KR20150072114A - Low gloss thermoplastic resin composition with a enhanced gloss deviation in weld-part - Google Patents

Abstract

The present invention relates to a low-gloss thermoplastic resin composition and a manufacturing method thereof. More specifically, the present invention can reduce the gloss difference across a weld unit after the moulding process and improving the heat resistance. The present invention also relates to a product used as an interior material used in a large equipment. The low-gloss moulding resin includes: (a) a graft copolymer resin including butadiene rubber having the particle sizes of 2,000-4,000 Å; (b) an ABS-based graft copolymer resin including the butadiene rubber having the particle sizes of 1.5~4.0 μm; (c) heat-resistant SAN resin; (d) SAN resin; (e) cross-linked acrylic nitrile-based resin; and (f) amorphous inorganic materials.

Description

TECHNICAL FIELD [0001] The present invention relates to a low-temperature thermoplastic resin composition having improved gloss variation,

The present invention relates to a low-thermoplastic resin composition and a method for producing the same. More particularly, the present invention relates to a low-heat-thermoplastic resin composition having improved gloss variation of a welded portion during injection and improved heat resistance, To a product that requires unpainted low light.

Demands for uncolored low gloss ABS (acrylonitrile-butadiene-styrene) resins have been increasing as the demand for sensitive resin deviates from the cold feeling of automobile interior air quality regulations and glossy materials.

Korean Patent No. 0992537 granted to Cheil Industries Co., Ltd. discloses a method for producing a low-temperature thermoplastic resin composition having excellent surface texture, using a rubber-like particle having a graft ratio of 40 to 90% and an average particle size of 6 to 20 占 퐉, To thereby produce a low-light effect. In this method, although the deviation of gloss in the weld line portion is small, in order to produce a special rubber particle having a very large size with an average particle size of 6 to 20 탆, a separate self-production equipment is required and heat resistance is low It is difficult to use it as an automobile.

Korean Patent No. 1072037 issued to LG Chemical Co., Ltd. discloses a method of mixing an acrylonitrile copolymer for a low-gloss filler in order to produce a low-heat thermoplastic resin having excellent heat resistance and impact resistance. Although this method has excellent heat resistance and impact resistance, there is a problem that when the amount of the acrylonitrile copolymer used increases for the low gloss, the gloss deviation easily occurs in the weld line portion of the molded product.

Accordingly, there is a continuing need for a low-refractive-index thermoplastic resin which is excellent in impact resistance and heat resistance and can be used for automobiles while having less deviation in glossiness in the weld line portion.

A problem to be solved by the present invention is to provide a low-temperature thermoplastic resin for automobiles, which is excellent in impact resistance and heat resistance while having less variation in gloss in the weld line portion.

Another problem to be solved by the present invention is to provide a method for producing a low-temperature thermoplastic resin for automobile, which is excellent in impact resistance and heat resistance while having less variation in gloss in the weld line portion.

The low-gloss resin for injection according to the present invention

(a) a graft copolymer resin having an average particle diameter of 2,000 to 4,000 A butadiene rubber and

(b) a large-diameter ABS-based copolymer resin including a butadiene-based rubber having an average particle diameter of 1.5 to 4.0 탆,

(c) heat-resistant SAN resin,

(d) SAN resin,

(e) a crosslinked acrylonitrile-based resin, and

(f) an amorphous inorganic material.

The low-gloss resin composition for injection according to the present invention comprises

(a) 10 to 40% by weight of a graft copolymer resin having an average particle diameter of 2,000 to 4,000 A butadiene rubber,

(b) 4 to 15% by weight of a large-diameter ABS copolymer resin containing a butadiene-based rubber having an average particle diameter of 1.5 to 4.0 m

(c) 5 to 40% by weight of a heat-resistant SAN resin,

(d) 10 to 80% by weight of SAN resin,

(e) 0.1 to 9% by weight of a crosslinked acrylonitrile-based resin, and

(f) 0.1 to 5% by weight of an amorphous inorganic material.

Although not theoretically limited, the present invention can provide a low-gloss thermoplastic resin by introducing an acrylonitrile-based resin and an amorphous inorganic material crosslinked together with a diene rubber component having a different particle size as described above, When only a combination of a copolymer resin and a graft copolymer is introduced, only a desired level of gloss can not be obtained, and simultaneously a low light effect of reducing the gloss deviation of the weld line portion while exhibiting excellent moldability it's difficult. For example, when a crosslinked acrylonitrile-based resin alone is used, the desired low light can be obtained, but the gloss variation of the injection-molded article can not be reduced and mechanical properties such as impact resistance become difficult to manifest. Hereinafter, the present invention will be described in more detail.

(a) a graft copolymer resin

In the present invention, the butadiene-based rubber used for the graft copolymer resin is a rubber in which a small amount of an unsaturated monomer copolymerizable with butadiene or butadiene, for example, styrene or acrylonitrile, is copolymerized, Is preferably 70% by weight or more, and more preferably 90% by weight or more.

In the present invention, the graft copolymer resin is a resin obtained by graft copolymerizing an aromatic vinyl compound and a vinyl cyanoacrylate monomer on a butadiene rubber. The grafted aromatic vinyl compound is a styrene-based monomer, and the styrene-based monomer is a monomer selected from styrene, alpha-methylstyrene, p-methylstyrene, vinyltoluene, and mixtures of two or more thereof. The grafted vinyl cyan monomer may be, for example, acrylonitrile, methacrylonitrile, a mixture thereof, and the like, preferably acrylonitrile. The aromatic vinyl compound and the vinylcyanic monomer may preferably be grafted at a graft ratio of 30 to 90%.

In the present invention, the butadiene rubber preferably has a diameter of 2,000 to 4,000 Å, more preferably 3,500 to 4,000 Å. When the size of the rubber is too large, the impact resistance is excellent. However, the difference in rubber particle size between the ABS resin and the large-diameter rubber is reduced to make it difficult to adjust the gloss. When the rubber is too small, the smoothness of the resin increases, .

In the present invention, the graft copolymer is contained in an amount of 10 to 40% by weight, more preferably 20 to 30% by weight, of the total resin composition. In the practice of the present invention, the graft copolymer resin may be prepared by emulsion-polymerizing a butadiene-based rubber to prepare a latex, adding the styrene-based monomer and acrylonitrile monomer to the latex to react, Followed by drying.

(b) Large diameter ABS copolymer resin

In the present invention, the above-mentioned large diameter ABS resin is a bulk ABS resin containing a butadiene rubber having an average particle diameter of 1.5 to 4.5 占 퐉, preferably an average particle diameter of 2.5 to 3.5 占 퐉. The bulk ABS is commercially available from various manufacturers and may be, for example, MA221 grade of LG Chemical Co., Ltd.

When the rubber particle size of the above-mentioned large diameter ABS copolymer resin is too small, the ability to lower the smoothness of the resin is reduced and high gloss is exhibited. When the rubber particle size is more than 4.5 μm, the impact resistance is improved. There is a problem that heat resistance is lowered.

(c) heat-resistant SAN resin

In the present invention, the heat-resistant SAN resin is used so as to have heat resistance required in automotive products, and one of alpha-methylstyrene and phenylmaleimide or a mixture thereof is copolymerized with a styrene-based monomer and a vinylcyano- Is a circular or quaternary copolymer. The preparation of the terpolymer or quaternary copolymer can be prepared according to Korean Patents Nos. 922,700 and 915,114, which are hereby incorporated by reference and are entirely incorporated herein by reference.

In one preferred embodiment of the present invention, the heat-resistant SAN may be a quaternary copolymer, the content of the alphamethylstyrene is 40 to 50 wt%, the content of the phenylmaleimide is 15 to 25 wt% The content of the styrene-based monomer is 5 to 10% by weight, and the content of the vinyl cyanide monomer is 15 to 25% by weight.

In the present invention, the content of the heat-resistant SAN is 5 to 40 wt%, preferably 8 to 20 wt%, and when the heat-resistant SAN is less than 5 wt%, the impact resistance and flowability of the resin are improved, On the other hand, if it is 40 wt% or more, the heat resistance of the resin is improved, but the impact resistance and flowability are too low. In the practice of the present invention, a product having a weight average molecular weight of 80,000 to 120,000 can be used as the molecular weight of the heat resistant SAN.

(d) SAN resin

In the present invention, the SAN resin is a styrene-based vinylene copolymer resin. The styrene-based vinyl cyanide copolymer resin is prepared by copolymerizing a mixture containing a mixture of a styrene monomer and a vinyl cyan monomer or a mixture containing a small amount of a vinyl monomer copolymerizable therewith, for example, less than 15% by weight , Preferably a copolymer of styrene and acrylonitrile, and can have a weight average molecular weight of 80,000 to 120,000, and can be commercially obtained from various manufacturers. The styrene-vinylene-based monomer is preferably a copolymer containing 60 to 85% by weight of styrene and 15 to 40% by weight of acrylonitrile.

In the present invention, the styrene-based vinyl cyanide copolymer is preferably used in an amount of 10 to 80% by weight, more preferably 40 to 70% by weight, and the styrene- %, There is a problem that the content of the other components, particularly the heat resistant SAN, is high and the impact resistance and the moldability are poor. When the content exceeds 80% by weight, the content of the heat resistant SAN is small and the heat resistance of the resin may be deteriorated.

In the present invention, the production method of the styrene-based vinyl cyanide copolymer is not particularly limited as long as it can satisfy the molecular weight and the molecular weight distribution described above, and can be produced using conventional emulsion polymerization, bulk polymerization or suspension polymerization have. In the practice of the present invention, the acrylonitrile-styrene copolymer preferably employs bulk polymerization for appearance.

(e) Crosslinked acrylonitrile resin

In the present invention, the crosslinked acrylonitrile-based resin is used as a low-gloss filler, and is a copolymer prepared by adding diepoxide, which is an epoxide-based electrolyte, to an acrylonitrile monomer and polymerizing. The above components can be polymerized by emulsion polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization or solution polymerization, and they can be commercially purchased from various manufacturers.

In the present invention, the content of the crosslinked acrylonitrile-based resin is preferably 0.1 to 9% by weight, more preferably 1 to 7% by weight, based on the whole resin. If the content of the crosslinked acrylonitrile-based resin is less than 0.1% by weight, the impact resistance and flowability are improved but the effect of lowering the light-shielding effect is small. When the content exceeds 9% by weight, the light- So that the surface gloss of the surface is increased.

(f) atypical inorganic matter

The amorphous inorganic material used in the present invention is an amorphous inorganic material whose shape is not constant. Although it is not theoretically limited, the amorphous inorganic material is dispersed in the resin together with the above-mentioned large-diameter rubber and has an effect of scattering light and lowering gloss. In the practice of the present invention, the amorphous inorganic material is preferably an inorganic material having an average particle diameter of about 1 to 15 μm, and examples thereof include calcium carbonate, clay, talc, mica, calcium oxide ) And sepiolite can be used. The content of the amorphous inorganic material is 0.1-5 wt%, preferably 0.5-2 wt%, of the whole resin. If the amount is less than 0.1 part by weight, the effect of reducing the gloss will not be exhibited properly and it will be difficult to reduce the partial gloss deviation in the weld line portion. If the amount is more than 5% by weight, the effect of reducing the light- And the specific gravity becomes excessively high.

(g) Others

In addition, in the present invention, ordinary additives can be used for improving the physical properties of the resin to be produced, and examples thereof include phenolic heat stabilizers, lubricants, silicon oil, and methyl methacrylate emulsion-polymerized with a polymer , But the material is not limited thereto. If the amount of the additive is less than 0.01 parts by weight, it may cause discoloration and kneading problems during processing due to lack of thermal stability. If the amount is more than 3 parts by weight, Problems such as generation of gas due to pyrolysis and volatilization of the additive may occur.

The present invention relates to a graft copolymer resin; Styrene acrylonitrile (SAN) resins and heat-resistant SAN, bulk ABS and non-rigid inorganic materials, cross-linked acrylonitrile resins and conventional additives are mixed and extruded to provide excellent physical properties and excellent moldability It is effectively used for products that can produce a luxurious atmosphere because of low gloss variation of the weld line and interior parts for automobiles or heavy equipment.

1 is a plan view of a mold for producing a weld line gloss measurement specimen.

Hereinafter, this embodiment will be described in detail. It should be noted that the following examples are intended to illustrate the invention and are not to be construed as limiting the scope of the invention in any way. The preparation examples were carried out according to the following Table 1 and were produced in a 250 占 폚 twin extruder.

Examples 1 to 5 and Comparative Examples 1 to 3

1) graft copolymer resin: an average size of 3500 to 4000 Å, a rubbery content of 58.5% by weight, styrene and acrylonitrile of 41.5% by weight (styrene / acrylonitrile weight ratio = 7/3)

2) Average size of rubber is 2.5 ~ 3.0 ㎛, content of rubber is 13.5% (MA221 of LG Chemical)

3) a styrene monomer content of 68% by weight, acrylonitrile of 32% by weight, and a weight average molecular weight of 120,000

4) a quaternary copolymer having a weight average molecular weight of 100,000 and copolymerizing alpha methyl styrene and phenyl maleimide together with styrene and vinyl cyanide monomers, the content of alpha methyl styrene being 40% by weight, The content is 20% by weight, the styrene monomer content is 15% by weight, the vinylcyanide monomer is 25% by weight,

5) AM-10 of one nanotech

6) Talc having an average particle size of 4 탆: KCM-6300 manufactured by KOCHONE

7) Lubricant: ethylene bis-stearamide

8) Antioxidant: Songwon Industry SN 147BF.

Property evaluation method

(1) Impact strength: Measured according to ASTM D256.

(2) Flow Index: Measured according to ASTM D1238.

(3) Tensile strength: Measured according to ASTM D638.

(4) Heat resistance (HDT): Measured according to ASTM D648.

(5) Luster measurement: Measured according to ASTM D523.

(6) Weld line gloss variation: Measured according to ASTM D523. The gloss discrepancy between the weld line part and the normal forming part of the specimen ejected from the mold of Fig. 1 was measured and calculated as ΔGloss.

(7) Weld line gloss measurement specimen: The mold shown in FIG. 1 was produced in order to force the weld line at the time of injection.

As a result of comparative analysis of Examples and Comparative Examples in Table 2, it was found that when the graft copolymer and bulk ABS, general SAN, heat resistant SAN, crosslinked acrylonitrile resin and amorphous inorganic material were used simultaneously, high impact resistance, , The flowability, the low gloss characteristic and the gloss variation of the weld line become small, and thus the appearance quality of the finished product is excellent.

Claims (7)

(a) 10 to 40% by weight of a graft copolymer resin having an average particle diameter of 2,000 to 4,000 A butadiene rubber,
(b) 4 to 15% by weight of a large-diameter ABS copolymer resin containing a butadiene-based rubber having an average particle diameter of 1.5 to 4.0 m
(c) 5 to 40% by weight of a heat-resistant SAN resin,
(d) 10 to 80% by weight of SAN resin,
(e) 0.1 to 9% by weight of a crosslinked acrylonitrile-based resin, and
(f) 0.1 to 5% by weight of an amorphous inorganic material. The low-gloss resin composition for injection molding according to claim 1, wherein the graft copolymer resin further comprises a lubricant and an antioxidant. The low-gloss resin composition for injection molding according to claim 1, wherein the butadiene rubber in the graft copolymer resin has an average particle diameter of 3,500 to 4,000 ANGSTROM. The low-gloss resin composition for injection molding according to claim 1, wherein the large-diameter ABS copolymer resin is a bulk ABS resin comprising a butadiene-based rubber having an average particle diameter of 2.5 to 3.5 占 퐉. The heat-resistant SAN resin according to claim 1, wherein the heat-resistant SAN resin has a content of alpha methylstyrene of 40 to 50 wt%, a content of phenylmaleimide of 15 to 25 wt%, a content of the styrene monomer of 5 to 10 wt% And the vinylcyanide monomer is 15 to 25% by weight based on the total weight of the composition. The low-gloss resin composition for injection molding according to claim 1, wherein the crosslinked acrylonitrile-based resin is used in an amount of 1 to 7% by weight. The low-gloss resin composition for injection molding according to claim 1, wherein the amorphous inorganic material is an inorganic material having an average particle diameter of 1 to 15 탆.

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