KR20120071208A - High-flow thermoplastic resin comprising polyamide-abs - Google Patents

Abstract

PURPOSE: A thermoplastic resin is provided to have excellent miscibility even when comprising polyamide and ABS, thereby having excellent impact strength, and flowability, to have simple types of used resin, thereby having simple production processes. CONSTITUTION: A thermoplastic resin comprises 19-70 weight% of polyamide resin, 29-80 weight% of acrylonitrile-butadiene-styrene resin, and 1-30 weight% of modified aromatic vinyl based compound/maleimide copolymer. At least a part of butadiene rubber is 5000 angstrom. The thermoplastic resin additionally comprises an ethylene-propylene-diene compound by weight of the thermoplastic resin. The butadiene rubber is manufactured by bulk polymerization. The acrylonitrile-butadiene-styrene copolymer(ABS) comprises 10-40 weight% of butadiene.

Description

High flow thermoplastic resin composition containing polyimide and ABS {High-flow Thermoplastic Resin comprising Polyamide-ABS}

The present invention relates to a thermoplastic resin composition capable of molding various products having excellent moldability, good mechanical properties, and excellent fluidity and having a complicated structure. More specifically, the present invention relates to a high flow thermoplastic resin mainly comprising polyimide and ABS. It relates to a composition.

Polyamide resin is obtained by ring-opening polymerization of caprolactam, which is commonly known, and has excellent heat resistance, mechanical properties, and chemical resistance, and can easily reinforce inorganic materials such as glass fiber, carbon fiber, and talc, and thus can express very high strength. have. However, since the impact resistance is small and the crystalline resin has a large molding shrinkage rate, there is a problem in that deformation easily occurs.

On the other hand, acrylonitrile-butadiene-styrene copolymer has excellent secondary workability such as molding processability, impact resistance, heat resistance, coating, plating, etc. by changing the structure and controlling the content of the composition by the manufacturing method, and it is dimensional stability because it is an amorphous resin. great. However, since the rigidity and heat resistance are inferior, they are used in the form of impact reinforcing materials alone or blended with engineering plastic resins in industries such as electrical, electronics and automobiles.

Accordingly, attempts have been made to harmonize the properties of polyamide with the processability of ABS. However, polyamide resins and ABS resins do not have good compatibility, but often have adverse effects. Accordingly, development of various compatibilizers has been made.

For example, U.S. Pat.No. 5,248,726 uses acrylonitrile-butadiene-styrene copolymer (ABS) resins and carboxylated nitrile rubbers in polyamide resins to compensate for dimensional stability and impact resistance. This is not very high, and if the impact resistance is high, there is a problem that the heat resistance is poor.

In another U.S. Patent No. 5,010,138, a compatibilizer made by extruding a polyamide resin and an α-methylstyrene / acrylonitrile / t-butylacrylate copolymer is used to form a polyamide resin and styrene-acrylonitrile. It is added to the coalescing (SAN) and ABS resin to improve the impact resistance and dimensional stability, but has a disadvantage in terms of process because the heat resistance is poor and the two-step extrusion process must be performed.

Another U.S. Patent No. 5,202,379 has a high impact from low temperature to room temperature by mixing styrene / N-phenylmaleimide copolymer and styrene / acrylonitrile / methyl methacrylate copolymer in polyamide resin and ABS resin. Although strength and dimensional stability are expressed, the strength, elastic modulus and heat resistance are too low overall.

In addition, Korean Patent No. 434640, issued to Rhodia Polyamide Co., Ltd., contains a copolymer of a modified aromatic vinyl compound / maleimide containing polyamide as a main material and a modified EPDM elastomer with high butadiene content to improve shrinkage after molding. A method of kneading ABS resin is disclosed, and Korean Patent No. 830133, issued to Espolymer Co., Ltd., uses a maleated ethylene-octene copolymer together with a modified aromatic vinyl compound / maleimide copolymer in a polyamide and ABS resin mixture. It suggests a way to do it.

In the case of using such a compatibilizer, the physical properties are improved, but the melt flowability of the resin is lowered by the maleic hydride having a reactive group, and thus there is a problem in that moldability is remarkably lowered. As a result, products with complex shapes could not be manufactured.

Accordingly, Patent Publication No. 10-2010-0099830 invented by Jung, Myung-Wook et al. Discloses a new composition in which polyamide and ABS are commercialized with a modified aromatic vinyl compound / maleimide copolymer and a low viscosity maleated ethylene-propylene-diene compound. It is starting. However, these compositions contain at least four kinds of different resins, resulting in a complicated production and manufacturing process.

An object of the present invention is to provide a new thermoplastic resin composition containing polyamide and ABS, excellent compatibility, good impact strength, good fluidity, simple resin and simple production and manufacturing process.

Another object of the present invention is to provide a molded article of a complex shape consisting of a highly flexible polyamide-ABS resin and one compatibilizer.

In order to solve the above problems, the thermoplastic resin according to the present invention comprises a polyamide resin, an acrylonitrile-butadiene-styrene resin, and a modified aromatic vinyl compound / maleimide copolymer, but more than 5000 kPa butadiene It is characterized by including a rubber.

Although not limited in theory, when the rubber particle size having an impact reinforcing effect is large, the impact reinforcement efficiency is increased, and even a small amount of the particle can exert a certain impact or more. Becomes possible.

In the present invention, the resin composition is used for automotive parts requiring high fluidity, and the impact resistance and surface gas problems required during molding are solved, and the thermal stability is improved.

Examples of the polyamide resin (A) which can be used in the present invention include polyamides obtained by ring-opening polymerization of commonly known lactams such as ε-caprolactam, ω-dodecaractam, aminocapronic acid, 11-aminoundecanoic acid, Polyamides obtained from amino acids such as 12-aminododecanoic acid, ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2, 4,4-trimethylhexamethylenediamine, 5-methylnonahexamethylenediamine, metaxylenediamine, paraxylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, 1-amino-3 -Aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (4-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) Propane, bis (aminoph Aliphatic, cycloaliphatic and aromatic diamines such as piperazine and aminoethylpiperazine and adipic acid, subberic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methyl Polyamides obtained from aliphatic, cycloaliphatic and aromatic dicarboxylic acids such as isophthalic acid and the like, copolymers of such polyamides and mixtures thereof, in particular aliphatic polyamides, aromatic polyamides such as polyamide-6, Polyamide-66, polyamide-610, polyamide-11, polyamide-12, terephthalic acid and isophthalic acid polyamides, and copolymers thereof and mixtures thereof. Commercially, polyamide-6, polyamide-66, or a polyamide 66/6 copolymer which is a copolymer thereof and the like can be used, and it is preferable to use them separately according to the characteristics according to the required physical properties.

In the present invention, the polyamide resin is preferably polyamide-6 having a melting point of 220 ° C. to improve the fluidity of the final resin, and more preferably using a 2.4-3.0 polyamide resin having a Relative Viscosity.

In the present invention, the polyamide resin may be used 19-70% by weight, more preferably 30-60% by weight, most preferably 35-55% by weight in the resin composition. If the content is small, it is difficult to obtain mechanical properties and it is difficult to maintain the intrinsic properties of the polyamide. In addition, when the content of polyamide is increased, the content of ABS resin having good impact strength and formability is relatively low, thereby deteriorating impact properties and formability.

In the present invention, the acrylonitrile-butadiene-styrene copolymer may be made of butadiene rubber, styrene and acrylonitrile, and may be prepared by various methods such as bulk polymerization, emulsion polymerization, sus polymerization, and commercially. It can be purchased and used.

In the present invention, the butadiene rubber may be a butadiene rubber obtained by polymerizing butadiene alone or a rubber containing butadiene copolymerized with butadiene and a small amount of copolymerizable vinyl monomers. In the practice of the invention, small amounts of copolymerizable vinylic monomers are styrene, acrylonitrile, or mixtures thereof, up to 30% by weight, more preferably up to 20% by weight, even more preferably 10% by weight in rubber. It may be included as follows.

In the present invention, the styrene and acrylonitrile may be grafted or present independently in the butadiene-based rubber, and preferably some of the grafted on the butadiene rubber to improve the compatibility of the butadiene rubber and styrene and acrironitrile It is preferred that the squeeze and some be present independently.

In the present invention, the acrylonitrile-butadiene-styrene copolymer (ABS) has a butadiene content of 10-40% by weight, preferably 20-40% by weight, the remainder consisting of styrene and acrylonitrile, where The weight ratio of styrene and acrylonitrile should be about 60:40 to 80:20.

In the present invention, the butadiene rubber includes a large particle butadiene rubber of 5000 kPa or more, preferably rubber of 5000-10,000 kPa, more preferably 5000-8000 kPa.

In the present invention, it is preferable that the above-mentioned large particle size butadiene rubber of 5000 kPa or more is commercially purchased and used.

In the present invention, when the bulk polymerized ABS has a low rubber content, it is possible to use a mixture of emulsion-polymerized ABS or ABS / SAN having a high rubber content.

In the practice of the present invention, the ABS or ABS / SAN having a high rubber content is preferably made of butadiene rubber of about 2000 to 4000 kPa, preferably about 3000 to 3500 kPa.

In the present invention, the acrylonitrile-butadiene-styrene copolymer is 29-80% by weight, more preferably 40-70% by weight, and more preferably the largest component in the composition.

In the present invention, the modified aromatic vinyl compound / maleimide copolymer is a compatibilizer used to increase the kneading resistance and heat resistance impact resistance of the resin composition, the modified aromatic vinyl compound / maleimide copolymer content in the resin composition Preference is given to using 1-30% by weight, more preferably 2-10% by weight, most preferably 3-7% by weight. When the amount of the modified aromatic vinyl compound / maleimide copolymer is small, there is no compatibility between the polyamide resin and the ABS resin, and when used in an excessive amount, there is no improvement in compatibility, but rather the physical properties are lowered. .

In the present invention, the modified aromatic vinyl compound / maleimide copolymer is a copolymer of an aromatic vinyl compound, maleimide, unsaturated dicarboxylic acid or unsaturated dicarboxylic anhydride, preferably aromatic vinyl compound 30 to 80 Weight percent, 19 to 69 weight percent maleimide, and 1 to 10 weight percent unsaturated dicarboxylic acid or unsaturated dicarboxylic anhydride.

In the practice of the present invention, the aromatic vinyl compound contains styrene, α-methylstyrene, p-methylstyrene, etc. as a main component, and may include a small amount of other copolymerizable vinyl compounds. The unsaturated dicarboxylic acid or unsaturated dicarboxylic anhydride may be maleic anhydride, methyl maleic anhydride, 1,2-dimethylmaleic anhydride, ethyl maleic anhydride, phenylmaleic anhydride, acrylic acid, methacrylic acid and their It can be selected from the group consisting of mixtures. As the monomer copolymerizable with the aromatic vinyl compound, the vinyl compound may be methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, Decyl (meth) acrylate, octadecyl (meth) acrylate, hydroxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, glycidyl (meth) acrylate, etc. are preferable.

In the practice of the present invention, the modified aromatic vinyl-based compound / maleimide copolymer can be prepared by a known method or commercially available to use, preferably using a graft of maleic anhydride in the range of 1 to 10% by weight Good to do. When the amount of the maleic hydride is small, the compatibility may be lowered, and when the amount is large, the fluidity of the resin may be lowered and gelation may occur.

Products using a polyamide resin, an acrylonitrile-butadiene-styrene resin, and a thermoplastic resin composed of a modified aromatic vinyl compound / maleimide copolymer according to the present invention may be used in order to maintain the impact strength of the final product. The content of butadiene rubber in the product should be 10-20% by weight, more preferably 12-18% by weight, most preferably 13-17% by weight, and the bulk polymerized butadiene rubber with a diameter of 5000 mm 3 or more and 4000 mm 3 It is preferable that less than emulsion-polymerized butadiene rubber is resin or molded article mixed.

In the present invention, the thermoplastic resin composition may optionally further include a maleated ethylene-propylene-diene compound copolymer rubber, preferably in the range of 0.1-30 parts by weight based on 100 parts by weight of the thermoplastic resin composition according to the present invention. It is good to use as. In the present invention, the maleated ethylene-propylene-diene compound copolymer rubber is a small amount of maleic anhydride chemically bonded, the ethylene group content of 30 to 75% by weight, the propylene group content of 20 to 50% by weight of the diene As a copolymer having a compound content of 0 to 20% by weight, it may be prepared by synthesizing by a known method, or may be commercially available and used.

In the present invention, the maleated ethylene-propylene-diene compound copolymer rubber reinforces the impact property of the resin composition, while using a low-viscosity product to prevent the fluidity decrease caused by the maleimide contained in the compatibilizer It is preferable. In the practice of the present invention, the maleated ethylene-propylene-diene compound copolymer is 0.1-10% by weight of maleic ene hydride. In a preferred embodiment of the present invention, the viscosity of the rubber is preferably 10-60 (1 + 4,100 ° C.), and when the viscosity of the rubber becomes too large, the fluidity of the overall resin decreases remarkably, and the viscosity of the rubber is too small. Ground physical properties will be degraded.

In the practice of the present invention, the maleated ethylene-propylene rubber may be commercially available and available, for example from Dow Chemical fusabond 416D, ExxonMobil Exxelor 1801,1803.

In the present invention, in addition to the above components, additives such as stabilizers, pigments, plasticizers, ultraviolet absorbers, lubricants, fillers and the like which are commonly used may be added.

The resin composition of the present invention can be produced by blending a resin composition using a general mixed melt processing apparatus such as a Banbury mixer or an extruder by blending.

In this way, the resin composition having excellent extrusion and injection moldability can be obtained by mixing the appropriate ratio in consideration of composition molecular weight difference control and compatibility with each component.

As described above, the present invention relates to a thermoplastic resin composition having excellent moldability and good mechanical properties. The present invention relates to a polyamide and an acrylonitrile-butadiene-styrene copolymer content to adjust the balance of heat deformation temperature and mechanical strength. In addition, a low viscosity resin was used to improve moldability. The impact strength reduction property due to the use of low viscosity has developed a resin composition having excellent impact properties and excellent moldability by using a maleated ethylene-propylene-diene compound copolymer and Bulk ABS.

Hereinafter, the present invention will be described in detail with reference to the following examples, but are not limited to the examples.

Examples 1-5

Polyamide; Bulk ABS + emulsified ABS; The modified aromatic vinyl compound / maleimide three components were mixed in the mixing ratios shown in Table 1.

Example 6-7

Polyamide; Bulk ABS + emulsified ABS; It carried out by further mixing a maleated ethylene-propylene-diene compound copolymer with 100 weight part of modified aromatic vinyl compounds / maleimide three components.

Comparative Example 1

In Comparative Example, four components consisting of polyamide, ABS, modified aromatic vinyl compound / maleimide, and maleated ethylene-propylene-diene compound copolymer were mixed, and ABS used butadiene rubber of about 3500 GPa by emulsion polymerization. It was carried out by.

With the composition ratio shown in Table 1, the mixing temperature was sufficiently mixed with a small tumbler mixer for uniform mixing, and the extrusion temperature was 220? Extruded at 250 ℃, cooled and solidified into pellets, dried for 4 hours in a circulating hot air dryer maintained at 100 ℃, and then changed at an injection temperature of 230-250 ℃ in a 160-ton injection machine and dried at a mold temperature of 65 ℃. The pellets were molded to form the joining line, and mechanical strength test specimens were prepared. The melt flow index was also measured to examine the melt flow.

Comparative example  One

Specimens were prepared in the same manner as in the compositions and compositions described in Table 1 above.

Test Example  One

Example 1 above? After the specimen prepared according to 7 and Comparative Example 1 was left for 24 hours, physical properties were measured according to the following method, and pellets were measured for fluidity after drying, and the results are shown in Table 1 below.

<Test method>

(1) Tensile strength (kgf / ㎠)

The test was conducted using a tensile test equipment according to the test method of ASTM D638.

(2) Izod impact strength 6.4mm (kgf? Cm / cm)

Tests were made using an Izod impactor using the ASTM D256 method. Notched Izod Impact Strength was measured with a 6.4 mm specimen thickness.

(3) Heat deflection temperature (℃)

ASTM D648 was used and measured under 18.6 kgf / cm 2 load.

(4) Meltflow Index (g / 10min)

ASTM D1238 method was used, and measured at a load of 230 ° C. and 10 kg.

The liquidity index is over 30 based on actual experiments and field experience.

It was judged to be advantageous for molding in injection molding.

(5) Surface of molded article (Gas mark)

The surface state of the speaker grill molded product was observed during molding at 250 ° C.

     Item Example Comparative example One 2 3 4 5 6 7 One Composition
(weight%) A Low viscosity 40 40 45 45 50 50 50 50 B Midpoint 50 Low Viscosity 1 30 25 30 25 30 25 45 Bulk
ABS 25 30 20 25 15 20 Composition
(PHR) C 5 5 5 5 5 5 5 5 D 3 5 5 characteristic The tensile strength
(400 or more) 450 470 450 480 460 440 420 390 Izod
Impact strength
(20 or more) 26 23 25 20 24 28 24 27 Heat deformation
Temperature
(80 ℃ or more) 85 88 87 89 87 82 78 75 Melt flow
Index index 42 45 43 47 44 47 38 32 Surface of moldings
(Gas mark) Good Good Good Good Good Good usually Bad

(week)

A) Polyamide Resin (Low Viscosity: RV 2.45 ± 0.03): Hyosung Nylon 1011 BRT

B) acrylonitrile butadiene styrene copolymer

Emulsified ABS Mid-weight, AN 13 wt%, BD 45 wt%, SM 42 wt%, MI 15, rubber size 3000-3500 Å

Emulsified ABS low viscosity, 15% AN, 40% BD, 45% SM. MI 35, Rubber Size 3000-3500 Å

Bulk ABS, LG Chem MA-201, Butadiene about 10% by weight, Rubber size 5000-8000 Å

C) Modified Aromatic Vinyl Compound / Maleimide Copolymer

Copolymer consisting of 46% by weight of styrene, 53% by weight of N-phenylmaleimide and 1.0% by weight of maleic anhydride (Polyimilex® PSX-371, manufactured by Nihon Shokubai).

D) Maleated ethylene-propylene-diene compound copolymer: ExxonMobil Exxelor 1803,

Pattern viscosity 20 (1 + 4,100 ° C.), ethylene 40 wt%, propylene 59 wt%, butadiene 0 wt%, maleimide 1 wt%

Examples 1 to 5 are compounds of low viscosity nylon, bulk ABS, emulsified low viscosity ABS, modified aromatic vinyl compound maleimide, and have excellent impact strength, heat deformation temperature, tensile strength, and moldability even at low butadiene rubber content. Got good results.

Examples 6 to 7 are compounds of low viscosity nylon, bulk ABS, emulsified low viscosity AB, modified aromatic vinyl compound maleimide, and maleated ethylene-propylene-diene compound, which are excellent in quality but bulk at heat deformation temperature. It was confirmed that the fall slightly compared to the ABS alone.

Comparative Example 1 is a compound of low viscosity nylon, medium viscosity ABS, maleated ethylene-propylene-diene compound, the heat resistance and fluidity is inferior, and molding failure occurred.

As can be seen from the table above, low viscosity nylon should be used for resins that require high fluidity, such as the speaker grille surface, and also maleic ethylene-propylene-diene compound copolymers, especially rubber particles, for impact reinforcement. It is advantageous for various properties while using bulk ABS of large size.

Claims (11)

A high flow thermoplastic resin comprising a polyamide resin, an acrylonitrile-butadiene-styrene resin, and a modified aromatic vinyl compound / maleimide copolymer, wherein at least a part of butadiene rubber is 5000 kPa or more. The thermoplastic resin according to claim 1, further comprising an ethylene-propylene-diene compound copolymer with respect to 100 parts by weight of the thermoplastic resin. According to claim 1, wherein the thermoplastic resin is 19 to 70% by weight of polyamide, 29 to 80% by weight of acrylonitrile-butadiene-styrene copolymer, 1 to 30% by weight of modified aromatic vinyl compound / maleimide copolymer Thermoplastic resin, characterized in that. The thermoplastic resin according to claim 1 or 2, wherein the butadiene rubber of 5000 kPa or more is produced by bulk polymerization. The thermoplastic resin according to claim 1 or 2, wherein the acrylonitrile-butadiene-styrene copolymer (ABS) has a butadiene content of 10-40 wt%. The thermoplastic resin according to claim 1 or 2, wherein the butadiene rubber is a mixture of a bulk polymerized rubber and an emulsion polymerized rubber. The thermoplastic resin according to claim 1 or 2, wherein the polyamide resin average relative viscosity is 2.4 to 3.0. The thermoplastic resin according to claim 1 or 2, wherein the modified aromatic vinyl compound / maleimide copolymer has a maleic anhydride of 1 to 10% graft. 3. The maleic ethylene-propylene-diene compound copolymer according to claim 2 has a viscosity of 10-60, 0.1-10 wt% maleic anhydride, 30-75 wt% ethylene, 20-50 wt% propylene and a diene compound content A thermoplastic resin composition, characterized in that the copolymer consists of 0 to 20% by weight. Polyamide resin, acrylonitrile-butadiene-styrene resin, and modified aromatic vinyl compound / maleimide copolymer, the content of butadiene rubber is 10-20% by weight, the acrylonitrile-butadiene-styrene resin A thermoplastic resin composition, characterized in that the mixture of the bulk polymerized ABS resin and the emulsion-polymerized ABS resin. The thermoplastic resin composition of claim 10, wherein the thermoplastic resin composition comprises 15-30% by weight of bulk ABS.