KR100245948B1 - Low gloss, high thermal stable and light stable thermoplastic resin composition - Google Patents

Abstract

The present invention (A) aromatic polycarbonate resin 10-90% by weight

(B) 10-90 wt% of styrene resin

(C) 1-90 parts by weight of a thermoplastic resin showing low glossiness relative to 100 parts by weight of the components (A) and (B).

(D) A copolymer in which styrene or acrylonitrile-styrene copolymer or poly methyl methacrylate is block copolymerized to ethylene glycidyl methacrylate copolymer with respect to 100 parts by weight of the components (A) and (B). It relates to a thermoplastic resin composition, characterized in that composed of 0.1-20 parts by weight.

Description

Thermoplastic resin composition with low gloss characteristics, heat resistance and light aging resistance

The present invention relates to a thermoplastic resin composition excellent in low gloss characteristics, heat resistance and light aging resistance.

More specifically, the present invention relates to a thermoplastic resin composition having improved low gloss characteristics and moldability by mixing a composition composed of polycarbonate and styrene resin with a thermoplastic resin exhibiting low gloss characteristics and a compatibilizer having excellent heat and light resistance.

Generally, polycarbonate and styrene-based resins, especially acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) alloys, have excellent thermal stability, impact resistance and self-extinguishing properties of polycarbonate, and processability and economy of acrylonitrile-butadiene-styrene. It has been developed for use, and engineering plastics are rapidly increasing the amount of use in the interior and exterior of automobiles and housing of office equipment.

In general, high gloss was generally required in the past, but recently, as environmental problems are raised, there is a tendency to remove a painting or padding process and to use a low gloss resin directly, and related researches are actively being conducted worldwide.

As a method of making low-gloss polycarbonate / acrylonitrile-butadiene-styrene alloys, U.S. Patent No. 4,906,689 introduces a method having a low glossiness to a certain amount of rubber at 40 wt% or more by emulsion polymerization. It is.

However, this method has a disadvantage in that it is difficult to obtain low gloss of less than 30% at 60 ° measured by a Gardner gloss meter.

In addition, EP 0, 315, 490, and A2 show a method of blending a low-gloss thermoplastic resin composed of methacrylic acid / styrene / acrylonitrile / α-methylstyrene and a metal compound with polycarbonate. Due to this, injection problems and partial gloss problems for large injection molding products or complicated shape products are likely to occur. In addition, when a matt resin is used for exterior parts, discoloration and physical property degradation after light aging are great in this method.

US Patent No. 4, 624, 986 by mass polymerization of the ABS resin is made of a macro rubber particles of 1㎛ or more, and has a certain low gloss. However, this method is difficult to obtain excellent low gloss, and when there is a good low gloss property, the physical properties, particularly impact strength is severely reduced.

There is a method in which a thickener having low glossiness is added to an alloy of polycarbonate and acrylonitrile-butadiene-styrene resin.

However, this method is excellent in formability and has a certain low glossiness, while low glossiness is severely deteriorated in physical properties, particularly impact strength.

The present inventors endeavored to improve the above problems, and excellent low gloss property, heat resistance, and light aging resistance when mixed with a ABS resin having excellent low gloss characteristics, and a compatibilizer capable of improving heat discoloration and discoloration problems and physical property degradation problems after light aging. Knowing the properties to complete the present invention.

That is, the present invention (A) aromatic polycarbonate resin 10-90% by weight

(B) 10-90 wt% of styrene resin

(C) 1-90 parts by weight of a thermoplastic resin showing low glossiness relative to 100 parts by weight of the components (A) and (B).

(D) A copolymer in which styrene or acrylonitrile-styrene copolymer or polymethyl methacrylate is block copolymerized to ethylene glycidyl methacrylate copolymer with respect to 100 parts by weight of the components (A) and (B). It is related with the thermoplastic resin composition excellent in the low glossiness characteristic, heat resistance, and photoaging resistance characterized by consisting of 0.1-20 weight part.

Hereinafter, the present invention will be described.

The aromatic polycarbonate resin (A) component of the present invention is a polycarbonate resin produced by condensation polymerization of bisphenol-A and phosgene or by transesterification of bisphenol-A with diphenyl carbonate. Preferably it is resin which has a number average molecular weight of 20, 000-100, 000, and a terminal group has a carboxyl group or a hydroxyl group. The usage-amount of (A) component is 10-90 weight%, Preferably it is 30-80 weight%, When it uses out of the said range, improvement of a thermal characteristic and a mechanical characteristic cannot be expected.

The styrene resin of the component (B) used in the present invention may be a homopolymer of styrene monomers or may contain monomers such as α-methylstyrene, acrylonitrile, methyl methacrylate, etc. that are easy to copolymerize as comonomers. , High impact polystyrene (HIPS), Acrylonitrile-Butadiene-Styrene (ABS), Acrylonitrile-Butylacrylate-Styreneterpolymer (AAS), Acrylonitrile-Ethylene-Propylene-dieneterpolymer-Styrene polymer (AES) or Methylmethacrylate-Butadiene )-Styreneterpolymer) At least one resin is used.

Of these, copolymers of styrene monomers and vinyl cyan monomers (SAN) and ABS resins are preferred, and SAN resins are resins prepared by copolymerizing styrene monomers and vinyl cyan monomers by emulsion polymerization, suspension polymerization or bulk polymerization. .

Styrene-based monomers are usually 40-80% by weight of styrene, α-methylstyrene, p-methylstyrene, or the like. Vinyl cyan monomer is an acrylonitrile monomer is used is a copolymer containing usually 20-60% by weight, a resin having a number average molecular weight of 30, 000-120, 000, preferably 50, 000-100, 000 The styrene monomer and the vinyl cyan monomer of the ABS resin are the same components as above, and the particle size of the rubber latex is 0.1-3 μm, and is a resin produced by emulsion polymerization or bulk polymerization.

As for the usage-amount of the said (B) component, 10-90 weight% is used.

Within the range of the component (B), 10-90% by weight of ABS resin is used and 40% by weight or less of SAN resin is used.

The thermoplastic resin exhibiting low glossiness of component (C) of the present invention is obtained by polymerizing ethylene unsaturated carboxylic acid with at least one monomer selected from alkenylaromatic compounds, alkenylcyanide compounds and other copolymerizable monomers in the presence of rubber polymer latex. The polymer modifier is a graft copolymer having a content of 1-30% by weight of the ethylene-unsaturated carboxylic acid component and a content of 10-60% by weight of the rubber polymer latex in the polymer modifier.

The rubber polymer latex includes polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylic copolymer, ethylene-propylene copolymer, chlorine-containing polyethylene, and polyurethane, and polybutadiene is preferable. The amount of rubber polymer latex is preferably 10-60% by weight, less than 10% by weight of the impact strength is reduced, and over 60% by weight of the appearance is not good.

Ethylene-unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid and fumaric acid, and acrylic acid and methacrylic acid are suitable. Ethylene-unsaturated carboxylic acid is suitably 1-30% by weight, preferably 2-230% by weight of the graft copolymer. If it exceeds 30% by weight, there is a decrease in impact strength. Copolymers other than ethylene-unsaturated carboxylic acids are selected from alkenylaromatic compounds and alkenylcyanide compounds. Alkenylaromatic compounds include styrene, α-methylstyrene and bromostyrene. α-methylstyrene is preferred.

Alkenyl cyanide compounds include acrylonitrile and methacrylonitrile, with acrylonitrile being preferred. The copolymerizable alkenyl monomers include acrylamide and maleimide including amino groups, and methyl methacrylate is preferable.

Alkenylaromatic compounds / alkenylcyanide compounds / other copolymerizable alkenylmonomers are suitable in the range of 50-90 / 10-40 / 0-40% by weight, preferably 60-80 / 20-30 / 0-30% by weight. . Examples of monomers used to obtain the graft copolymer are acrylic acid-styrene-acrylonitrile, methacrylic acid-styrene-acrylonitrile, methacrylic acid-styrene-acrylonitrile-α-metalstyrene and methacrylic acid- Styrene-acrylonitrile-methylmethacrylate, of which methacrylic acid-styrene-acrylonitrile-methylmethacrylate is most preferred. The said (C) component uses 1-90 weight part with respect to 100 weight part of said (A) and (B) components.

The low gloss thermoplastic resin used in the present invention is a kind of organic filler as a polymer modifier for low gloss containing ethylene unsaturated carboxylic acid as a copolymer, and the surface of the molded article made from the resin scatters light to reduce surface gloss or There is no property like reduction of impact strength like organic fillers.

In the present invention, at least monovalent, divalent, and trivalent metal compounds are used as compounding additives in order to improve very good low gloss and surface appearance. Metal compounds are metals of Groups 1-5 in the periodic table capable of producing monovalent to trivalent metal ions, including hydroxides, oxides, salts and alcoholates. Examples of metal ions include Li ⁺ , Na ⁺ , K ⁺ , Ag ⁺ , Be ⁺ , Mg ²⁺ , Ca ²⁺ , Zn ²⁺ , Ba ²⁺ , Al ³⁺ , Fe ²⁺ , Fe ³⁺ , The hydroxides include Zn (OH) ₂ , Al (OH) ₃ , KOH, Ca (OH) ₂ , Sn (OH) ₂ , Fe (OH) ₂ , Na (OH), Ba (OH) ₂ , Hg ( OH) ₂ , and oxides include ZnO, Al ₂ O ₃ , K ₂ O, CaO, SnO, FeO, NA ₂ O, BaO, MgO, ZnCl ₂ , Zn (C ₂ H ₃ O ₂ ) ₂ , ZnSO ₄ , AlCl ₃ , Al ₂ (SO ₄ ) ₂ , KCl, KC ₂ H ₃ O ₂ , K ₂ SO ₄ , CaCl ₂ , Ca (C ₂ H ₃ O ₂ ) ₃ , CaSO ₄ , SnCl ₂ , SnSO ₄ , FeCl ₂ , Fe (C ₂ H ₃ O ₂ ) ₂ , FeSO ₄ , NaCl, NaC ₂ H ₃ O ₂ , Na ₂ SO ₄ , BaCl ₂ , Ba (C ₂ H ₃ O ₂ ) ₂ , BaSO ₄ , MgCl ₂ , NG (C ₂ H ₃ O ₂ ) ₂ , MgSO ₄ , zinc stearate, calcium stearate, barium stearate, tin stearate and the like.

Preferred metal compounds are oxides, in particular ZnO, Al ₂ O ₃ , K ₂ O, CaO, SnO, FeO, Na ₂ O, BaO, MgO. The metal compound is preferably 0.1-2 moles, preferably 0.2-1.5 moles per mole of ethylenically unsaturated carboxylic acid in the present composition. If it is less than 0.1 mol, the gloss deterioration effect is reduced, and if it is more than 2.0 mol, the impact strength is decreased.

The compatibilizer in which styrene or acrylonitrile-styrene copolymer or polymethyl methacrylate is block copolymerized to the ethylene glycidyl methacrylate copolymer of component (D) used in the present invention is ethylene glycidyl methacrylate. The copolymer has an ethylene content of 40-95% by weight, preferably 85% by weight, and glycidyl methacrylate contains 5-60% by weight, preferably 15% by weight and consequently accounts for the ethylene glyce as a whole. Cidyl methacrylate includes 30-90% by weight, preferably 50-70% by weight. Block copolymerized styrene, polymethylmethacrylate and styrene-acrylonitrile contain 10-70% by weight and in styrene-acrylonitrile 40-80% by weight, preferably 60-70% by weight, acrylic Ronitrile comprises 20-60% by weight, preferably 30-40% by weight. The said (D) component uses 0.1-20 weight part with respect to 100 weight part of said (A) and (B) component.

In addition to the components (A)-(D), antioxidants, light stabilizers, lubricants and the like commonly used in polycarbonate / ABS blend resins may be used alone or in combination.

In addition to the above-mentioned (A)-(D) component, a thickener (e.g., KF-710 or KF-708 from RHOM & HASS) can be used in combination.

The composition of the present invention can be obtained by dry blending each of the above components followed by melt polymerization at the same time. The temperature of the melt polymerization is 230-300 ° C. The melt polymerization method can be performed in a single screw or twin screw extruder, a Benbury mixer, a roll mill, or the like.

Hereinafter, the present invention will be described in more detail in the Examples.

[How to measure]

Impact Strength: ASTM D 256-54T

Izod, notch. 23 ℃

-Surface glossiness: Reflected light is measured using a digital gloss measurement device at an incidence angle of 60 °. (GLOSS METER UD, Toyo Seili)

-Light aging: Maintained at 88 ℃ for 300 hours using XENON ARC LAMP

Specimen shape for gloss measurement: 8 in × 8 in × 1/8 in specimens with 75ton injection machine.

[Production example]

The raw materials shown in Table 1 were polymerized in an internal 100 L stainless steel polymerization reactor with four stage paddles.

The reactor contents are heated by stirring the paddles at 90 RPM. Potassium persulfate (POTASSIUM PERSULFATE) is added when the temperature of the contents is 50 ° C., and 0.1 parts by weight of diethylhydroxyamine (DIETHYLHYDROXYAMINE) is added when the conversion rate is 90%. The reaction mixture was subjected to steam distillation to remove unreacted monomers to obtain rubber polymer latex (R-1).

The average particle diameter of the resulting rubber polymer latex was measured by COULTER NANOSIZER (manufactured by NIGAKU KIKAI).

100 parts by weight of ion-exchanged water, 0.5 parts by weight of sodium dodecylbenzene sulfate, 0.01 parts by weight of potassium hydroxide, 0.1 part by weight of t-dodecylmercaptan in a 7L glass flask equipped with a stirrer, The components of R-1) and Table 2 were added at each component ratio, followed by stirring to heat. The mixture temperature is 45 parts by weight of sodium ethylene-diaminetetraacetate 0.1 parts by weight, ferrosulphate 0.003 parts by weight, formaldehyde sodium sulfoxylate dihydrate 0.2 parts by weight, ion-exchanged water 15 parts by weight, diisopropylbenzene hydroperoxide After adding 0.1 parts by weight of an aqueous solution (AQUEOUS ACTIVATOR SOLUTION), the reaction was carried out at a reaction temperature of 70 ° C. for 1 hour. Thereafter, 0.2 parts by weight of various monomers and diisopropylbenzene hydroperoxide shown in Table 2 at 70 ° C. for 3 hours, 0.1 part by weight of t-dodecylmercaptan, 0.02 part by weight of potassium-hydroxide, and 0.1 degree of sodium dodecylbenzene sulfate The reaction was continued while continuously adding 50 parts by weight of ion-exchanged water. After completion of the reaction, stirring was continued for 1 hour. Then 0.2 part by weight of 2,2-methylene-bis (4-ethyl-6-t-butylphenol) was added and the reaction mixture was taken out of the flask. The reaction product was solidified with 2 parts by weight of potassium chloride, desorbed, washed and dried to recover the graft polymer (G-1) in powder form.

Example 1

55% by weight of polycarbonate resin (PC, IUPILON, Mitsubishi Gas Chem.) And 35% by weight of acrylonitrile-butadiene-styrene resin (ABS, Lucky.) Low-gloss thermoplastic resin prepared in the above preparation 15 parts by weight, 1% by weight of agrochemical (KF-710 RHOM & HASS Co., Ltd.), 1% by weight of acrylonitrile-styrene resin (SAN, Lucky.) 10% by weight of SAN-EGMA After mixing, extrusion was carried out to prepare pellets. The extruder used Kneader MDK-46 from Buss, Inc., at a temperature of 250 ° C. The pellets thus prepared were dried at 110 ° C. for 6 hours, and then injected at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. with an injection capacity of 75 tons to produce specimens for measuring properties and gloss measurement. The prepared specimens were measured for 24 hours at 23 ° C., and then measured for physical properties according to ASTM. The results are shown in Table 4 below.

Example 2-5

The composition of Table 3 was carried out as in Example 1, and the results are shown in Table 4.

Comparative Example 1-5

The composition of Table 5 was carried out as in Example 1, and the results are shown in Table 6.

ABS (1): ABS resin

ABS (2): Low Gloss Resin

Claims (5)

(A) 10 to 90% by weight of aromatic polycarbonate resin, (B) styrene homopolymer, styrene copolymer containing alphamethylstyrene, acrylonitrile or methyl methacrylate as comonomer, high impact polystyrene (HIPS) , Acrylonitrile-butadiene-styrene (ABS), acrylonitrile-butylacrylate-styrene (AAS), acrylonitrile- (ethylene-propylene-diene trimer) -styrene (AES) and methylmethacrylate-butadiene 10 to 90% by weight of a styrene resin selected from the group consisting of styrene (MBS) resins, and (C) ethylenically unsaturated carbide in the presence of a rubber polymer latex with respect to 100 parts by weight of the components (A) and (B). In a low gloss graft copolymer 1 in which at least one monomer selected from an acid, an alkenylaromatic compound, an alkenylcyanide compound, an amino group-containing compound, and methyl methacrylate is polymerized 90 parts by weight, and (D) Block air in which styrene, acrylonitrile-styrene copolymer or polymetal methacrylate is copolymerized with ethylene glycidyl methacrylate copolymer with respect to 100 weight part of said (A) and (B) component. Thermoplastic resin composition, characterized in that composed of 0.1 to 20 parts by weight of coalescing. The thermoplastic resin composition of claim 1, wherein the aromatic polycarbonate resin has a number average molecular weight of 1,000 to 200,000. The thermoplastic resin composition of claim 1, wherein the styrene-based resin comprises 10-90 wt% of acrylonitrile-butadiene-styrene (ABS) resin and 40 wt% or less of styrene-acrylonitrile (SAN) resin. The thermoplastic resin composition according to claim 1, wherein the content of the unsaturated carboxylic acid component in the graft copolymer is 1-30% by weight and the content of the rubber polymer latex is 10-60% by weight. 7. The thermoplastic resin composition according to claim 1 or 6, wherein the rubber polymer latex is polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylic polymer, ethylene-propylene copolymer, chlorine-containing polyethylene or polyurethane.