (IV) can be blended with 100 parts by weight of the resin component containing [).

Examples of the above-mentioned inorganic fillers include powder-like, tabular, scaly, acicular, spherical or hollow, and fibrous, and specifically, 1il! Im calcium, 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 powdery granular fillers; Metal foils such as mica, glass plates, sericite, pyrophyllite, and aluminum flakes, flat or scaly fillers such as graphite; hollow fillers such as shirasu balloons, metal balloons, glass balloons, and pumice; glass fibers, Carbon fiber, graphite tape, whiskers, gold imm, silicon carbide fiber, asbestos,
Examples include mineral fibers such as wostonite.

If the amount of filler added exceeds 150 loads, the impact strength of the molded article will decrease, which is not preferable.

In addition, the surface of the inorganic filler is treated with stearic acid, oleic acid, palmitic acid or their metal salts, paraffin wax, polyethylene wax or modified products thereof, organic silane, organic borane, organic titanate, etc. It is preferable to apply

The thermoplastic composition of the present invention comprises polyamide resin and A
It is manufactured by mixing BS resins while melting them at a temperature in the range of 200 to 300°C.

The melt-mixing order may be such that all the components are melt-mixed at the same time, or the polyamide resin or ABS resin and the multiphase thermoplastic resin are melt-mixed in advance, and then the other resin is melt-mixed. Good too.

The melt-mixing method can be carried out using a commonly used kneading machine such as a Banbury mixer-1 pressure kneader-1 kneading extruder, a twin-screw extruder, or a mixing roll.

In the present invention, other thermoplastic resins such as polyolefin resins, polyvinyl chloride resins, polyvinylidene chloride resins,
polyester resin, polyphenylene sulfide resin,
Polsulfone resin, natural rubber, synthetic rubber, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, organic flame retardants such as halogen-based and phosphorus-based, organic fillers such as this powder, antioxidants, and ultraviolet inhibitors. Additives such as lubricants, coupling agents, dispersants, foaming agents, crosslinking agents, and coloring agents may be added.

[Example] Next, the present invention will be explained in more detail with reference to Examples.

LLf2L (manufacture of multiphase thermoplastic resin (I)) In a stainless steel autoclave with a capacity of 51, pure water 2.
500 g was added, and 2.5 Q of polyvinyl alcohol was further dissolved therein as a suspending agent. In this, ethylene/glycidyl methacrylate copolymer (containing glycidyl methacrylate 15% by weight) is used as an epoxy group-containing olefin copolymer.
[Product name: Lexpar J-3700J (manufactured by Nippon Petrochemicals Co., Ltd.) 7000 was added and dispersed by stirring under a nitrogen atmosphere. Separately, benzoyl peroxide as a radical polymerization initiator "Product name: Niver BJ (manufactured by NOF Corporation, 10 hours half-life temperature 74℃>1.5o1 t-butylberoxymethacryloyl as a radical (co)polymerizable organic peroxide 6 g of loxethyl carbonate was dissolved in styrene 30C1 as a vinyl monomer, and this solution was poured into the autoclave and stirred.The autoclave was then heated to 60-65°C and stirred for 2 hours to initiate radical polymerization. A vinyl mono-omega substance containing a radical (co)polymerizable organic peroxide and a radical (co)polymerizable organic peroxide was impregnated into an epoxy group-containing ethylene copolymer.Then, the impregnated vinyl monomer and a radical (co)polymerizable organic peroxide were impregnated into an epoxy group-containing ethylene copolymer. After confirming that the total amount of material and radical polymerization initiator is 50% by weight of the initial amount, the temperature is raised to 80-85°C, maintained at that temperature for 7 hours to complete polymerization, and washed with water. and dried to obtain a grafted precursor.

Next, this grafted precursor was extruded at 240° C. using a Laboplast Mill-axial extruder [manufactured by Toyo Seiki Seisakusho Co., Ltd.] to cause a grafting reaction, thereby obtaining a multiphase thermoplastic resin (III).

This multiphase-structured thermoplastic resin was examined using a scanning electron microscope rJE.
When observed with OL JSM 'D300J (product name, manufactured by JEOL Ltd.), the particle size was 0.3 to 0.4.
It was a thermoplastic resin with a multiphase structure in which perfectly spherical resin of μm was uniformly dispersed.

At this time, the grafting efficiency of the styrene polymer was 77.
It was 1 mm%.

Nylon 6/6 (Toshiku Co., Ltd.) 11 as polyamide resin
, trade name "Amilan CM3001-NJ"), an ABS resin having the composition shown in Table 1, and a multiphase structure thermoplastic resin obtained in Reference Example were melt-mixed in the proportions shown in Table 2.

The melt-mixing method involved supplying the materials to a co-directional twin-screw extruder (manufactured by Plastic Engineering Research Institute Co., Ltd.) with a screw diameter of 30 mm and a cylinder temperature of 250° C., and melt-mixing within the cylinder. After the mixed resin is granulated, 15
After drying at 0° C. for 3 hours, test pieces were prepared by injection molding. The size of the test piece is as follows.

Izotsu impact test piece 131111X esmmx
6mm (with notch) Load deflection temperature test piece 1311111X 13011
1111 X 61111 The test method is as follows.

(1) Izot impact value (with notch): JIS
1110 (2) Deflection temperature under load: JIS K7207 Regarding chemical resistance, the test piece was immersed in methanol at 75°C for 30 days, and then its appearance was observed.

O...No change.

Δ...Cracks occur on the surface Some of it is eluted.

X: Significant surface elution.

In addition, whether or not the resin peeled off in layers from the fractured portion of the test piece was examined to determine whether the compatibility was good or bad.

Table 3 shows an example in which the grafted multiphase thermoplastic resin of the above example was replaced with the grafted precursor obtained in the reference example. This case also shows the same effect as the grafted multiphase thermoplastic resin.

Examples 14-19 In addition to the above examples, average! l fiber length 5.0mm.

Table 4 shows an example in which glass fibers with a diameter of 10 μm were blended.

Table 4 shows an example in which modified ethylene-glycidyl methacrylate copolymer and vinyl acetate copolymer were used in Shell M.2 Apart from the above examples.

Table 1 Table 3 Table 4 Table 5 ** Maleic anhydride 0.5% by weight adduct [Effects of the invention] The thermoplastic resin composition of the present invention has the advantages of polyamide resin and ABS resin. It is a resin composition with excellent heat resistance, impact resistance, and adhesive properties. Therefore, it is widely used in, for example, automobile parts, electrical/electronic parts, and industrial parts.

Patent applicant Nippon Petrochemical Co., Ltd. Procedural amendment 1. Description of the case Patent Application No. 276710 of 1988 2, Name of the invention Thermoplastic resin composition and its manufacturing method 3, Person making the amendment Relationship to the case Patent applicant name Nippon Petrochemical Co., Ltd. 4, Agent address Minami-Aoyama-1-chome, Minato-ku, Tokyo, January 5, Date of amendment order (voluntary) (Shipping date) Showa, Month, Day 7, Contents of amendment (1) The scope of the patent claims is corrected as shown in the attached sheet.

(2) “Acid resistance” on page 15, line 13 of the specification is “acetic acid”
I am corrected.

(3) Add the following sentence between the second and third lines of page 30.

In the present invention, the amounts of (I) and (II) are selected depending on the intended use of the composition.

That is, if the purpose is to improve the impact resistance, dimensional stability, heat resistance, and rigidity, which are disadvantages of polyamide resin while maintaining its characteristics, the polyamide resin should be used in an amount of 50 to 99% by weight, preferably 60 to 95% by weight. is necessary.

The reason for this is that if the polyamide resin is less than 50% by weight, the moldability, chemical resistance, and weather resistance, which are characteristics of polyamide resin, will be impaired; This is because it does not have the effect of improving properties, dimensional stability, heat resistance, and rigidity.

In addition, if the purpose is to improve the chemical resistance and weather resistance, which are disadvantages of ABS resin while maintaining the characteristics of ABS resin, 50 to 99% by weight, preferably 60% to 95% by weight of ABS resin is required. be.

If the ABS resin is less than 50% by weight, the heat resistance, resistance**, and rigidity of the ABS resin cannot be exhibited, and if it exceeds 99% by weight, the moldability, chemical resistance, and It is not preferred because it has no effect on improving weather resistance.

The multiphase structured thermoplastic resin of the present invention has (I)+(II)1
It can be used in an amount of 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight.

If the amount of the multiphase thermoplastic resin is less than 0.1111 parts, it is not preferable because there is no compatibilizing effect and the impact strength decreases, and delamination occurs in the molded product and the appearance deteriorates. Also, 10
If the weight exceeds 0 weight, the heat resistance of the composition will decrease, which is not preferable. (4) Same, page 36, lines 12 to 13, “Ethylene-
"glycidyl methacrylate" is corrected to "ethylene-glycidyl methacrylate J."

(5) Table 2 on page 38 of the same is corrected as shown in the attached sheet.

(6) Table 3 on page 39 of the same is amended as shown in the attached sheet.

(7) Table 4 on page 40 of the same is corrected as shown in the attached sheet.

(8) Table 5 on page 41 of the same is corrected as shown in the attached sheet.

Above 2, Claims (1) (I) Polyamide resin 99-1%, (II
) ABS resin Resin 1 to Step 9 For 8 parts by weight of the above (I) + (I[), (III> Epoxy group-containing olefin copolymer 5 to 95
1iffi% and at least one kind of vinyl monomer.
Multiphase thermoplastic resin 0.1 to 10 in which one (co)polymer forms a dispersed phase with a particle size of 0.001 to 10 μm
0 parts by weight, and (IV) 0 to 150 parts by weight of an inorganic filler per 100 parts by weight of the above (I) + (ff) + (I[[).

(2) The thermoplastic resin with a multi-phase structure comprises at least one vinyl monomer and the following general formula (a) or (b) [wherein R1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, RR is a hydrogen atom or a methyl group, 2ゝ7 R6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, RR
and RR each have 31 carbon atoms and 4
8ゝ9 1-4 alkyl group, RR represents an alkyl group having 1-12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3-12 carbon atoms, m is 1 or 2, and n is 0, 1 or 2. Grafting precursor (A) 1 to 100 in which at least one radical (co)polymerizable organic peroxide represented by ) is copolymerized in epoxy group-containing olefin copolymer particles
Weight %, epoxy group-containing olefin copolymer (B) 0-
99% by weight, and 0 to 99% by weight of a vinyl (co)polymer (C) obtained by (co)polymerizing at least one vinyl monomer and/or once tsaa'- The thermoplastic resin composition according to claim 1, which is a grafted product consisting of:

(3) The epoxy group-containing olefin copolymer contains 60 to 99.5% by weight of ethylene, 40 to 0.5% by weight of glycidyl (meth)acrylate, and 0 to 39% of other unsaturated monomers.
Claims 1 to 5 are copolymers consisting of 5% by weight.
Thermoplastic resin composition according to any one of Item 2.

(4) The vinyl (co)polymer contains 5 of the vinyl monomers.
The thermoplastic resin composition according to claim 2 or 3, wherein 0% by weight or more of the thermoplastic resin composition comprises a vinyl aromatic monomer.

(5) The vinyl monomer is a vinyl aromatic monomer, (meth)
Claim 1, which is one or more vinyl monomers selected from the group consisting of acrylic ester type suspensions, (meth)acrylic nitrile monomers, and vinyl ester monomers; or Thermoplastic resin composition according to item 2.

<6) To an aqueous suspension of an epoxy group-containing olefin copolymer, at least one vinyl monomer, at least one radical (co)polymerizable organic peroxide, and a radical polymerization initiator are added, and radical polymerization is carried out. The vinyl monomer, the radical (
Co) A polymerizable organic peroxide and a radical polymerization initiator are impregnated into an epoxy group-containing olefin copolymer, and when the impregnation rate reaches the initial 50 or more layers, the temperature of this aqueous suspension is raised. , Grafting precursor (A) 1 to 10 in which a vinyl monomer and a radical (co)polymerizable organic peroxide are copolymerized in an epoxy group-containing olefin copolymer.
0% by weight, epoxy group-containing olefin copolymer (B) 0
~99% by weight, and 0~99% by weight of vinyl (co)polymer (C) obtained by polymerizing at least one vinyl monomer with polyamide resin (I) and ABS resin (I). Melt mix or prepare the (A>, (B) and (C)) in advance.
1. A method for producing a thermoplastic resin composition, which comprises melt-mixing in a temperature range of 00 to 300[deg.] C. to obtain a multiphase thermoplastic resin (II[), and melt-mixing the resin with (I) and (II).

(7) The radical (co)polymerizable organic peroxide has the following general formula (a) or (b) (blank below) [In the formula, R1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, RR is hydrogen atom or methyl group, 2ゝ7 R6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R3
, R4, R8, and R9 are each an alkyl group having 1 to 4 carbon atoms, and RR is an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted) engineering group, or a cycloalkyl group having 3 to 12 carbon atoms. and m
is 1 or 2, and n is 0, 1 or 2. ] The method for producing a thermoplastic resin composition according to claim 6, which is one or a mixture of two or more peroxycarbonate compounds represented by:

(8) The vinyl monomer is a vinyl aromatic monomer, (meth)
Claim 6 or 7, which is one or more vinyl monomers selected from the group consisting of acrylic acid ester congeners, (meth)acrylonitrile monomers, and vinyl ester monomers. A method for producing the thermoplastic resin composition described above.

(9) The epoxy group-containing olefin copolymer contains 60 to 99.5 percent ethylene, 40 to 0.5 percent glycidyl (meth)acrylate, and 0 to 3 percent of other unsaturated materials.
A method for producing a thermoplastic resin composition according to any one of claims 6 to 8, which is a copolymer containing 9.5% by weight.

(10) The vinyl (co)polymer is made of
A method and method for producing a thermoplastic resin composition according to claim 6, wherein 50% by weight or more of the thermoplastic resin composition is comprised of a vinyl aromatic monomer.

Claims (10)

[Claims] (1) (I) 99-1% by weight of polyamide resin, (II
) 1 to 99% by weight of ABS resin, based on 100 parts by weight of the above (I) + (II), (III) 5 to 95% by weight of an epoxy group-containing olefin copolymer, and at least one vinyl monomer. 95 to 5% by weight of the obtained vinyl-based (co)polymer, and one of the (co)polymers forms a dispersed phase with a particle size of 0.001 to 10 μm. - 100 parts by weight, and a thermoplastic resin composition containing 0 to 150 parts by weight of (IV) an inorganic filler to 100 parts by weight of the above (I) + (II) + (III). (2) A thermoplastic resin with a multi-phase structure contains at least one vinyl monomer and the following general formula (a) or (b) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(a) ▲Mathematical formulas, chemical formulas, There are tables etc.▼(b) [In the formula, R_1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R_2 and R_7 are hydrogen atoms 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, R_9 each have 1 to 4 carbon atoms.
The alkyl group, R_5, R_1_0 represents 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. ] Grafting precursor (A) 1 to 100 in which at least one radical (co)polymerizable organic peroxide represented by is copolymerized in epoxy group-containing olefin copolymer particles.
Weight%, epoxy group-containing olefin copolymer (B) 0-99% by weight, and vinyl-based (co)polymer (C) obtained by (co)polymerizing at least one vinyl monomer 0-99 % by weight and/or a grafted product. (3) The epoxy group-containing olefin copolymer contains 60 to 99.5% by weight of ethylene, 40 to 0.5% by weight of glycidyl (meth)acrylate, and 0 to 39% of other unsaturated monomers.
Claims 1 to 5 are copolymers consisting of 5% by weight.
Thermoplastic resin composition according to any one of Item 2. (4) The vinyl (co)polymer contains 5 of the vinyl monomers.
The thermoplastic resin composition according to claim 2 or 3, wherein 0% by weight or more of the thermoplastic resin composition comprises a vinyl aromatic monomer. (5) The vinyl monomer is a vinyl aromatic monomer, (meth)
Claim 1 or 2 is one or more vinyl monomers selected from the group consisting of acrylic acid ester monomers, (meth)acrylonitrile monomers, and vinyl ester monomers. The thermoplastic resin composition described in . (6) Add 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, and perform radical polymerization. The vinyl monomer, the radical (
Co) A polymerizable organic peroxide and a radical polymerization initiator are impregnated into an epoxy group-containing olefin copolymer, and when the impregnation rate reaches the initial 50% by weight or more, the temperature of this aqueous suspension is raised. , a grafting precursor (A) in which a vinyl monomer and a radical (co)polymerizable organic peroxide are copolymerized in an epoxy group-containing olefin copolymer.
1 to 100% by weight, epoxy group-containing olefin copolymer (B) 0 to 99% by weight, and vinyl (co)polymer obtained by polymerizing at least one vinyl monomer (C) 0 to 99% by weight of polyamide resin (I) and ABS resin (II), or melt-mix (A), (B) and (C) in advance at a temperature of 200 to 300°C to form a multiphase structure. A method for producing a thermoplastic resin composition, which comprises preparing a thermoplastic resin (III) and melt-mixing the thermoplastic resin (I) and (II). (7) The radical (co)polymerizable organic peroxide has the following general formula (a) or (b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (b ) [In the formula, R_1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R_2 and R_7 are 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, R_9 each have 1 to 4 carbon atoms.
The alkyl group, R_5, R_1_0 represents 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 method for producing a thermoplastic resin composition according to claim 6, which is one or a mixture of two or more peroxycarbonate compounds represented by: (8) The vinyl monomer is a vinyl aromatic monomer, (meth)
Claim 6 or 7 is one or more vinyl monomers selected from the group consisting of acrylic acid ester monomers, (meth)acrylonitrile monomers, and vinyl ester monomers. A method for producing a thermoplastic resin composition as described in Section 1. (9) The epoxy group-containing olefin copolymer contains 60 to 99.5% by weight of ethylene, 40 to 0.5% by weight of glycidyl (meth)acrylate, and 0 to 39% of other unsaturated monomers.
Claims 6 to 5 are copolymers consisting of 5% by weight.
A method for producing a thermoplastic resin composition according to any one of Item 8. (10) Vinyl (co)polymer is vinyl monomer,
7. The method for producing a thermoplastic resin composition according to claim 6, wherein 50% by weight or more is comprised of a vinyl aromatic monomer.