KR102023517B1 - Polyamide resin composition and molded products produced therefrom - Google Patents

Polyamide resin composition and molded products produced therefrom Download PDF

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KR102023517B1
KR102023517B1 KR1020150159342A KR20150159342A KR102023517B1 KR 102023517 B1 KR102023517 B1 KR 102023517B1 KR 1020150159342 A KR1020150159342 A KR 1020150159342A KR 20150159342 A KR20150159342 A KR 20150159342A KR 102023517 B1 KR102023517 B1 KR 102023517B1
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polyamide resin
resin composition
weight
compound
copolymer
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KR1020150159342A
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Korean (ko)
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KR20170056140A (en
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양재경
김재화
이상록
이수민
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주식회사 엘지화학
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The polyamide resin composition of the present disclosure comprises (A) 10 to 70 wt% of a polyamide resin; (B) 0.1 to 55% by weight of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer resin; (C) 20 to 35% by weight of polycarbonate resin; (D) 0 to 5% by weight of styrene-maleimide copolymer; And (E) 0 to 10% by weight of maleic anhydride graft styrene-ethylene-butylene-styrene block copolymer; to provide a polyamide resin composition with remarkably improved heat resistance, and an extrusion molded product thereof.

Description

POLYAMIDE RESIN COMPOSITION AND MOLDED PRODUCTS PRODUCED THEREFROM}

The present disclosure relates to a polyamide resin composition and a molded article, and more particularly, based on a polyamide resin, having excellent mechanical properties and heat resistance with a heat deflection temperature of 82 ° C. or higher at a load of 18.6 kgf / cm 2 according to ASTM D648 standard. The outstanding polyamide resin composition and its extrusion molded article are related.

Polyamide resin, a kind of engineering plastic, has excellent mechanical strength, abrasion resistance, heat resistance, chemical resistance, electrical insulation, and arc resistance, and thus is used in a wide range of applications such as automobiles, electrical and electronic parts, and industrial materials.

However, in case of interior and exterior materials of automobiles, not only mechanical properties but also heat resistance should be excellent. For this purpose, glass type such as glass fiber, glass bead, or inorganic materials such as talc, kaolin, wollastonite, or mica The method of mixing a filler, the method of alloying an acrylonitrile- butadiene-styrene (ABS) resin with a polyamide resin, the method of adding the additive which can act as a nucleophile, etc. are used. However, when the inorganic filler is added to the polyamide resin, the heat resistance is improved, but the toughness is decreased. When the ABS resin is alloyed, the elongation and the impact strength are improved, but the heat resistance is limited. Although a nucleophilic agent is used to obtain high heat resistance, there is a problem that it is difficult to obtain heat resistance of 80 ° C. or higher under high load, and the toughness is still reduced.

Therefore, there is still a need to develop a technology for a polyamide resin composition which can significantly improve heat resistance while having excellent mechanical properties.

Korean Registered Patent No.0252296

An object of the present disclosure is to provide a polyamide resin composition having a heat deflection temperature of 82 ° C. or higher at a load of 18.6 kgf / cm 2 according to ASTM D648 standard, in which a polyamide resin is difficult to reach.

Another object of the present disclosure is to provide a molded article including the polyamide resin composition having excellent mechanical properties and significantly improved heat resistance.

The above objects of the present disclosure can all be achieved by the present disclosure described below.

The present substrate is (A) 10 to 70% by weight of a polyamide resin; (B) 0.1 to 55% by weight of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer resin; (C) 20 to 35% by weight of polycarbonate resin; (D) 0 to 5% by weight of styrene-maleimide copolymer; And (E) 0 to 10% by weight maleic anhydride graft styrene-ethylene-butylene-styrene block copolymer; provides a polyamide resin composition comprising a.

In addition, the present disclosure provides a molded article manufactured by including the polyamide resin composition.

According to the present disclosure, it is excellent in mechanical properties and excellent heat resistance of 82 ° C. or higher under a high load of 18.6 kgf / cm 2, which is difficult to reach by simply including acrylonitrile-butadiene-styrene copolymer in a polyamide resin. There is an effect of providing a polyamide resin composition and a molded article comprising the same.

Hereinafter, the present description will be described in detail.

The polyamide resin composition of the present disclosure comprises (A) 10 to 70 wt% of a polyamide resin; (B) 0.1 to 55% by weight of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer resin; (C) 20 to 35% by weight of polycarbonate resin; (D) 0 to 5% by weight of styrene-maleimide copolymer; And (E) 0 to 10% by weight maleic anhydride graft styrene-ethylene-butylene-styrene block copolymer; characterized in that it comprises a.

As another example, (A) the polyamide resin may be included in 10 to 60% by weight, or 13 to 45% by weight, there is an effect excellent in impact resistance and heat resistance within this range.

The polyamide resin (A) may be, for example, a polymer polycondensed with a ring structure lactam or w-amino acid, and may be a polymer polycondensed with diacids and diamines.

Specific examples of the (A) polyamide resin include poly caprolactam (nylon 6), poly hexamethylene diamine adiamide (nylon 6,6), poly hexamethylene seba amide (nylon 6,10), poly hexamethylenediamine It may be at least one selected from lauamide (nylon 6,12), polytetra methylenediamine adiamide (nylon 4,6), and polylaurolactam (nylon 12).

As another example, the (B) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer may be included in an amount of 10 to 55% by weight, or 30 to 50% by weight, and excellent heat resistance and physical property balance within this range. There is.

The (B) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer is not particularly limited, but may include, for example, a polymerized rubber core including a conjugated diene compound; And a shell surrounding the core and polymerized with an aromatic vinyl compound and a vinyl cyan compound, or an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth) acrylate compound.

The aromatic vinyl compound may be, for example, one or more selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, and vinyltoluene. Specifically, styrene is used, but is not limited thereto.

The vinyl cyan compound may be, for example, one or more selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile, and specifically, acrylonitrile is used, but is not limited thereto.

The conjugated diene compound is for example one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene It may be more than, specifically, 1,3-butadiene is used, but is not limited thereto.

The alkyl (meth) acrylate compound may include both an alkyl acrylate monomer and an alkyl methacrylate monomer.

The alkyl group of the alkyl (meth) acrylate monomer is, for example, preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, most preferably a methyl group or an ethyl group. The alkyl (meth) acrylate monomer is more preferably methyl methacrylate, but is not limited thereto.

As another example, the (C) polycarbonate resin may be included in 20 to 35% by weight, there is an effect excellent in tensile strength and thermal stability within this range.

For example, the polycarbonate resin (C) may have a melt index (300 ° C., 1.2 kg) of 3 to 30 g / 10 minutes, or 10 to 20 g / 10 minutes, and excellent impact strength and elongation within this range. Can be provided.

The content of the (A) polyamide resin may be, for example, less than or equal to the sum of the contents of (B) vinylcyan compound-conjugated diene compound-aromatic vinyl compound copolymer resin and (C) polycarbonate resin, in which case heat resistance The characteristic is maximized and the impact strength is excellent.

The weight ratio of the polyamide resin (A) and the polycarbonate resin (C) may be 1: 0.1 to 5, 1: 0.4 to 3, or 1: 0.45 to 2.35, and the impact strength is excellent within this range. There is.

As another example, the (D) styrene-maleimide-based copolymer may be included in 0.1 to 5% by weight, or 2 to 5% by weight, and the impact strength and heat resistance are excellent in this range.

The (D) styrene-maleimide-based copolymer has a high thermal decomposition degree, and can improve compatibility between the polyamide resin and the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer resin.

The (D) styrene-maleimide-based copolymer may be, for example, a pyrolysis temperature measured by a thermogravimetric analyzer of 300 ° C. or higher, or 300 to 400 ° C.

For reference, the pyrolysis degree is a sample cut to a predetermined size using a thermogravimetric analyzer (TGA) to increase the temperature from room temperature to 600 ℃ at a temperature rising rate of 20 ℃ / min in a nitrogen atmosphere, followed by a temperature increase of 20 ℃ / min in oxygen atmosphere It can be measured after pyrolysis by heating up to 800 ° C. at a rate.

As a specific example, the styrene-maleimide-based copolymer may be a copolymer of 40 to 60% by weight, or 45 to 55% by weight of styrene monomer and 40 to 60% by weight, or 45 to 55% by weight of maleimide monomer. .

As another example, (D) the styrene-maleimide-based copolymer includes 40 to 50% by weight of styrene monomer, 40 to 50% by weight of maleimide monomer, and 0.1 to 10% by weight of maleic anhydride and have a weight average molecular weight of 120,000 to 145,000 g / mol terpolymer.

Herein, the maleimide monomer may be at least one selected from methyl maleimide, ethyl maleimide, butyl maleimide, cyclohexyl maleimide, and N-phenyl maleimide.

As another example, the maleic anhydride graft styrene-ethylene-butylene-styrene block copolymer (E) may be included in an amount of 0.1 to 10% by weight, or 1 to 5% by weight, and the impact strength and the heat resistance within this range. This has an excellent effect.

(E) Maleic anhydride graft styrene-ethylene-butylene-styrene block The copolymer may have, for example, a maleic anhydride content in the range of 0.1 to 5.0% by weight, 0.5 to 4% by weight, or 1 to 2% by weight in the block copolymer, and has an excellent balance of physical properties within this range.

(E) Maleic anhydride graft styrene-ethylene-butylene-styrene block The copolymer can improve the compatibility between the polyamide resin and the polycarbonate resin.

The polyamide resin composition may be a lubricant, an antioxidant, a light stabilizer, a chain extender, a catalyst, a release agent, a pigment, a dye, an antistatic agent, an antibacterial agent, a processing aid, a metal inactivator, a smoke suppressant, within a range that does not adversely affect physical properties. It may further comprise at least one selected from inorganic fillers, glass fibers, frictional agents, abrasion and coupling agents.

For example, the polyamide resin composition may have a heat deflection temperature of 82 ° C. or higher, 85 ° C. or higher, or 85 to 130 ° C. or higher at a load of 18.6 kgf / cm 2 according to ASTM D648 standard.

For example, the polyamide resin composition may have a tensile elongation of 140% or more, 150% or more, or 150 to 160% according to ASTM D638 standard.

The polyamide resin composition may be, for example, nucleophile free, wherein the nucleophile free refers to no nucleophile in principle, but for example, 0.01 part by weight or less or 0.001 part by weight or less It may also contain a nucleophilic agent.

The polyamide resin composition of the present disclosure is optionally mixed with the above additives in a mixer or a supermixer, and then 180 to 180 using one of various compounding machines such as a twin screw extruder, a single screw extruder, a roll mill, a kneader, or a shortbari mixer. After melt-kneading at a temperature range of 300 ° C or 200 to 290 ° C, extrusion may be performed.

The present disclosure provides a molded article manufactured by including the polyamide resin composition, and may provide automotive interior and exterior parts that require a heat deformation temperature of 82 ° C. or more in addition to mechanical properties as the molded article.

Hereinafter, preferred examples are provided to aid in understanding the present disclosure, but the following examples are merely illustrative of the present disclosure, and it is apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present disclosure. It goes without saying that changes and modifications belong to the appended claims.

EXAMPLE

Example  1 to 5

The ingredients shown in Table 1 below were added to the super mixer at the content described therein and kneaded, melt kneaded at a barrel section of 260 ° C. using a twin screw extruder, and then prepared in pellet form by extrusion processing (using a pelletizer). After drying, a resin composition specimen was prepared using an injection machine at an injection temperature of 250 to 280 ° C.

Comparative example  1 to 9

Specimens were prepared in the same manner as in Example 1 except that the ingredients shown in Table 2 were used in the amounts described.

Raw materials used in Examples and Comparative Examples are as follows.

PA (polyamide resin): Poly caprolactam (nylon 6) was used.

* ABS (Acrylonitrile-butadiene-styrene): 30.4 wt% acrylonitrile, 60 wt% butadiene and 9.6 wt% styrene copolymerized

* PC (Polycarbonate Resin): Polycarbonate with melt index (300 ℃, 1.2kg) of 15g / 10min

* SMI (Styrene-N-Phenylmaleimide-Maleic anhydride Copolymer): TGA pyrolysis measured at 350 ℃, weight average molecular weight 135,000 g / mol, 47.5 wt% styrene, 6.2 wt% maleic anhydride, 46.3 wt% N-phenyl maleimide Copolymerized copolymer

SEBS-MAH (maleic anhydride graft styrene-ethylene-butylene-styrene block copolymer): Kraton FG1901X (Shell) with 1.7 wt% maleic anhydride as functional group

* F (nucleophilic agent): nanoclay (93A from Closite)

* SAN (Polystrene-co-acrylonitrile): 81HF (LG Chemistry)

The physical properties of the specimens prepared in Examples 1 to 5 and Comparative Examples 1 to 9 were measured by the following method, and the results are shown in Tables 1 and 2 below.

* Tensile Strength (kgf / cm 2 ), Tensile Elongation (%): Tensile strength and tensile elongation were measured according to ASTM D638 standard.

* Flexural Strength (kg / cm 2 ), Flexural Modulus (kg / cm 2 ): Flexural strength and flexural modulus were measured according to ASTM D790.

Izod impact strength (1/4 notched at 23 ° C., kgf · cm / cm): Measured according to ASTM D256 standard.

* HDT (heat deformation temperature, 18.6kgf / ℃; ℃): measured according to the ASTM D648 standard.

division Example 1 Example 2 Example 3 Example 4 Example 5 PA 23.0 13.0 41.0 18.0 28.0 ABS 47.0 47.0 32.0 47.0 47.0 PC 20.0 30.0 20.0 25.0 20.0 SMI 5.0 5.0 2.0 5.0 5.0 SEBS 5.0 5.0 5.0 5.0 - Nucleophile - - - - - The tensile strength 384 420 435 400 410 Tensile elongation 158 150 150 150 140 Flexural strength 558 600 647 585 590 Flexural modulus 17,020 18,100 18,920 17,800 18,000 Impact strength 30 45 20 38 23 HDT 100 120 85 115 105

division Comparative example
One Comparative example
2 Comparative example
3 Comparative example
4 Comparative example
5 Comparative example
6 Comparative example
7 Comparative example
8 Comparative example
9 PA 48.0 48.0 48.0 38.0 56.0 51.0 20.0 17.0 87.0 ABS 47.0 47.0 47.0 47.0 32.0 32.0 47.0 47.0 3.0 PC 0 0 0 5.0 5.0 10.0 20.0 20.0 5 SMI 5 5 5 5.0 2.0 2.0 8.0 5.0 5 SEBS - - - 5.0 5.0 5.0 5.0 11.0 - Nucleophile - One 4 - - - - - - The tensile strength 450 443 455 415 495 465 405 348 720 Tensile elongation 60 47 30 180 180 190 120 175 70 Flexural strength 680 670 690 600 700 685 578 505 950 curve
Modulus 21,700 21,000 22,140 17,590 20,500 19,200 17,800 15,820 26,400 Impact strength 43 39 25 65 58 25 18 42 6 HDT 75 80 80 80 70 70 100 88 57

Through Tables 1 and 2, Examples 1 to 5 comprising the polyamide resin composition provided according to the composition of the present substrate, while maintaining the existing mechanical properties compared to Comparative Examples 1 to 9 that do not satisfy the composition of the present substrate It was confirmed that the heat deflection temperature was 82 ° C. or higher at a high load of 18.6 kgf / ° C.

In addition, the polyamide resin composition according to the present invention had an effect of a heat deformation temperature of 82 ° C. or more without using a nucleophilic agent.

Claims (14)

(A) 10 to 70% by weight of polyamide resin;
(B) 0.1 to 55% by weight of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer resin;
(C) 20 to 35% by weight of polycarbonate resin;
(D) 0 to 5% by weight of styrene-maleimide copolymer; And
(E) 0-10% by weight maleic anhydride graft styrene-ethylene-butylene-styrene block copolymer;
Including,
Heat deformation temperature is 100 to 120 ℃ at 18.6kgf / cm 2 load according to ASTM D648 standard,
The weight ratio of said (A) polyamide resin and (C) polycarbonate resin is 1: 0.71-2.31, The polyamide resin composition characterized by the above-mentioned.
The method of claim 1,
The polyamide resin (A) is polycaprolactam (nylon 6), poly hexamethylene diamine adipamide (nylon 6,6), poly hexamethylene seba amide (nylon 6,10), poly hexamethylenediamine lauamide (Nylon 6,12), polytetra methylenediamine adipamide (nylon 4,6), and polylaurolactam (nylon 12). Polyamide resin composition, characterized in that at least one member.
The method of claim 1,
(B) the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer includes a rubber core polymerized including a conjugated diene compound; And a shell surrounding the core and polymerized with an aromatic vinyl compound and a vinyl cyan compound, or an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth) acrylate compound.
The method of claim 1,
The polyamide resin composition (C) is characterized in that the melt index is 3 to 30 g / 10 minutes.
The method of claim 1,
The content of the polyamide resin (A) is less than or equal to the sum of the contents of (B) vinylcyan compound-conjugated diene compound-aromatic vinyl compound copolymer resin and (C) polycarbonate resin. .
delete The method of claim 1,
The (D) styrene-maleimide copolymer is at least one member selected from the group consisting of styrene-N-phenylmaleimide-maleic anhydride copolymer, N-phenylmaleimide-maleic anhydride copolymer, and phenylmaleimide. Polyamide resin composition, characterized in that.
The method of claim 1,
The polyamide resin composition may include a lubricant, an antioxidant, a light stabilizer, a chain extender, a catalyst, a mold release agent, a pigment, a dye, an antistatic agent, an antibacterial agent, a processing aid, a metal deactivator, a smoke suppressant, an inorganic filler, a glass fiber, and an antifriction agent. , Polyamide resin composition characterized in that it further comprises one or more selected from the group consisting of a wear resistant agent and a coupling agent.
The method of claim 1,
The polyamide resin composition is a polyamide resin composition, characterized in that the heat deformation temperature is 82 ℃ or more at a load of 18.6kgf / cm 2 according to the ASTM D648 standard.
The method of claim 1,
The polyamide resin composition is a polyamide resin composition characterized in that the tensile elongation of 140% or more according to ASTM D638 standard.
The method of claim 1,
The polyamide resin composition is a nucleophile-free polyamide resin composition.
(A) 10 to 70% by weight of polyamide resin; (B) 0.1 to 55% by weight of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer resin; And (C) 20 to 35 weight percent of a polycarbonate resin; (D) 0 to 5% by weight of styrene-maleimide copolymer; And (E) 0 to 10% by weight maleic anhydride graft styrene-ethylene-butylene-styrene block copolymer; melt kneading and extruding;
Heat deformation temperature is 100 to 120 ℃ at 18.6kgf / cm 2 load according to ASTM D648 standard,
The weight ratio of said (A) polyamide resin and (C) polycarbonate resin is 1: 0.71-2.31, The manufacturing method of the polyamide resin composition characterized by the above-mentioned.
A molded article comprising the polyamide resin composition according to any one of claims 1 to 5 or 7 to 11.
The method of claim 13,
The molded article is a molded article, characterized in that the vehicle interior and exterior parts.
KR1020150159342A 2015-11-13 2015-11-13 Polyamide resin composition and molded products produced therefrom KR102023517B1 (en)

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KR102172087B1 (en) * 2017-12-14 2020-10-30 주식회사 엘지화학 Polycarbonate-polyamide alloy resin composition, and method for preparing the resin composition
KR101960535B1 (en) * 2018-04-25 2019-03-20 (주)우성케미칼 Polyamide master batch composition, polyamide resin composition having the same and product prepared therefrom

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100529206B1 (en) * 2000-04-12 2005-11-17 로디아 엔지니어링 플라스틱스 에스.에이. Thermoplastic polymeric compositions
KR100821066B1 (en) * 2005-11-11 2008-04-10 제일모직주식회사 Nylon/ABS/PMMA alloy having improved mechanical properties
JP2014051581A (en) * 2012-09-06 2014-03-20 Daicel Polymer Ltd Additive for thermoplastic resin

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KR100252296B1 (en) 1997-11-28 2000-04-15 정몽규 Thermoplastic resin composition
KR100503576B1 (en) * 1997-12-31 2005-10-21 로디아폴리아마이드 주식회사 Thermoplastic resin composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100529206B1 (en) * 2000-04-12 2005-11-17 로디아 엔지니어링 플라스틱스 에스.에이. Thermoplastic polymeric compositions
KR100821066B1 (en) * 2005-11-11 2008-04-10 제일모직주식회사 Nylon/ABS/PMMA alloy having improved mechanical properties
JP2014051581A (en) * 2012-09-06 2014-03-20 Daicel Polymer Ltd Additive for thermoplastic resin

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