JPS63162750A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which is useful as an engineering material such as a material for automobile parts and has excellent impact resistance, weld appearance and weld strength, consisting of a polytetramethylene adipamide resin and a specified styrene polymer. CONSTITUTION:95-60wt% arom. vinyl compd. (a) such as styrene and 5-40wt% vinyl cyanide compd. (b) such as acrylonitrile are added to 0.5-20wt% (based on the amount of the compsn.) unsaturated compd. (c) having at least one functional group selected from the group consisting of COOH, acid anhydride, epoxy, OH, NH2 groups, etc. 10-50wt% butadiene and/or ethylene/alpha-olefin rubbery polymer (d) such as polybutadiene having a 1,2-bonded vinyl unit content not higher than 10wt% in the form of particles having an average particle size of 2,000-10,000Angstrom is dispersed in the polymn. system. The mixture is solution- polymerized at 60-150 deg.C under a pressure of 1-40kg/cm<2> to obtain a styrene polymer (B). 5-95pts.wt. polytetramethylene adipamide (A) composed of repeating units of the formula is melt-kneaded with 95-5pts.wt. component B.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a thermoplastic resin composition having excellent impact resistance, weld appearance, and weld strength.

b; Conventional technology Polyamide resin has traditionally been used as an engineering plastic material due to its excellent balance of physical properties.
It is widely used in various industrial fields such as automobiles, electricity, and electronics. However, nylon 6 used in the above industrial fields
Polyamide resins such as , nylon 6.6, etc. generally still lack impact resistance, so those reinforced with glass fiber or the like are usually used. However, even such polyamide resin compositions reinforced with glass fibers still cannot be said to have sufficient impact resistance, and also have the disadvantage that the strength of the welded portions is weak.

Therefore, compositions in which ethylene-propylene rubber modified with maleic anhydride or the like is mixed with the polyamide resin are known, but these compositions have the disadvantage of poor weld appearance and weld strength.

On the other hand, A obtained by polymerizing acrylonitrile and styrene in the presence of an ethylene-propylene rubbery polymer
BS resin has excellent impact resistance and moldability, so it is widely used in the automobile field, light electrical field, etc. However, polyamide resin compositions containing such ABS resin have poor weld appearance and weld strength. It had the following drawback.

Problems to be Solved by the C0 Invention In order to improve these drawbacks, nylon 6.6 and polybutadiene-styrene-acrylonitrile copolymer (hereinafter referred to as A
Various studies were conducted on compositions consisting of BS resin (BS resin) and nylon 6.6 and ABS resin, but these resins had poor compatibility with each other, exhibited peeling phenomena, and were extremely brittle. . However, during the polymerization of the ABS resin or the composition of ABS resin and nylon 6, nylon 6.6, the composition of ABS resin and nylon 6, nylon 6.6, which is obtained by copolymerizing acrylamide, acrylic acid, maleic anhydride, etc. Although the solubility was improved and impact resistance was achieved, the weld appearance and weld strength were still not improved. As a result of intensive studies on thermoplastic resin compositions with excellent impact resistance, weld appearance, and weld strength, we found that a rubbery polymer modified with an unsaturated compound having a specific functional group, a modified styrenic polymer, and polytetramethylene were developed. Adipamide resin (hereinafter referred to as nylon 4)
The inventors have discovered that the above object can be fully achieved by a thermoplastic resin composition consisting of a thermoplastic resin composition comprising the following:

That is, the present invention provides a styrenic polymer obtained by polymerizing (a) 5 to 95% by weight of a polytetramethylene adipamide resin and (b) an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubber polymer. In the thermoplastic resin composition consisting of 95 to 5 wt% A thermoplastic resin composition characterized by containing a compound as a copolymerization component.

C3 Detailed description of the invention (al Polytetramethylene adipamide resin component The polytetramethylene adipamide resin (hereinafter referred to as nylon 4.6) used in the present invention has a repeating structure represented by the general formula % formula %) It is a polyamide resin consisting essentially of units.

The polytetramethylene adipamide resin is disclosed in, for example, JP-A-5
Specification No. 6-149430, Specification No. 56-149431, Specification No. 5B-83029, Special Publication wA60-2
Mention may be made of the polytetramethylene adipamide resin produced by the method described in Publication No. 884.3.

In order to obtain the thermoplastic resin composition of the present invention, the relative viscosity (ηre
d; Polymer 1 in 97% sulfuric acid Loom It at 30°C
Preference is given to using nylon 4,6, which has a hardness of 100 g (measured in solution).

The proportion of nylon 4.6 used in the thermoplastic resin composition of the present invention is 5 to 95% by weight, preferably 10 to 90% by weight,
For office work, it is preferably used in a range of 50 to 90% by weight. If the amount used is less than 5% by weight, the weld appearance and weld strength will not be improved, and if it exceeds 95% by weight, the impact resistance, weld appearance and weld strength will not be improved.

(b) Rubbery polymer-modified styrenic polymer component The rubbery polymer-modified styrenic polymer, which is the component (b) in the thermoplastic resin composition of the present invention, has aromatic properties in the presence of the rubbery polymer. It is obtained by polymerizing a vinyl compound and a vinyl cyanide compound, and is an unsaturated compound having at least one functional group selected from a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group, and an amino group. It has been denatured.

Aromatic vinyl compounds The aromatic vinyl compounds used here include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, p-tertiary -butylstyrene, ethylstyrene,
Examples include vinylnaphthalene, preferably styrene, α
-Methylstyrene. Korababa is used alone or in combination of two or more.

Vinyl cyanide Vinyl cyanide compounds include acrylonitrile, methacrylaterile, and the like. The usage ratio of the aromatic vinyl compound and vinyl cyanide compound in the component (b) is generally aromatic vinyl compound/vinyl cyanide compound = 9515~
60/40, preferably 90/10 to 65/35 (
(% by weight).

Furthermore, other vinyl compounds copolymerizable with these vinyl compounds can be copolymerized within a range that does not impair the object of the present invention.

Other copolymerizable vinyl compounds include (meth)acrylic acid alkyl esters and maleimide compounds, which may be used alone or in combination of two or more.

The (meth)acrylic acid alkyl esters include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate,
Acrylic acid alkyl esters such as phenyl acrylate and benzyl acrylate, and methyl methacrylate, ethyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, Examples include methacrylic acid alkyl esters such as benzyl methacrylate. The maleimide compounds include maleimide-% N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, hydroxyphenylmaleimide, N(
Examples include p-bromophenyl)maleimide.

The amount of these other copolymerizable vinyl compounds used is (b)
It can be used generally in an amount of 0 to 50% by weight, preferably 0 to 30% by weight, in the components excluding the rubbery polymer.

Rubbery polymers to be present during the polymerization of the aromatic vinyl compound and vinyl xylene compound include polybutadiene, butadiene-isoprene copolymer, butadiene-(
Diene rubbers such as meth)acrylic acid ester copolymers, butadiene-styrene copolymers, butadiene-acrylonitrile copolymers, polychloroprene, olefin-based rubbers such as ethylene-propylene copolymers, and ethylene-propylene-polyene copolymers Rubber, acrylic rubber such as polyacrylic acid ester, styrene-butadiene block copolymer, styrene-isoprene block copolymer, styrene-isoprene-butadiene block copolymer, and water addition of the block copolymer. Examples include styrene-grafted ethylene-propylene elastomer, thermoplastic elastomer, and ethylene-based ionomer copolymer. These rubbery polymers can be used alone or in combination of two or more. Among these rubbery polymers, butadiene rubbery polymers and ethylene-α-olefin rubbery polymers are preferred. The amount of rubbery polymer in component (b) is not particularly limited, but industrially it is 10 to 50.
! It is advantageous to use within a range of %.

The butadiene-based rubbery polymers include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-isoprene copolymer, butadiene-(meth)acrylic acid alkyl ester copolymer, and butadiene-styrene block. There are copolymers, hydrogenated products of butadiene-styrene block copolymers, etc., and these may be used alone or in combination of two or more. The butadiene-based rubbery polymer is polybutadiene, butadiene-isoprene copolymer, or butadiene-(meth)acrylic, in which the amount of vinyl bond in the polybutadiene portion is 10% by weight or less, from the viewpoint of thermal stability of the produced thermoplastic resin composition. Preferably, it is an acid alkyl ester copolymer.

Among these, butadiene-alkyl (meth)acrylate copolymer is particularly preferred. Said (meta)
All of the above-mentioned acrylic acid alkyl esters can be used, but preferred (meth)acrylic acid alkyl esters include ester compounds of acrylic acid and alcohols in which the alkyl group in the alkyl ester has 2 to 12 carbon atoms. Specific examples include ester compounds of (meth)acrylic acid such as ethyl, butyl, hexyl, octyl, 2-ethylhexyl, and lauryl, which may be used alone or in combination of two or more. Particularly preferred is n-butyl acrylate. Further, a preferred composition ratio of butadiene and (meth)acrylic acid ester in the copolymer is within the range of butadiene/(meth)acrylic acid alkyl ester = 575 to 8/2 (weight ratio).

The preferred composition ratio in the butadiene-isoprene copolymer is within the range of butadiene/isoprene = 773 to 4/6 (weight ratio). Further, the ethylene-α-olefin rubbery polymer is a copolymer of ethylene and α-olefin or a copolymer of ethylene, α-olefin, and polyene.

The α-olefin used here has 3 to 3 carbon atoms.
It is an unsaturated hydrocarbon compound having 20 atoms, specifically propylene, butene-1, pentene-1, hexene-1.
1, heptene-1,4-methylbutene-14-methylpentene-1, and the like. Particularly preferred are propylene and butene-1.

As the polyene compound, 1,4-pentadiene,
1,5-hexadiene, 2-methyl-1,5-hexadiene, 3,3-dimethyl-1,5-hexadiene, 1
．． 7-octadiene, 1,9-decadiene, 6-methyl-1,5-hexadiene, 1,4-hexadiene, 7-
Methyl-1,6-”octadiene, 9-methyl-1,9
-undecane, 1,3-pentadiene, 1,4,9-decatriene, 4-vinyl-1-cyclohexane, cyclopentadiene, 2-methyl-2,5-norbornadiene, 5-methyl-2-norbornene, 5-ethylidene -2
-norbornene, 5-isopropylidene-2-norbornene, 5-isopropenyl-2-norbornene, dicyclopentadiene, tricyclopentadiene, and the like.

When the above polyene compound is used, the iodine value is 2 to 40.
Preferably, the range is .

When propylene is used as the α-olefin, the weight ratio of ethylene and propylene is generally 95:5 to 5:95,
The ratio is preferably in the range of 95:5 to 20:80, more preferably 92:8 to 60:40. moreover,
Particularly preferably 70:30-50 from the viewpoint of low-temperature impact.
: Within the range of 50. Furthermore, when butene-1 is used as the α-olefin, the weight ratio of ethylene and butene-1 is generally 95:40 to 5:60, preferably 9
5:60 to 5:40, more preferably 95:
It is within the range of 70 to 5:30.

In addition, butadiene-based rubbery polymers and ethylene-α-olefin-based rubbery polymers, which are preferable rubbery polymers in the rubbery polymer, may be used in combination with other rubbery polymers other than these if the amount is 40% by weight or less. It may be used in combination with a polymer.

Other rubbery polymers that may be mixed and used here include acrylic rubber, polychloroprene, polyisoprene, ethylene ionomer, and the like.

Particularly preferred rubbery polymers include polybutadiene, butadiene-isoprene copolymer, butadiene-(meth)acrylic acid ester copolymer, and ethylene-α-olefin copolymer having a 1,2-vinyl bond amount of 10% by weight or less. The thermoplastic resin composition of the present invention using these rubbery polymers does not exhibit any other properties even when molded under severe conditions such as high temperature molding conditions or long residence conditions at high temperatures. Compared to rubbery polymers, a thermoplastic resin composition with less discoloration and less decrease in strength and excellent heat resistance stability can be obtained.

The above-mentioned rubbery polymer has the following excellent properties in addition to heat resistance stability.

(a) Polybutadiene: Especially excellent in falling weight impact strength and mechanical strength.

(b) Butadiene-isoprene copolymer: particularly excellent in processability and paintability.

(c) Butadiene-(meth)acrylic acid ester copolymer: Particularly good surface gloss and chemical resistance of molded products.

(d) Ethylene-α-olefin copolymer: Excellent surface gloss of molded products, especially after residence at high temperatures for a long time.

(The amount of rubbery polymer in the BL component is not particularly limited, but 10 to 60% by weight is industrially advantageous. Also, the amount of resinous polymer grafted to the rubbery polymer is The amount of rubbery polymer in the thermoplastic resin composition of the present invention is preferably in the range of 3 to 3 parts by weight based on 100 parts by weight of the combined material.
It is preferably in the range of 0% by weight.

(C) Unsaturated compound having a functional group In order to achieve the object of the present invention, the rubbery polymer-modified styrenic resin as the component (b) must contain a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group, and an amino group. It is necessary that the copolymerization component contains an unsaturated compound having at least one functional group selected from the group consisting of: The rubbery polymer-modified styrenic polymer can be obtained by copolymerizing the unsaturated compound having the above functional group into a styrenic polymer.

The amount of the unsaturated compound having a specific functional group to be copolymerized in the rubbery polymer-modified styrenic polymer is preferably 0.
．． It is in the range of 5 to 20% by weight, more preferably 0.5 to 15% by weight, particularly preferably 1 to 15% by weight.

Carboxyl-containing 1''' encapsulation compounds Examples of carboxyl group-containing unsaturated compounds used here include acrylic acid, methacrylic acid, crotonic acid,
Examples include cinnamic acid, itaconic acid, and maleic acid, with acrylic acid and methacrylic acid being preferred.

These may be used alone or in combination of two or more.

Acid anhydride 4 Unsaturated compounds containing human acid anhydride groups include maleic anhydride, itaconic anhydride, chloromaleic anhydride, citraconic anhydride, butenylsuccinic anhydride, and tetrahydrophthalic anhydride. A particularly preferred unsaturated acid anhydride is maleic anhydride.These may be used alone or in combination of two or more.

Epoxy The epoxy group-containing unsaturated compound is a compound that has an epoxy group and an unsaturated group that can be copolymerized with olefins and ethylenically unsaturated compounds in the molecule.

For example, the following general formulas (I), (n) and (III)
These are unsaturated epoxidized metals such as unsaturated glycidyl esters, unsaturated glycidyl ethers, epoxy alkenes, and p-glycidyl styrenes.

Specifically, glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butene carboxylic acid esters, allyl glycidyl ether, 2-
Methyl allyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxybutene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-
Examples include 1-pentene, 3.4-epoxy-3-methylpentene, 5.6-epoxy-1-hexene, vinylcyclohexene monoxide, and p-glycidylstyrene. These can be used alone or in combination of two or more.

Hydroxyl-containing ・' Human hydroxyl group-containing unsaturated compounds are compounds that have at least one unsaturated bond (double bond, triple bond) and also contain a hydroxyl group.

Typical examples include alcohols with double bonds, alcohols with triple bonds, esters of -valent or divalent unsaturated carboxylic acids and unsubstituted dihydric alcohols,
Examples include esters of the unsaturated carboxylic acid with unsubstituted trihydric alcohols, esters with unsubstituted tetrahydric alcohols, and esters with unsubstituted trihydric or higher alcohols.

Among the hydroxyl compounds used in the present invention,
Representative examples of suitable ones include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene.
butene, 3-hydroxy-2-methyl-1-propene,
cis-5-hydroxy-2-pentene, trans-5-
Hydroxy-2-pentene, cis-1,4-dihydroxy-2-butene, trans-1,4-dihydroxy-2
-Butene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl crotonate, 2,3°4.
5.6-pentahydroxyhexyl acrylate, 2,
Examples include 3.4,5.6-pentahydroxyhexyl methacrylate, 2,3.4.5-tetrahydroxypentyl acrylate, and 2,3,4.5-tetrahydroxypentyl methacrylate.

These may be used alone or in combination of two or more.

Examples of the unsaturated compound containing an amino group include a vinyl monomer having at least one type of amino group or substituted amino group represented by the following general formula, and a specific example is aminoethyl acrylate. , alkyl ester derivatives of acrylic acid or methacrylic acid such as propylaminoethyl acrylate, dimethylaminoethyl methacrylate, aminopropyl methacrylate, phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate;
Vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, allylamine derivatives such as allylamine, methacrylamine and N-methylarylamine, and aminostyrenes such as p-aminostyrene are used. Among them, allylamine, aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene, and the like are particularly preferably used because they can be obtained economically on an industrial scale. These amino group- or substituted amino group-containing unsaturated compounds may be used alone or in combination of two or more.

Amide monounsaturated compound As the unsaturated compound containing an amide group, acrylamide and acrylamide derivatives such as N-methylacrylamide can be used.

Among the unsaturated compounds having a functional group, compounds containing one selected from a carboxyl group, an epoxy group, a hydroxyl group and an amino group are preferred.

(DL polymerization) Methods for obtaining the BL component, which is a component of the present invention, include known polymerization methods such as emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization, bulk-solution polymerization, and bulk-suspension polymerization. Among them, emulsion polymerization method and solution polymerization method are preferable.Polymerization initiator, polymerization solvent,
All known polymerization initiation aids, suspending agents, emulsifiers, etc. can be used.

When using the emulsion polymerization method, the rubbery polymer used is one obtained by emulsion polymerization and/or one that has been emulsified.

Polymerization temperature is generally 40°C to 110°C, preferably 40°C
The temperature range is 90°C. The average number of rubbery polymer particles dispersed in the polymer is within the range of 2,000 to 10,000 particles, preferably 2,000 to 5,000 particles, particularly preferably 2,300 to 3,500 particles. It is desirable that the particles be dispersed with a diameter of .

When using the solution polymerization method, the polymerization temperature is generally 60°C to 1
50°C, preferably in the range of 80°C to 120°C, and the polymerization pressure is generally 0.1 to 4 kg/cd, preferably 0.2 to 120°C.
It is in the range of 2 kg/crA. The rubbery polymer particles dispersed in the polymer have an average particle size of 2,000 to 30,000 particles.
00 people, preferably 2,000 to 20,000 people.

The rubbery polymer-modified styrenic polymer modified with an unsaturated compound having a functional group obtained by the above polymerization generally contains 12 to 85% by weight of aromatic vinyl compound units,
Preferably 23 to 81% by weight, vinyl cyanide units generally 1 to 36% by weight, preferably 3.5 to 31% by weight, rubbery polymers generally 10 to 60% by weight, preferably 10 to 50% by weight, Generally 0.5 to 20% by weight, preferably 0.5 to 15% by weight of unsaturated compound units having functional groups.
% by weight, particularly preferably from 1 to 15% by weight.

In addition, the unsaturated compound having a functional group used as a modifier is bonded as a copolymerization component in the polymer, and by forming a polymer containing this unsaturated compound having a functional group as a copolymerization component, It is believed that the impact resistance, weld appearance, and weld strength of the thermoplastic resin composition of the present invention are improved by improving the compatibility with the polytetramethylene adipamide resin component, which is the component (a). It will be done.

+81 Manufacture of Composition The thermoplastic resin composition of the present invention is produced by mixing the (al polytetramethylene adipamide resin component and the (b) rubbery polymer-modified styrene polymer component) in various extruders or Banbury mixers. -, generally 200 to 3 for kneader, roll, etc.
It can be obtained by kneading at a temperature of 50°C, preferably 280 to 330°C. A preferred kneading method is a method using an extruder, and a particularly preferred method is a method using a twin-screw extruder at a maximum barrel set temperature of 290°C.
The mixture was kneaded at a temperature of 340°C to 340°C.

Although the thermoplastic resin composition of the present invention can be used as is, aromatic vinyl may be added to the rubbery polymer-modified styrene copolymer in the thermoplastic resin composition. - A graft blend type copolymer which is a blend of vinyl cyanide copolymer, or a blended rubber modified styrene copolymer which is a blend of rubber modified styrene graft copolymers with different rubbery polymers, or the blended rubber modified styrene graft copolymer. It is also possible to mix the polymer and the aromatic vinyl-vinyl cyanide copolymer. Inorganic fillers such as glass fiber, carbon fiber, metal fiber, glass peas, asbestos, wallasnite, mica, talc, clay, calcium carbonate, and barium sulfate can be added alone or in combination. Among these inorganic fillers, glass fibers and carbon fibers preferably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more. These fillers can be contained in an amount of preferably 2 to 200 parts by weight, more preferably 5 to 150 parts by weight, particularly preferably 7 to 100 parts by weight, based on 100 parts by weight of the thermoplastic resin.

Additionally, known additives such as flame retardants, stabilizers, plasticizers, colorants, and lubricants may be added.

Preferred flame retardants are those based on a combination of a bromine compound and atimmon trioxide, and examples of the bromine compound include brominated polystyrene, brominated polyphenylene ether, and brominated epoxy oligomer. Further, as a stabilizer, a combination of copper iodide/potassium iodide is particularly preferred.

Furthermore, other polymers may be used depending on the required performance, such as polyethylene, polypropylene, nylon 6.6, nylon 6, nylon 12, nylon 11, PBT, PET.
.

A blend of PPE, POM, PPS resin, PBB/K, polysulfone, etc. may be used.

The thermoplastic resin composition of the present invention can be used for injection molding, sheet extrusion,
It can be used as various molded products by vacuum forming, irregular shaping, foam molding, etc. The various molded products obtained by this molding method can be used for automobile exteriors, interior parts, various electrical and electronic related parts, housings, etc. by utilizing their excellent properties.

f. Examples The present invention will be explained in more detail by the following examples and manufacturing examples, but these are merely illustrative and do not limit the content of the present invention.

In addition, in each side below, parts and % indicate parts by weight and % by weight, respectively.

Example 1 (l) Production of polytetramethylene adipamide resin Polytetramethylene adipamide resin was prepared from 1,4-diaminobutane and adipic acid according to the method of Example 1 of JP-A-56-149431. was manufactured.

The relative viscosity ηreβ of the resulting resin (measured with a solution of 1 g of polymer in 10° IIIE of 97% sulfuric acid at 30° C.) is 3.5.
Met.

(2) Production of butadiene-n-butyl acrylate copolymer (rubber polymer-1) After sufficiently purging the inside of a stainless steel reaction vessel equipped with four-stage paddle blades with nitrogen, 50 parts of n-butyl acrylate, 1,
50 parts of 3-butadiene, 0.2 parts of potassium stearate, 1.5 parts of potassium laurate, 0.1 part of sodium alkylnaphthalene sulfonate, 0.1 part of potassium hydroxide, 1.5 parts of potassium chloride, and ion-exchanged water. 75 parts were added thereto, and the temperature was raised while stirring at 90 r, p, m, and when it reached 45°C, 0.25 parts of potassium persulfate was added to start the polymerization reaction.

10 hours after the start of the reaction, the temperature of the jacket was raised to 50°C.
After a further 20 hours, the temperature was raised to 55°C, and the polymerization reaction was continued for up to 45 hours. The polymerization conversion rate was 90%. Then, 0.1 part of diethylhydroxylamine was added to stop the reaction, and unreacted monomers were substantially distilled off by steam distillation to obtain a latex of butadiene-n-butyl acrylate copolymer.

The average particle size of the rubbery polymer measured using a Nanosizer (manufactured by Nikkaki) was 2,800. 2(3) Production of styrenic polymer Nll After the inside of the stainless steel reaction vessel was sufficiently purged with nitrogen, 40 parts of the butadiene-n-butyl acrylate copolymer rubber latex (as solid content), 0.5 part of potassium rosinate, Potassium hydroxide 0.0
1 part, 110 parts of neon exchange water, 11.68 parts of styrene,
4.32 parts of acrylonitrile, 4.0 parts of acrylamide, and 0.18 parts of tert-dodecylmercaptan were charged. Next, circulate hot water at 70°C through the jacket, and when the internal temperature reaches 40°C, 0.2
A solution prepared by dissolving 0.25 parts of grape W, 0.004 parts of ferrous sulfate in 10 parts of ion-exchanged water, and 0.07 parts of cumene hydroperoxide were added, and a polymerization reaction was carried out for 2 hours.

Thereafter, 23.36 parts of styrene and 8 parts of acrylonitrile were added.
64 parts, acrylamide 8.0 parts, potassium rosinate 1
．． 0 parts, potassium hydroxide 0.02 parts, ion exchange water 50
An emulsion containing 0.13 parts of cumene hydroperoxide was added continuously over a period of 4 hours to carry out a polymerization reaction.

In addition, 0.07 parts of sodium birophosphate, 0.0 part of glucose
8 parts of ferrous sulfate, 0.001 part of ferrous sulfate, and 4 parts of ion-exchanged water, and 0.05 part of cumene hydroperoxide were added, and a polymerization reaction was carried out for 1 hour.

After the reaction was completed, the mixture was cooled, an antioxidant was added, and the mixture was solidified using calcium chloride. The coagulated material was washed with water, dehydrated, and then dried to produce styrenic polymer 11 shown in Table 1.

(4) Production of thermoplastic resin composition Table 2 shows the polytetramethylene adipamide resin, rubbery polymer, and styrene polymer produced by the above method.
The mixture was mixed in the proportions shown below.

A co-rotating twin-screw extruder was used as an extruder, the temperature at the highest point of the barrel was set at 305° C., and kneading was carried out at screw rotation speeds of 30 Or, p, m.

After sufficiently drying the obtained pellet-shaped thermoplastic resin composition in a dehumidifying dryer, a test piece was prepared using an injection molding machine,
Evaluation was made according to the following evaluation criteria.

Impact resistance: Thickness A# according to ASTM D256, notched,
Measured at 23°C.

A molded product with a welded part was injection molded, and the welded part was bent to examine its strength. Evaluation was made according to the following evaluation criteria.

02 Strong △: Slightly weak ×: Weak Weld portion of the test piece for evaluation of 1J Jinmi student weld strength was visually observed and evaluated according to the following evaluation criteria.

O: The weld part is not noticeable. △: The weld part is a little noticeable ×: Weld part is noticeable The results are shown in Table-2.

Examples 2 to 5 The same method as Example 1 was carried out except that the styrene polymer was used under the conditions shown in Table 1.

The results are shown in Table-2.

Example 6 The same method as Example 1 was carried out except that the rubbery polymer was prepared using the method shown below.

The results are shown in Table-2.

(2) Production of butadiene-isoprene copolymer (rubber polymer-2) After sufficiently purging the inside of a stainless steel reaction vessel equipped with four-stage paddle blades with nitrogen, 40 parts of isoprene and 60 parts of 1°3-butadiene were added. , 70 parts of ion-exchanged water, 2 parts of potassium rosinate
part, potassium hydroxide 0.04 part, sodium alkylnaphthalene sulfonate 0.1 part, potassium carbonate 1.2 part,
0.2 part of tert-dodecylmercaptan and 0.25 part of potassium persulfate were added. The polymerization reaction was started while circulating hot water at 55°C through the jacket.

40 hours after the start of the reaction, the temperature of the jacket was raised to 60°C to carry out the reaction, and 50 hours after the start of the reaction, the temperature of the jacket was raised to 65°C to carry out the polymerization reaction for an additional 5 hours. The polymerization conversion rate was 90%.

The reaction was stopped by adding 0.1 part of diethylhydroxyalumine, and unreacted monomers were substantially distilled off by steam distillation to obtain a latex of butadiene-isoprene copolymer.

The average particle diameter of the rubbery polymer measured by the above method was 2.7.
There were 00 people.

Examples 7 to 9 Thermoplastic resin compositions were manufactured in the same manner as in Example 1, except that the blending ratios are shown in Table 2.

The results are shown in Table-2.

Comparative Examples-1 to 5 The method of Example-1 was followed except that the types or proportions shown in Table-2 were changed in the preparation of the thermoplastic resin composition of Example-1. .

In addition, the nylon 6.6 is Amiran CM300 manufactured by Toshi.
6 was used.

The results are shown in Table-2.

Example-1O (1) Production of polytetramethylene adipamide resin A resin was produced in the same manner as in Example-1.

(21 EPR, production of EPDM rubber polymer list 3 in a 2001 autoclave reactor, n-hexane supply amount (e/hr) 80 gas phase ethylene/propylene (molar ratio) 1.0 gas phase hydrogen concentration (mol%) 12, and ethylaluminum sekis chloride (mol/12
-Hexane 4.1 Xl0-
'Vanadium oxytrichloride (mol/l-hexane) 5
．． Polymerization temperature ("C) 38 Polymerization pressure (kg/cTl) 6.
Continuous polymerization was carried out under the polymerization conditions of No. 5.

A small amount of water was added as a reaction terminator to the polymerization liquid taken out from the reactor, the solvent was expelled from the system by steam distillation, and the rubber was dried in a finishing step.

The characteristics of the obtained rubbery polymer are shown in Table 3.

(3) Production of styrenic polymer Kan 8 In a 10β stainless steel reaction vessel equipped with a paddle-type stirring blade, 20 parts of rubbery polymer Kan 3, 10 parts of acrylamide, 18 parts of acrylonitrile, 52 parts of styrene, and 100 parts of toluene were added. Stir at 50°C until the rubber is completely dissolved, add 0.2 part of ter-dodecyl mercaptan and t
After adding 0.5 part of er-butyl peroxybenzoate, a polymerization reaction was carried out at 100°C for 10 hours.

The solvent was removed by a conventional method, and after drying, it was pelletized using an extruder, and after drying at 80° C. for 10 hours, styrenic polymer-8 shown in Table 4 was obtained.

(4) Production of thermoplastic resin composition Table 5 shows the polytetramethylene adipamide resin, rubbery polymer and styrene polymer produced by the above method.
The mixture was mixed in the proportions shown below.

A co-rotating twin-screw extruder was used as an extruder, the temperature at the highest point of the barrel was set at 305° C., and crosstalk was performed at screw rotation speeds of 30 Or, p, and m.

After thoroughly drying the obtained pellet-shaped thermoplastic resin composition in a dehumidifying dryer, test pieces were prepared using an injection molding machine and evaluated.

The results are shown in Table-5.

Example 11-17 The same method as Example 10 was carried out except that the styrene polymer was used under the conditions shown in Table 4.

The results are shown in Table-5.

Examples 18 to 20 The same method as in Example 10 was carried out except that the rubbery polymer was changed to rubbery polymers 4 to 6 shown in Table 3.

The results are shown in Table-5.

Examples 21 and 22 The same method as in Example 10 was conducted except that the styrene polymers shown in Table 4 were used in the amounts shown in Table 5.

The results are shown in Table-5.

Example 23 The same method as in Example 1 was carried out except that glass fiber (GF, chopped strand with a diameter of 13 μm and a length of 3 strands) was used.

The results are shown in Table-5.

Comparative Examples-6 to 10 The method of Example-10 was followed except that the blended materials in the production of the thermoplastic resin composition of Example-8 were changed to the types or proportions shown in Table-5. .

The AS resin is a copolymer of acrylonitrile and styrene, and the acrylonitrile content is 26%, [η] (30℃,
(measured with methyl ethyl ketone solvent) of 0.60 was used.

The results are shown in Table-5.

g1 Effects of the Invention As described in the Examples, the thermoplastic resin composition of the present invention is composed of a polytetramethylene adipamide resin and a rubbery polymer-modified styrene resin having excellent impact resistance, weld appearance, and weld strength. A composition comprising a polymer,
Due to its excellent balance of physical properties, it is useful as an engineering material such as materials for automobile parts, materials for electrical parts, and materials for electronic parts.In particular, compositions blended with inorganic fillers such as glass fibers have high rigidity and are extremely useful in industrial applications. It is a useful material.

Claims (6)

[Claims] (1) (a) Polytetramethylene adipamide resin 5 to 9
(b) 95 to 5% by weight of a styrenic polymer obtained by polymerizing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer. b) Component contains as a copolymerization component an unsaturated compound having at least one functional group selected from a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group, and an amino group. Thermoplastic resin composition. (2) The thermoplastic resin composition according to claim (1), wherein the rubbery polymer is a butadiene-based rubbery polymer and/or an ethylene-α-olefin-based rubbery polymer. (3) The butadiene-based rubbery polymer is polybutadiene, and the 1,2 vinyl content in the polybutadiene is 10% by weight.
The thermoplastic resin composition according to claim (2), which is as follows. (4) The thermoplastic resin composition according to claim (2), wherein the butadiene-based rubbery polymer is a butadiene-isoprene copolymer. (5) The thermoplastic resin composition according to claim (2), wherein the butadiene-based rubbery polymer is a butadiene-(meth)acrylic acid alkyl ester copolymer. (6) The ethylene-α-olefin rubbery polymer is an ethylene-α-olefin rubber.
2) The thermoplastic resin composition described in item 2).