JPH0621215B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION a. TECHNICAL FIELD The present invention relates to a thermoplastic resin composition excellent in impact resistance, weld appearance, and weld strength.

b. Conventional technology Conventionally, polyamide resin has an excellent balance of physical properties, so as an engineering plastic material,
Widely used in various industrial fields such as automobiles, electricity, and electronics. However, polyamide resins such as nylon 6, nylon 6,6 and the like used in the above industrial fields are generally still insufficient in impact resistance, and therefore those reinforced with glass fiber or the like are usually used. However,
The polyamide resin composition reinforced with such glass fibers still has a drawback that the impact resistance is still insufficient and the strength of the weld portion is weak.

Therefore, a composition in which ethylene-propylene rubber modified with maleic anhydride or the like is mixed with the polyamide resin is known, but the composition has a drawback that the weld appearance and weld strength are poor.

On the other hand, AE obtained by polymerizing acrylonitrile and styrene in the presence of ethylene-propylene rubber polymer
Since S resin is excellent in impact resistance and molding processability, it is widely used in the fields of automobiles, light electric fields, etc., but the polyamide resin composition containing such AES resin has poor weld appearance and weld strength. It had a drawback.

c. Problems to be Solved by the Invention For the purpose of improving such drawbacks, nylon 6,6 and a polybutadiene-styrene-acrylonitrile copolymer (hereinafter referred to as AB
S composition), nylon 6,6 and AES
Various studies were conducted on a composition comprising a resin, but these resins were poorly compatible with each other, a peeling phenomenon was observed, and they were very brittle. However, during polymerization of the ABS resin or AES
A composition of ABS resin or AES resin obtained by copolymerizing acrylamide, acrylic acid, maleic anhydride, etc. at the time of resin polymerization with nylon 6 and nylon 6,6 has improved compatibility and improved impact resistance. However, the weld appearance and weld strength were not improved.

d. Means for Solving the Problems In view of the above problems, the present inventors have diligently studied impact resistance, a weld appearance and a thermoplastic resin composition having excellent weld strength, and as a result, unsaturated having a specific functional group. Compound modified rubbery polymer modified styrenic polymer and polytetramethylene adipamide resin (Nylon 4,
The present invention has been completed by finding that the above objects can be sufficiently achieved by a thermoplastic resin composition consisting of 6).

That is, the present invention relates to a styrene-based polymer obtained by polymerizing (a) 5 to 95% by weight of polytetramethylene adipamide resin, and (b) an aromatic vinyl compound and a vinyl cyan compound in the presence of a rubbery polymer. In the thermoplastic resin composition consisting of 95 to 5% by weight, the component (b) has at least one functional group selected from a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group and an amino group. A thermoplastic resin composition containing a saturated compound as a copolymerization component.

e. DETAILED DESCRIPTION OF THE INVENTION (a) Polytetramethylene adipamide resin component The polytetramethylene adipamide resin (hereinafter referred to as nylon 4, 6) used in the present invention has the general formula Is a polyamide resin consisting essentially of the repeating structural unit represented by

The polytetramethylene adipamide resin is described, for example, in JP-A-56
-149430, 56-149431, 58-83029, and JP-B-60-28843, etc. You can

To obtain the thermoplastic resin composition of the present invention, at least
Relative viscosity of 1.5, preferably 2.5-5.0 (ηrel; 97 at 30 ° C
%, Measured with a solution of 1 g of polymer in 100 ml of sulfuric acid), it is preferred to use nylon 4,6.

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, more preferably 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, impact resistance, weld appearance and weld strength will not be improved.

(B) rubbery polymer modified styrene-based polymer component The rubbery polymer-modified styrene-based polymer which is the component (b) in the thermoplastic resin composition of the present invention is an aromatic compound in the presence of the rubbery polymer. An unsaturated compound which is obtained by polymerizing a vinyl compound and a vinyl cyan compound and which has 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 modified.

Aromatic Vinyl Compound Examples of the aromatic vinyl compound used here include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, p- There are tertiary butyl styrene, ethyl styrene, vinyl naphthalene and the like, preferably styrene and α-methyl styrene. These are used alone or in combination of two or more.

Vinyl Cyan Compound Examples of the vinyl cyan compound include acrylonitrile and methacrylonitrile. The use ratio of the aromatic vinyl compound and the vinyl cyan compound in the component (b) is generally aromatic vinyl compound / vinyl cyan compound = 95/5 to 60/40,
It is preferably within the range of 90/10 to 65/35 (% by weight).

Other Copolymerizable Vinyl Compound Further, another vinyl compound copolymerizable therewith can be copolymerized within a range not impairing the object of the present invention.
Other vinyl compounds that can be copolymerized include (meth) acrylic acid alkyl esters and maleimide compounds, and these are used alone or in combination of two or more.

Examples of the (meth) acrylic acid alkyl ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate. Acrylic acid alkyl esters such as, and methyl methacrylate, ethyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate,
Examples include methacrylic acid alkyl esters such as octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate and benzyl methacrylate. Examples of the maleimide-based compound include maleimide, N-methylmaleimide, N-
Ethyl maleimide, N-butyl maleimide, N-lauryl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, hydroxyphenyl maleimide, N
-(P-bromophenyl) maleimide and the like.

The amount of the other copolymerizable vinyl compound used can be generally 0 to 50% by weight, preferably 0 to 30% by weight in the components excluding the rubbery polymer as the component (b). .

Rubbery Polymer As the rubbery polymer which is present during the polymerization of the aromatic vinyl compound and the vinylcyan compound, polybutadiene, butadiene-isoprene copolymer, butadiene-
(Meth) acrylic acid ester copolymer, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, diene rubber such as polychloroprene, ethylene-
Olefin rubber such as propylene copolymer and ethylene-propylene-polyene copolymer, acrylic rubber such as polyacrylic acid ester, styrene-butadiene block copolymer, styrene-isoprene block copolymer, styrene-isoprene Examples thereof include a butadiene block copolymer, a water additive of the block copolymer, a styrene-grafted ethylene-propylene elastomer, a thermoplastic elastomer, and an ethylene-based ionomer copolymer. These rubber polymers are used alone or in combination of two or more. Among these rubbery polymers, butadiene-based rubbery polymers and ethylene-α-olefin-based rubbery polymers are preferable. The amount of the rubbery polymer in component (b) is not particularly limited, but industrially 10 to 50% by weight.
It is advantageous to use within the range.

Examples of the butadiene rubbery polymer include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-isoprene copolymer, butadiene- (meth) acrylic acid alkyl ester copolymer, butadiene-styrene block. There are copolymers and hydrogenated products of butadiene-styrene block copolymers, and these are used alone or in combination of two or more. The butadiene rubber polymer is a polybutadiene having a vinyl bond content of 10% by weight or less in the polybutadiene portion, a butadiene-isoprene copolymer, or butadiene- (meth) acrylic acid from the viewpoint of the thermal stability of the resulting thermoplastic resin composition. It is preferably an alkyl ester copolymer. Of these, a butadiene-alkyl (meth) acrylate copolymer is particularly preferable. As the (meth) acrylic acid alkyl ester, all of those described above can be used, but as the preferred (meth) acrylic acid alkyl ester, the alkyl group in the alkyl ester is an alcohol having 2 to 12 carbon atoms and allyl acid. And specifically, ester compounds such as ethyl, butyl, hexyl, octyl, 2-ethylhexyl, and lauryl of (meth) acrylic acid are mentioned, and these are used alone or in combination of two or more. Particularly preferably n
-Butyl acrylate. The preferred composition ratio of butadiene and (meth) acrylic acid ester in the copolymer is in the range of butadiene / (meth) acrylic acid alkyl ester = 5/5 to 8/2 (weight ratio). The preferred composition ratio in the butadiene-isoprene copolymer is within the range of butadiene / isoprene = 7/3 to 4/6 (weight ratio). 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 10 carbon atoms.
It is an unsaturated hydrocarbon compound having 20 compounds, specifically, propylene, butene-1, pentene-1, hexene-
1, heptene-1, 4-methylbutene-1, 4-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, disixpentadiene, tricyclopentadiene and the like can be mentioned.

When the above polyene compound is used, it preferably has an iodine value in the range of 2-40.

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

In addition, the butadiene-based rubbery polymer and the ethylene-α-olefin-based rubbery polymer, which are preferable rubbery polymers in the rubbery polymer, are rubbers other than these as long as the amount is 40% by weight or less. You may use it, mixing with a polymer. Examples of other rubbery polymers to be mixed and used here include acrylic rubber, polychloroprene, polyisoprene, and ethylene ionomer.

Particularly preferred rubbery polymers include polybutadiene and butadiene-containing 1,2-vinyl bond content of 10% by weight or less.
An isoprene copolymer, a butadiene- (meth) acrylic acid ester copolymer, and an ethylene-α-olefin copolymer, and the thermoplastic resin composition of the present invention using these rubbery polymers is molded at a high temperature. Compared to other rubbery polymers even when molded under severe conditions such as conditions or conditions where they are allowed to stay for a long time at high temperature, there is less discoloration and lowering of strength, and a thermoplastic resin composition with excellent heat stability is obtained. can get.

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

(A) Polybutadiene: Particularly excellent in drop impact strength and mechanical strength.

(B) Butadiene-isoprene copolymer: Particularly excellent in processability and paintability.

(C) Butadiene- (meth) acrylic acid ester copolymer: The surface gloss and chemical resistance of molded products are particularly good.

(D) Ethylene-α-olefin copolymer: Particularly excellent in surface gloss of a molded product after staying at a high temperature for a long time.

The amount of the rubbery polymer in the component (b) is not particularly limited, but industrially 10 to 60% by weight is advantageous. The amount of resinous polymer grafted on the rubbery polymer is 100% by weight.
It is preferably in the range of 10 to 100 parts by weight with respect to parts by weight. In order to achieve the object of the present invention, the amount of the rubbery polymer in the thermoplastic resin composition of the present invention is preferably in the range of 3 to 30% by weight.

(c) Unsaturated compound having a functional group In order to achieve the object of the present invention, the rubber polymer modified styrenic resin of the component (b) is a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group and an amino group. It is necessary to contain an unsaturated compound having at least one functional group selected from the groups as a copolymerization component. The rubbery polymer-modified styrene-based polymer is achieved by copolymerizing an unsaturated compound having the above functional group into the styrene-based polymer.

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

Carboxyl group-containing unsaturated compound As the carboxyl group-containing unsaturated compound used here, for example, acrylic acid, methacrylic acid, crotonic acid,
There are cinnamic acid, itaconic acid, maleic acid and the like, and acrylic acid and methacrylic acid are preferable. These are used alone or in combination of two or more.

Acid anhydride group-containing unsaturated compound As the acid anhydride group-containing unsaturated compound, maleic anhydride, itaconic anhydride, chloromaleic anhydride, citraconic anhydride, butenyl succinic anhydride, tetrahydrophthalic anhydride, etc., The preferred unsaturated acid anhydride is maleic anhydride. These are used alone or in combination of two or more.

Epoxy Group-Containing Unsaturated Compound The epoxy group-containing unsaturated compound is a compound having an unsaturated group capable of copolymerizing with an olefin and an ethylenically unsaturated compound, and an epoxy group in the molecule.

For example, unsaturated glycidyl esters represented by the following general formulas (I), (II) and (III), unsaturated glycidyl ethers, epoxy alkenes, unsaturated epoxy compounds such as p-glycidyl styrenes. .

Specifically, glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butenecarboxylic acid esters, allyl glycidyl ether, 2-
Methylallyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxybutene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-
1-Pentene, 3,4-epoxy-3-methylpentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, p-glycidylstyrene and the like can be mentioned. These may be used alone or in combination of two or more.

Hydroxyl Group-Containing Unsaturated Compound The hydroxyl group-containing unsaturated compound is a compound having at least one unsaturated bond (double bond, triple bond) and containing a hydroxyl group. Typical examples thereof include an alcohol having a double bond, an alcohol having a triple bond, an ester of a monovalent or divalent unsaturated carboxylic acid and an unsubstituted dihydric alcohol, and an unsubstituted trivalent unsaturated carboxylic acid. Examples thereof include esters with polyhydric alcohols, esters with unsubstituted tetrahydric alcohols, and esters with unsubstituted pentavalent or higher alcohols.

Among the hydroxyl compounds used in the present invention,
Typical examples of preferable ones include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-.
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,
Examples include 2,3,4,5,6-pentahydroxyhexyl methacrylate, 2,3,4,5-tetrahydroxypentyl acrylate, and 2,3,4,5-tetrahydroxypentyl methacrylate.

These are used alone or in combination of two or more.

Amino Group-Containing Unsaturated Compound The amino-containing unsaturated compound has the following general formula: Is a vinyl-based monomer having at least one of an amino group or a substituted amino group represented by, and specific examples include aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, aminopropyl methacrylate, and methacrylic acid. Acrylic acid or methacrylic acid alkyl ester derivatives such as phenylaminoethyl acid and cyclohexylaminoethyl methacrylate, vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, allylamine, methacrylamine and N-methylallylamine Allylamine derivatives such as and aminostyrenes such as p-aminostyrene are used. Among them, allylamine, aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene and the like are particularly preferably used since they are economically available on an industrial scale. These unsaturated compounds containing an amino group or a substituted amino group are used alone or in combination of two or more.

Amide Group-Containing Unsaturated Compound As the amide group-containing unsaturated compound, acrylamide and acrylamide derivatives such as N-methylacrylamide can be used.

Among the unsaturated compounds having the above-mentioned functional groups, compounds containing a compound selected from a carboxyl group, an epoxy group, a hydroxyl group and an amino group are preferable.

(d) Polymerization As a method of obtaining the component (b) which is a constituent of the present invention, known polymerization methods such as emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization, bulk-solution polymerization, bulk-suspension polymerization method are known. Etc. can be used, but among them, emulsion polymerization method and solution polymerization method are preferable. Polymerization initiator used in the above various polymerization, a polymerization solvent,
As the polymerization initiation aid, suspending agent, emulsifier and the like, all known ones can be used.

When the emulsion polymerization method is used, the rubbery polymer is obtained by emulsion polymerization and / or is emulsified. The polymerization temperature is generally 40 ° C to 110 ° C, preferably 40 ° C to 90 ° C. The rubbery polymer particles dispersed in the polymer have an average of 2,000Å to 10,000Å, preferably 2,000Å to 5,000Å,
Particularly preferably, it is desirable that the particles are dispersed with a diameter within the range of 2,300Å to 3,500Å.

When the solution polymerization method is used, the polymerization temperature is generally 60 ° C to 150 ° C.
℃, preferably in the range of 80 ℃ ~ 120 ℃, the polymerization pressure is generally
The range is 0.1 to 4 kg / cm ² , preferably 0.2 to ² kg / cm ² . The rubbery polymer particles dispersed in the polymer averaged 2,000.
It is desirable that the particles have a diameter within the range of Å to 30,000Å, preferably 2,000Å to 20,000Å.

The rubbery polymer-modified styrenic polymer modified with an unsaturated compound having a functional group obtained by the above-mentioned polymerization has an aromatic vinyl compound unit of generally 12 to 85% by weight, preferably 23 to 81% by weight, vinyl cyan. The compound unit is generally 1 to 36% by weight, preferably 3.5 to 31% by weight, the rubber polymer is generally 10 to 60% by weight, preferably 10 to 50% by weight, and the unsaturated compound unit having a functional group is generally 0.5 to 20% by weight, preferably 0.5-15% by weight, particularly preferably 1-15
% By weight.

Further, the unsaturated compound having a functional group used as a modifier is bound as a copolymerization component in the polymer, and the unsaturated compound having a functional group is used as a polymer containing the copolymerization component. It is considered that the compatibility with the polytetramethylene adipamide resin component which is the component (a) is improved to improve the impact resistance, weld appearance and weld strength of the thermoplastic resin composition of the present invention. To be

(e) Preparation of composition Kneading The thermoplastic resin composition of the present invention comprises the above-mentioned (a) polytetramethylene adipamide resin component and modified (b) rubbery polymer-modified styrene polymer component in various extruders. , Banbury mixer, kneader, roll, etc., generally at 200 to 350 ° C., preferably at 280 to 330 ° C. A preferable kneading method is a method using an extruder, and a particularly preferable method is a method in which a twin-screw extruder is used and kneading is performed at a maximum barrel setting temperature of 290 ° C to 340 ° C.

Other Blending Examples The thermoplastic resin composition of the present invention may be used as it is, but the thermoplastic resin composition may be used as an aromatic vinyl-cyanide compound in the rubbery polymer-modified styrene copolymer in the composition. A graft blend type copolymer obtained by blending a vinyl copolymer, a blend rubber modified styrene copolymer obtained by blending a rubber modified styrene graft copolymer having a different rubbery polymer, or the blend rubber modified styrene graft copolymer; It is also possible to mix an aromatic vinyl-vinyl cyanide copolymer. Inorganic fillers such as glass fiber, carbon fiber, metal fiber, glass beads, asbestos, wollastonite, mica, talc, clay, calcium carbonate and barium sulfate can be added alone or in combination. Of these inorganic fillers, the shape of glass fiber and carbon fiber is 6 to 60 μm and the fiber diameter is 6 to 60 μm.
Those having a fiber length of 30 μm or more are preferable. These fillers may 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.

Further, known additives such as flame retardants, stabilizers, plasticizers, colorants and lubricants can be added and used. A preferred flame retardant is a combination of a bromine compound and attimone trioxide, and the bromine compound is brominated polystyrene, brominated prephenylene ether, brominated epoxy oligomer, or the like. Also, as the stabilizer, copper iodide /
The combined use of potassium iodide is particularly preferred.

Further, other polymers such as polyethylene, polypropylene, nylon 6,6, nylon 6, nylon 12, nylon 11, PBT, PET, PPE, POM, PP depending on the required performance.
You may blend and use S resin, PEEK, polysulfone, etc.

The thermoplastic resin composition of the present invention is used for injection molding, sheet extrusion,
It can be used as various molded products by vacuum molding, modified molding, foam molding and the like. Various molded articles obtained by the molding method can be used for automobile exterior and interior members and various electric and electronic parts, housings and the like by utilizing their excellent properties.

f. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Production Examples, but these are merely examples and do not limit the content of the present invention.

In the following examples, parts and% indicate parts by weight and% by weight, respectively.

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

The resin obtained had a relative viscosity ηrel (measured with a solution of 1 g of polymer in 100 ml of 97% sulfuric acid at 30 ° C.) of 3.5.

(2) Production of butadiene-n-butyl acrylate copolymer (rubbery polymer-1) After sufficiently replacing the inside of a styrene reaction vessel equipped with a 4-stage paddle blade with nitrogen, 50 parts of n-butyl acrylate, 1, 3-
Butadiene 50 parts, potassium stearate 0.2 parts, potassium laurate 1.5 parts, sodium alkylnaphthalene sulfonate 0.1 parts, potassium hydroxide 0.1 parts, potassium chloride 1.
5 parts and 75 parts of ion-exchanged water were added, and when the temperature was raised to 45 ° C. with stirring at 90 rpm, 0.25 part of potassium persulfate was added to start the polymerization reaction.

After 10 hours from the start of the reaction, the temperature of the jacket was raised to 50 ° C., and further 20 hours later, to 55 ° C., and then the polymerization reaction was carried out for 45 hours. The polymerization conversion rate was 90%. Then, 0.1 part of diethylhydroxylamine was added to stop the reaction,
Unreacted monomers were substantially distilled off by steam distillation to obtain a latex of a butadiene-n-butyl acrylate copolymer. The average particle size of the rubbery polymer measured with Nanosizer (manufactured by Nikkaki Co., Ltd.) was 2,800Å.

(3) Manufacture of styrene-based polymer NO.1 After thoroughly replacing the inside of the styrene reaction vessel with nitrogen, 40 parts (as solid content) of the butadiene-n-butyl acrylate copolymer rubber latex, 0.5 part of potassium rosinate,
0.01 parts potassium hydroxide, 110 parts ion-exchanged water, 1 styrene
1.68 parts, acrylonitrile 4.32 parts, acrylamide 4.0
Parts and 0.18 part of tert-dodecyl methanecaptan. Next, while circulating hot water at 70 ° C through the jacket,
At 40 ℃, 0.2 parts sodium pyrophosphate, glucose
A solution prepared by dissolving 0.25 part and 0.004 part of ferrous sulfate in 10 parts of ion-exchanged water and 0.07 part of cumene hydroperoxide were added and a polymerization reaction was carried out for 2 hours.

After that, 23.36 parts of styrene, 8.64 parts of acrylonitrile,
An emulsion consisting of 8.0 parts of acrylamide, 1.0 part of potassium rosinate, 0.02 part of potassium hydroxide, 50 parts of ion-exchanged water and 0.13 part of cumene hydroperoxide was continuously added over 4 hours to carry out a polymerization reaction.

Further, a solution consisting of 0.07 part of sodium pyrophosphate, 0.08 part of glucose, 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 completion of the reaction, the mixture was cooled, an antioxidant was added, and the mixture was solidified with calcium chloride. The coagulated product was washed with water, dehydrated, and dried to produce styrene polymer NO.1 shown in Table-1.

(4) Production of thermoplastic resin composition The polytetramethylene adipamide resin, the rubbery polymer and the styrenic polymer produced by the above method are shown in Table-2.
They were mixed in the mixing ratio shown in.

A co-rotating twin-screw extruder was used as an extruder, the temperature of the highest part of the barrel was set to 305 ° C., and kneading was performed at a screw rotation speed of 300 rpm.

After sufficiently drying the obtained pellet-shaped thermoplastic resin composition with a dehumidifying dryer, a test piece is prepared with an injection molding machine,
It evaluated according to the following evaluation criteria.

Impact resistance Measured according to ASTM D256 at a thickness of 1/4 ", notched and at 23 ° C.

Weld Strength A molded product having a weld portion was injection-molded, and the weld portion was bent to check its strength. It evaluated according to the following evaluation criteria.

◯: Strong Δ: Slightly weak ×: Weak appearance Weld portion of the test piece for evaluating weld strength was visually observed and evaluated according to the following evaluation criteria.

◯: Weld portion is not easily noticeable Δ: Weld portion is slightly noticeable ×: Weld portion is noticeable The results are shown in Table 2.

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

The results are shown in Table-2.

Example-6 A procedure was carried out in the same manner as in Example-1 except that the rubber polymer was prepared by the method shown below.

The results are shown in Table-2.

(2) Production of butadiene-isoprene copolymer (rubbery polymer-2) After thoroughly replacing the inside of a styrene reaction vessel equipped with a 4-stage paddle blade with nitrogen, 40 parts of isoprene and 1,3-butadiene
60 parts, ion-exchanged water 70 parts, potassium rosinate 2 parts, potassium hydroxide 0.04 parts, sodium alkylnaphthalene sulfonate 0.1 parts, potassium carbonate 1.2 parts, tert-dodecyl mercaptan 0.2 parts, and potassium persulfate 0.25 parts were added. The polymerization reaction was started while circulating warm water of 55 ° C through the jacket.

After 40 hours from 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., and the polymerization reaction was further conducted for 5 hours. The polymerization conversion rate was 90%. The reaction was stopped by adding 0.1 part of diethylhydroxylalumine, and unreacted monomers were substantially distilled off by steam distillation to obtain a latex of a butadiene-isoprene copolymer.

The average particle size of the rubbery polymer measured by the above method is 2,700.
It was Å.

Examples-7 to 9 Production of the thermoplastic resin composition was performed in the same manner as in Example-1 except that the compounding ratios thereof are shown in Table-2.

The results are shown in Table-2.

Comparative Examples-1 to 5 Comparative Example-1 was carried out according to the method of Example-1 except that the compounding in the production of the thermoplastic resin composition of Example-1 was carried out by changing the kinds or proportions shown in Table-2. .

In addition, nylon 6,6 is Amylan CM3006 manufactured by Toray Industries, Inc.
Was used.

The results are shown in Table-2.

Example-10 (1) Production of polytetramethylene adipamide resin Production was carried out in the same manner as in Example-1.

(2) Manufacture of EPR and EPDM Rubber polymer No. 3 in 200 autoclave reactor, n-hexane supply amount (/ hr) 80 Gas phase ethylene / propylene (molar ratio) 1.0 Gas phase hydrogen concentration (mol %) 12, and ethylaluminum sesquichloride (mol /-hexane 4.1 × 10 ^-3 vanadium oxytrichloride (mol / -hexane) 5.1 × 10 ^-4 as a polymerization catalyst Polymerization temperature (° C) 38 Polymerization pressure Continuous polymerization was carried out under the polymerization conditions of (kg / cm ² ) 6.5.

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

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

(3) Production of styrene-based polymer NO.8 20 parts of rubbery polymer NO.3, 10 parts of acrylamide, 18 parts of acrylonitrile, 52 parts of styrene, and toluene were placed in a reaction vessel made of 10 stainless steel equipped with a paddle type stirring blade. Charge 100 parts and stir at 50 ° C until the rubber is completely dissolved.
After adding 0.2 part of r-dodecyl mercaptan and 0.5 part of ter-butyl peroxybenzoate, a polymerization reaction was carried out at 100 ° C. for 10 hours.

The solvent was removed by a conventional method, dried, pelletized by using an extruder, and dried at 80 ° C. for 10 hours to obtain a styrene polymer-8 shown in Table-4.

(4) Production of thermoplastic resin composition The polytetramethylene adipamide resin, the rubbery polymer and the styrene polymer produced by the above method are shown in Table-5.
They were mixed in the mixing ratio shown in.

A co-rotating twin-screw extruder was used as an extruder, the temperature of the highest part of the barrel was set to 305 ° C., and kneading was performed at a screw rotation speed of 300 rpm.

The pelletized thermoplastic resin composition thus obtained was sufficiently dried with a dehumidifying dryer, and then a test piece was prepared with an injection molding machine for evaluation.

The results are shown in Table-5.

Examples 11 to 17 The same procedure as in 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 procedure as in Example-10 was carried out except that the rubber polymer Nos. 4 to 6 shown in Table 3 were used instead of the rubber polymer.

The results are shown in Table-5.

Examples-21 and 22 The procedure of Example-10 was repeated, except that the styrene polymers shown in Table-4 were used and the amounts thereof were used in the proportions shown in Table-5.

The results are shown in Table-5.

Example-23 A procedure was performed in the same manner as in Example 1 except that glass fibers (GF; chopped strands having a diameter of 13 µm and a length of 3 mm) were used.

The results are shown in Table-5.

Comparative Examples-6 to 10 The procedure of Example-10 was repeated, except that the type and proportions shown in Table-5 were changed from those used in the production of the thermoplastic resin composition of Example-8. .

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

The results are shown in Table-5.

g. EFFECTS OF THE INVENTION The thermoplastic resin composition of the present invention, as described in Examples and the like, comprises a polytetramethylene adipamide resin having excellent impact resistance, weld appearance and weld strength, and a rubbery polymer-modified styrene-based resin. A composition comprising:
Due to its excellent balance of physical properties, it is useful as an engineering material such as materials for automobile parts, materials for electric parts and materials for electronic parts. In particular, a composition mixed with an inorganic filler such as glass fiber has strong rigidity and is industrially extremely It is a useful material.

Claims (6)

[Claims] 1. A styrene polymer obtained by polymerizing an aromatic vinyl compound and a vinyl cyan compound in the presence of (a) a polytetramethylene adipamide resin of 5 to 95% by weight, and (b) a rubbery polymer.
In the thermoplastic resin composition consisting of 95 to 5% by weight, the component (b) has at least one functional group selected from a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group and an amino group. A thermoplastic resin composition comprising a saturated compound as a copolymerization component. 2. The thermoplastic resin composition according to claim 1, wherein the rubbery polymer is a butadiene rubbery polymer and / or an ethylene-α-olefin rubbery polymer. 3. The thermoplastic resin composition according to claim 2, wherein the butadiene rubbery polymer is polybutadiene and the content of 1,2-vinyl in the polybutadiene is 10% by weight or less. 4. A butadiene-based rubbery polymer is butadiene-
The thermoplastic resin composition according to claim (2), which is an isoprene copolymer. 5. A butadiene-based rubbery polymer is butadiene-
The thermoplastic resin composition according to claim (2), which is a (meth) acrylic acid alkyl ester copolymer. 6. The thermoplastic resin composition according to claim 2, wherein the ethylene-α-olefin rubber polymer is an ethylene-α-olefin rubber.