KR20120100530A - Thermoplastic resin composition and method for preparing thereof - Google Patents

Abstract

PURPOSE: A thermoplastic resin composition and a manufacturing method thereof are provided to improve mechanical properties and weatherability by having the low coefficient of linear expansion. CONSTITUTION: A thermoplastic resin composition comprises 25-70 parts by weight of two kinds of acrylate-styrene-acrylonitrile-based graft copolymers having different average particle diameters, 20-65 parts by weight of heat-resistant copolymer which includes N-phenylmaleimide based copolymers and alpha-methylenestyrene based copolymers, and 0.1-5 parts by weight of silicon based coloring enhancers. The acrylate-styren-acrylonitrile based graft-copolymer comprises a first copolymer which has the average particle diameter of 500-2,000 angstrom, and a second copolymer which has the average particle diameter of 2,500-5,000 angstrom.

Description

Thermoplastic resin composition and its manufacturing method {THERMOPLASTIC RESIN COMPOSITION AND METHOD FOR PREPARING THEREOF}

The present invention relates to a thermoplastic resin composition and a method for producing the same.

Thermoplastic resins, such as acrylate-styrene-acrylonitrile-based resins (hereinafter referred to as ASA) resins, are increasingly used in a wide range of areas such as automobile interior materials, office equipment housings, and building materials.

In the past, the demand for high gloss resins was high, but in recent years, the demand for matte resins has been increasing in order to create a refined atmosphere as the demand for emotional quality increases. In particular, in the case of automobile interior parts, low-gloss resins are used to prevent driver's visual disturbance due to gloss and to harmonize with other component materials. In addition, as environmental problems arise, a separate matte coating or a step of covering the pad is omitted, and a low gloss resin is directly used.

In order to achieve a low gloss effect without matt coating or pads, the colorability of the resin is very important, but in general, ASA-based graft resins are significantly inferior in colorability to ABS (acrylate-butadiene-styrene) -based graft resins. In order to compensate for the drawback of the colorability, the ASA graft resin uses a larger amount of pigments and dyes, which causes a problem of lowering heat resistance, and decomposition of low molecular weight substances of pigments and dyes in the injection process. Is generated to cause gas marks on the appearance of the injection molded product and / or a defect of the weld line.

In addition, while ASA-based resins have excellent weather resistance and competitive price, they are often used as housing materials in combination with other materials because of their low impact strength. However, since the coefficient of linear expansion is larger than that of nylon and glass fiber reinforced materials serving as a supporting structure, a warping defect may occur due to the difference in coefficient of linear expansion between materials at high temperatures.

An object of the present invention is to introduce two kinds of acrylate-styrene-acrylonitrile-based graft copolymers, heat-resistant copolymers and silicone-based color improving agents having different diameters, and to prepare a thermoplastic resin composition having an optimal composition ratio therebetween. To provide a way.

The thermoplastic resin composition may include 25 to 70 parts by weight of two kinds of acrylate-styrene-acrylonitrile graft copolymers having different average particle diameters; 20 to 65 parts by weight of a heat resistant copolymer including an N-phenyl maleide copolymer and an alpha-methylene styrene copolymer; And 0.1 to 5 parts by weight of the silicone-based color improving agent.

In addition, the present invention provides a method for producing the thermoplastic resin composition.

The thermoplastic resin composition of the present invention is excellent in mechanical properties such as impact strength and heat resistance reliability, and has a low coefficient of linear expansion and therefore is excellent in weather resistance. In addition, the thermoplastic resin composition has a low gloss and excellent colorability, and thus may be variously used for automobile interior materials and electric and electronic products.

The thermoplastic resin composition according to the present invention,

25 to 70 parts by weight of two kinds of acrylate-styrene-acrylonitrile graft copolymers having different average particle diameters; 20 to 65 parts by weight of a heat resistant copolymer including an N-phenyl maleide copolymer and an alpha-methylene styrene copolymer; And 0.1 to 5 parts by weight of the silicone-based color improving agent. The thermoplastic resin composition having the above composition ratio is excellent in impact strength, thermal reliability and weather resistance, and has low gloss and excellent colorability.

The acrylate-styrene-acrylonitrile-based graft copolymer includes two kinds of graft copolymers having different particle diameters. In one embodiment, the acrylate-styrene-acrylonitrile graft copolymer, the first copolymer having an average particle diameter of 500 to 2,000 내지; And a second copolymer having an average particle diameter of 2,500 to 5,000 kPa. The acrylate-styrene-acrylonitrile graft copolymer, 20 to 45 parts by weight of the first copolymer; And 5 to 25 parts by weight of the second copolymer.

The first copolymer, 10 to 70 parts by weight of the acrylic rubber polymer having an average particle diameter of 500 to 2,500 Pa; 10 to 60 parts by weight of styrene monomer; And it may be a copolymer of acrylonitrile-based monomer 1 to 30 parts by weight.

In addition, the second copolymer, 10 to 70 parts by weight of the acrylic rubber polymer having an average particle diameter of 2,500 to 5,000 kPa; 10 to 60 parts by weight of styrene monomer; And it may be a copolymer of acrylonitrile-based monomer 1 to 30 parts by weight.

Hereinafter, the thermoplastic resin composition according to the present invention will be described in detail by dividing each of the compositions.

1. First copolymer

The first copolymer is a copolymer obtained by grafting a styrene-based monomer and an acrylonitrile-based monomer to an acrylic rubber polymer having an average particle diameter of 500 to 2,000 mm, and is 20 to 45 parts by weight, more preferably based on the total weight of the thermoplastic resin composition. Preferably 20 to 35 parts by weight is used. If the content of the first copolymer is less than 20 parts by weight, the coloring properties may be significantly lowered. If the content of the first copolymer exceeds 45 parts by weight, fluidity, hardness, and scratch resistance may be lowered.

The composition ratio of the first copolymer is 10 to 70% by weight of the acrylic rubber polymer; 10 to 60% by weight of styrene monomer; And 1 to 30% by weight of the acrylonitrile monomer is characterized in that the grafted copolymer.

The acrylic rubber polymer, the styrene monomer and the acrylonitrile monomer each of the components of the first copolymer will be described in more detail below.

(1-a) acrylic rubber polymer

The average particle diameter of the acrylic rubber polymer may be in the range of 500 to 2,000 mm 3, more preferably 700 to 1,500 mm 3. When the particle size of the acrylic rubber polymer is less than 500 mm, mechanical properties such as impact strength and tensile strength of the molded article are lowered, and the amount of emulsifier is increased, which may result in weak thermal stability. When the particle size of the acrylic rubber polymer exceeds 2,000 kPa, the colorability is lowered.

The content of the acrylic rubber polymer may be 10 to 70 parts by weight, preferably 30 to 50 parts by weight based on the total weight of the first copolymer. If the content of the acrylic rubber polymer is less than 10 parts by weight, the impact strength is lowered, and if it exceeds 70 parts by weight, the graft ratio is lowered, thereby reducing the hardness and scratch resistance.

In addition, the pH of the acrylic rubber polymer may be 5 to 9, more preferably 6 to 8.

The acrylic rubber polymer may be prepared by mixing an acrylate monomer, an emulsifier, a polymerization initiator, a graft agent, a crosslinking agent, an electrolyte, and water to emulsion polymerization. The acrylate monomers may be butyl acrylate, ethylhexyl acrylate or mixtures thereof, for example butyl acrylate. The content of the acrylate monomer may be 5 to 50% by weight, more preferably 10 to 45% by weight based on the total weight of the acrylic rubbery polymer.

The emulsifier may be an alkyl sulfosuccinic acid metal salt derivative having 12 to 18 carbon atoms, an alkyl sulfate ester or a sulfonic acid metal salt derivative having 12 to 18 carbon atoms in an aqueous solution. Examples of the alkyl sulfosuccinic acid metal salt derivative having 12 to 18 carbon atoms include dicyclohexyl sulfosuccinate sodium salt, dihexyl sulfosuccinate sodium salt, di (2-ethylhexyl) sulfosuccinate sodium salt and di (2-ethylhexyl). ) Potassium sulfosuccinate salt and di (2-ethylhexyl) lithium sulfosuccinate salt. In addition, the alkyl sulfate ester or sulfonic acid metal salt derivative having 12 to 20 carbon atoms may include, for example, sodium lauric sulfate, sodium dodecyl sulfate, sodium dodecyl benzenelic sulfate, sodium octadecyl sulfate, sodium oleate sulfate, and potassium dode It may be at least one selected from the group consisting of real sulfate and potassium octadecyl sulfate. The content of the emulsifier may be 1 to 4% by weight, more preferably 1.5 to 3% by weight based on the total weight of the acrylic rubbery polymer.

The polymerization initiator may be an inorganic or organic peroxide, for example, water-soluble initiators such as potassium persulfate, sodium persulfate or ammonium persulfate; Or fat-soluble initiators such as cumene hydroperoxide or benzoyl peroxide. The content of the polymerization initiator may be 0.05 to 3% by weight based on the total weight of the acrylic rubbery polymer.

As the graft agent, for example, aryl methacrylate, triaryl isocyanurate, triarylamine or diarylamine can be used. The content of the graft agent may be 0.01 to 0.07% by weight based on the total weight of the acrylic rubbery polymer.

As a crosslinking agent, for example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacryl Latex, neopentylglycol dimethacrylate, trimethylol propane trimethacrylate or trimethylolmethane triacrylate can be used. The content of the crosslinking agent may be 0.01 to 0.3% by weight based on the total weight of the acrylic rubbery polymer.

By adding the graft agent and the crosslinking agent, it is possible to increase the elasticity of the acrylic rubber polymer and to improve physical properties such as impact strength.

As the electrolyte, NaHCO ₃ , Na ₂ S ₂ O _7, or K ₂ CO ₃ may be used. The content of the electrolyte may be 0.05 to 0.4 wt% based on the total weight of the acrylic rubbery polymer.

 Water plays a role of medium in the emulsion polymerization, preferably ion-exchanged water, the amount of the remaining amount of the total weight of the acrylic rubber polymer except the acrylate monomer, emulsifier, polymerization initiator, graft agent, crosslinking agent and electrolyte described above Can be used.

The acrylic rubber polymer is introduced into the reactor by continuously adding acrylate monomers, emulsifiers, polymerization initiators, graft agents, crosslinking agents, and electrolytes, or by using both continuous and batch injections, and polymerization generally used in the art. It can be prepared by emulsion polymerization under the conditions.

(1-b) Styrene series  Monomer

Examples of styrenic monomers include one or more selected from the group consisting of styrene, alpha-methylstyrene and para-methylstyrene. The content of the styrene-based monomer may be 10 to 60 parts by weight, preferably 30 to 50 parts by weight based on the total weight of the first copolymer. If the content of the styrene monomer is less than 10% by weight, the graft rate is not good, and if the content of the styrene monomer exceeds 60% by weight, the amount of the acrylic rubber polymer is relatively low.

(1-c) Acrylonitrile  Monomer

The acrylonitrile-based monomer may be, for example, one or more selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile. The content of the acrylonitrile-based monomer may be 1 to 30 parts by weight, preferably 10 to 20 parts by weight based on the total weight of the first copolymer. If the content of the acrylonitrile-based monomer is less than 1 part by weight, the mechanical properties are lowered, and if it exceeds 30 parts by weight, the flowability of the resin is inferior.

(1-d) additive

The first copolymer may further contain an additive such as an emulsifier, a polymerization initiator, a molecular weight regulator and water, which are known to be usable in the art depending on the use, in addition to the acrylic rubber polymer, the styrene monomer and the acrylonitrile monomer.

The emulsifier is pH 9-13, and can use carboxylic acid metal salt derivatives, such as a fatty acid metal salt of 12 to 20 carbon atoms, or a rosin acid metal salt of 12 to 20 carbon atoms. As the fatty acid metal salt, fatty acid sodium, sodium laurate, sodium oleate or potassium oleate may be used, and as the rosin acid metal salt, sodium rosin or potassium rosin may be used. The content of the emulsifier may be 1 to 3 parts by weight based on the combined weight of the acrylic rubber polymer, the styrene monomer and the acrylonitrile monomer.

The polymerization initiator may use an inorganic or organic peroxide, and may include, for example, a water-soluble initiator such as potassium persulfate, sodium persulfate or ammonium persulfate; Or a fat-soluble initiator such as benzoyl peroxide. The content of the polymerization initiator may be 0.05 to 0.3 parts by weight based on the combined weight of the acrylic rubber polymer, the styrene monomer and the acrylonitrile monomer.

A mercaptan compound can be used as the molecular weight regulator, and for example, t-dodecyl mercaptan or n-octyl mercaptan can be used. The content of the molecular weight modifier may be 0.02 to 0.2 parts by weight based on the combined weight of the acrylic rubber polymer, the styrene monomer and the acrylonitrile monomer.

In addition, the water may be ion-exchanged water, it may be used in the general content used in the art.

In the first copolymer according to the present invention, a styrene monomer, an acrylonitrile monomer, and an additive may be continuously added to the acrylic rubber polymer described above to perform a polymerization reaction. When the polymerization reaction is carried out by collectively adding the components, the pH of the polymerization system is temporarily raised, so that grafting is difficult, and the stability of the copolymer particles is lowered, so that the internal structure of the particles may not be uniform. In addition, the polymerization method is not particularly limited, but an emulsion polymerization method may be used. For example, a first copolymer in which a styrene monomer and an acrylonitrile monomer are grafted to an acrylic rubber polymer backbone may be prepared. Can be. The pH of the prepared first copolymer may be 8 to 11, more preferably 9 to 10.5.

In addition, the first copolymer may be prepared in a powder state by aggregating using a metal salt or a metal flocculant and then washing, dehydrating and drying. The content of the metal salt or metal flocculant may range from 500 to 2,000 ppm, preferably 1,000 to 1,500 ppm, based on the total weight of the first copolymer.

The metal flocculant may comprise one or more metals selected from the group consisting of alkali metals and alkaline earth metals, for example, one or more metals selected from the group consisting of potassium, sodium, barium, magnesium and calcium. . In addition, the metal salt flocculant may include metal salts such as sulfuric acid, nitric acid, phosphoric acid, or hydrochloric acid, for example, a group consisting of potassium salt, sodium salt, barium salt, magnesium salt and calcium salt of sulfuric acid, nitric acid, phosphoric acid or hydrochloric acid. It may include one or more selected from, and preferably calcium chloride, magnesium sulfate, barium sulfate, potassium sulfate, sodium sulfate, sodium phosphate, magnesium phosphate and the like can be used.

After the first copolymer is subjected to the emulsion polymerization reaction of the composition described above, the first copolymer is aggregated at 80 ° C. to 85 ° C. and atmospheric pressure using a metal salt flocculant in the form of an aqueous solution, and aged at 90 to 98 ° C., and then aged. After dehydration and washing, it can be prepared by drying.

2. Second Copolymer

The second copolymer is a copolymer obtained by grafting a styrene monomer and an acrylonitrile monomer to an acrylic rubber polymer having an average particle diameter of 2,500 to 5,000 kPa, and is 20 to 45 parts by weight, more preferably based on the total weight of the thermoplastic resin composition. Preferably 20 to 35 parts by weight is used. If the content of the first copolymer is less than 20 parts by weight, the coloring properties may be significantly lowered. If the content of the first copolymer exceeds 45 parts by weight, fluidity, hardness, and scratch resistance may be lowered.

The composition ratio of the first copolymer is 10 to 70% by weight of the acrylic rubber polymer; 10 to 60% by weight of styrene monomer; And 1 to 30% by weight of the acrylonitrile monomer is characterized in that the grafted copolymer.

The acrylic rubber polymer, the styrene monomer and the acrylonitrile monomer each of the components of the first copolymer will be described in more detail below.

The second copolymer is a copolymer obtained by grafting a styrene monomer and an acrylonitrile monomer to an acrylic rubber polymer having an average particle diameter of 2,500 to 5,000 kPa, based on the total weight of the thermoplastic resin composition, 5 to 25 parts by weight, more preferably. It is preferable to use 10 to 25 parts by weight. If the content of the first copolymer is less than 10 parts by weight, the coloring properties may be significantly lowered. If the content of the first copolymer exceeds 25 parts by weight, fluidity, hardness, and scratch resistance may be lowered.

The composition ratio of the second copolymer is 10 to 70% by weight of the acrylic rubber polymer; 10 to 60% by weight of styrene monomer; And 1 to 30% by weight of the acrylonitrile monomer is characterized in that the grafted copolymer.

The acrylic rubber polymer, the styrene monomer and the acrylonitrile monomer each of the components of the second copolymer will be described in more detail below.

(2-a) acrylic rubber polymer

The average particle diameter of the acrylic rubber polymer may be in the range of 2,500 to 5,000 mm 3, more preferably 3,500 to 4,800 mm 3. If the particle size of the acrylic rubber polymer is less than 500 GPa, mechanical properties such as impact strength and tensile strength of the molded article are lowered. If the particle size is more than 5,000 GPa, problems such as fluidity, processability, glossiness, etc. may occur.

The content of the acrylic rubber polymer may be 10 to 70 parts by weight, preferably 30 to 50 parts by weight based on the total weight of the second copolymer. When the content of the acrylic rubber polymer is less than 10 parts by weight, the impact strength is lowered. When the content of the acrylic rubber polymer is more than 70 parts by weight, the graft ratio is lowered, thereby decreasing hardness and scratch resistance.

In addition, the pH of the acrylic rubber polymer may be from 5 to 9, more preferably from 6 to 8.

The acrylic rubber polymer may be prepared by mixing an acrylate monomer, an emulsifier, a polymerization initiator, a graft agent, a crosslinking agent, an electrolyte, and water to emulsion polymerization. The content of the emulsifier may be 0.1 to 1% by weight, more preferably 0.2 to 0.8% by weight based on the total weight of the acrylic rubbery polymer. Except for the content of the emulsifier, the components and contents of the polymerization initiator, the graft agent, the crosslinking agent, the electrolyte and the water are the same as those of the acrylic rubber polymer of the first copolymer described above.

 (2-b) Styrene series  Monomer

The components and contents of the styrene monomer are the same as those of the acrylic rubber polymer of the first copolymer described above.

(2-c) Acrylonitrile  Monomer

The components and contents of the acrylonitrile monomers are the same as those of the acrylic rubber polymer of the first copolymer described above.

 (2-d) additive

The second copolymer may further include additives such as emulsifiers, polymerization initiators, molecular weight modifiers and water known to be usable in the art, depending on the use, in addition to the acrylic rubbery polymer, the styrene monomer and the acrylonitrile monomer. Additives, such as an emulsifier, a polymerization initiator, a molecular weight regulator, and water, can use the thing of the same kind, characteristic, etc. which can be used for the 1st copolymer demonstrated above, The usage-amount can also be used within the same range.

The process of preparing the second copolymer, which is the composition of the present invention, can be prepared in substantially the same manner as in the case of the first copolymer, using the components described above.

3. Heat resistant copolymer

The heat resistant copolymer may include an N-phenyl maleide based copolymer and an alpha-methylene styrene based copolymer. The content of the heat resistant copolymer may be 20 to 65 parts by weight, more preferably 40 to 65 parts by weight based on the total weight of the thermoplastic resin composition. If the content of the heat resistant copolymer is less than 20 parts by weight, it may not exhibit sufficient heat resistance enhancement effect. If it exceeds 65 parts by weight, the impact strength is lowered.

The mixing ratio of the N-phenyl maleide copolymer and the alpha-methylene styrene copolymer may be 1: 1 to 1: 4 weight ratio, more preferably 1: 2 to 1: 3.5 weight ratio, which is compatible between the two components. And heat resistance improving effect are considered.

(3-a) N- Phenyl Maleimide  Copolymer

N-phenyl maleimide copolymers include N-phenyl maleide monomers; Acrylonitrile monomers; And copolymers of styrene monomers.

The content of the N-phenyl maleide monomer may include 30 to 70 parts by weight, more preferably 35 to 60 parts by weight based on the total weight of the N-phenyl maleimide copolymer. The content of acrylonitrile monomer may be 1 to 30 parts by weight, more preferably 5 to 25 parts by weight based on the total weight of the N-phenyl maleimide copolymer. In addition, the content of the styrene monomer may be 30 to 70 parts by weight, more preferably 40 to 65 parts by weight based on the total weight of the N-phenyl maleimide copolymer.

N-phenyl maleimide copolymer prepared by copolymerizing the components, based on the total weight of the N-phenyl maleimide copolymer, 1 to 5 parts by weight of maleic anhydride (MAH), more preferably 2 to 3 parts by weight It may include. If the content of maleic anhydride is less than 1 part by weight, the effect of improving the coefficient of linear expansion is insignificant, and if it exceeds 5 parts by weight, the fluidity decreases.

The method for producing the N-phenyl maleimide copolymer is not particularly limited, but can be produced by a continuous process consisting of a raw material input pump, a continuous stirring tank, a preheating tank, a volatilization tank, a polymer transfer pump, an extrusion processing machine, and the like.

(3-b) alpha-methylene Styrene series  Copolymer

The alpha-methylene styrene-based copolymer may be a copolymer of an alpha-methyl styrene monomer and an acrylonitrile monomer, and may further include a solvent, a molecular weight modifier, and an additive.

The content of the alpha-methyl styrene monomer may be 50 to 80 parts by weight, preferably 60 to 70 parts by weight based on the total weight of the alpha-methylene styrene-based copolymer. In addition, the content of the acrylonitrile monomer may be 20 to 50 parts by weight, preferably 30 to 40 parts by weight based on the total weight of the alpha-methylene styrene-based copolymer.

In the process of preparing the alpha-methylene styrene-based copolymer, the method of polymerizing the alpha-methyl styrene monomer and the acrylonitrile monomer is not particularly limited, and may be prepared through bulk polymerization. For example, a mixture of alpha-methyl styrene monomer, acrylonitrile monomer, toluene and t-dodecyl mercaptan can be polymerized at 140 ° C. to 170 ° C. for 2 hours to 4 hours, and a raw material input pump can be used. , Continuous stirring bath, preheating bath, volatilization tank, polymer transfer pump and extrusion process can be carried out in a continuous process.

4. Silicone Coloring Enhancer

The silicone type color improving agent may be, for example, at least one selected from the group consisting of phenylsilicone color improving agents, epoxy silicone type color improving agents, carbonyl silicon type color improving agents, amino silicon type color improving agents, polyester type color improving agents, and fluoroalkyl silicone type color improving agents. It may include.

The content of the silicone-based color improving agent may be 0.1 to 5 parts by weight, more preferably 0.1 to 2 parts by weight based on the total weight of the thermoplastic resin composition. If the content of the silicone-based color improving agent is less than 0.1 part by weight, the color improving effect is not sufficient, and if it exceeds 5 parts by weight, compatibility with other components is inferior, and the surface condition of the molded article is poor due to the remaining color improving agent. .

The thermoplastic resin composition of the present invention described above is a first copolymer; Second copolymer; Heat resistant copolymers; And in addition to the silicone-based color improving agent may further include an additive to obtain additional effects.

As the additive, a general one used in the art may be used. For example, a quencher, a lubricant, an antioxidant, an ultraviolet stabilizer, a weather stabilizer, a compatibilizer, a hydrolysis stabilizer, a mold release agent, a pigment, an antistatic agent, and a conductivity-imparting agent , At least one selected from the group consisting of a magnetic imparting agent, a filler, a crosslinking agent, an antibacterial agent, a processing aid and the like can be used. The amount of the additive used may be 0.05 to 10 parts by weight, more preferably 0.5 to 5 parts by weight based on the total weight of the thermoplastic resin composition.

The lubricant may be, for example, one or more selected from the group consisting of ethylene bis stearamide, polyethylene oxide wax and magnesium stearate. The amount of the lubricant may be 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight based on the total weight of the thermoplastic resin composition.

The antioxidant may be, for example, a phenolic antioxidant or a phosphate antioxidant, preferably stearyl-β- (3,5-di-t-butyl-4-hydrocyphenyl) propionate [ stearyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate]. The content of the antioxidant may be 0.5 to 2 parts by weight based on the total weight of the thermoplastic resin composition.

UV stabilizers can be used generally used in the art, for example, 2- (2H-benzotriazol-2-ol) -para-cresol [2- (2H-benzotriazol-2-yl) -p -cresol] and bis (2,2,6,6-tetramethyl-4-pyrididyl) sebacate [Bis (2,2,6,6-tetramethyl-4-piperidyl) sebaceate] have. The content of the UV stabilizer may be 0.5 to 2 parts by weight based on the total weight of the thermoplastic resin composition.

The thermoplastic resin composition according to the present invention has an impact strength (IMP, 1/8 ″, measured by ASTM D256) of 8 kgf · cm / cm or more, preferably 10 kgf · cm / cm or more. The coefficient of linear expansion (measured by ASTM D256) is 85 μm / m / ° C. or less, preferably 82 μm / m / ° C. or less. The heat deflection temperature (measured by ASTM D648) is at least 95 ° C, preferably at least 98 ° C. The glossiness (measured by ASTM D2457) is 30 or less, preferably 20 or less, and the weather resistance gray scale is 4.5 or more. Also, when measured according to the Commission International on Illumination (CIE) standard colorimetry, the L value may be 30 or less.

The present invention provides a method for producing a thermoplastic resin composition. The specific manufacturing method is as described above.

For example, the manufacturing method of the thermoplastic resin composition which concerns on this invention is an acryl-type copolymer whose average particle diameter is 200-2,000 kPa; Styrene monomers; And grafting the acrylonitrile-based monomer to prepare a first copolymer.

Acrylic copolymer with an average particle diameter of 2,500-5,000 kPa; Styrene monomers; And grafting the acrylonitrile-based monomer to prepare a second copolymer.

N-phenyl maleimide copolymer; And mixing the alpha-methylene styrene-based copolymer to prepare a heat resistant copolymer. And

20 to 45 parts by weight of the first copolymer; 5 to 25 parts by weight of the second copolymer; 20 to 65 parts by weight of the heat resistant copolymer; And mixing 0.1 to 5 parts by weight of the silicone-based color improving agent to prepare a resin composition.

Preparing the first copolymer; And the step of preparing the second copolymer, each independently, the styrene-based monomer and acrylonitrile-based monomer can be continuously added to the acrylic rubber polymer to perform the polymerization reaction.

In the step of preparing the resin composition, the first copolymer and the second copolymer, each independently, may be pH 8 to 11.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[ Example  One]

First Copolymer Preparation

Step 1: preparing acrylic rubber polymer

10 weight percent butyl acrylate (acrylate monomer) in the total weight of the reaction mixture in a 10 L reactor, 1.5 weight percent di (2-ethylhexyl) sulfosuccinate sodium salt (emulsifier), ethylene glycol dimethacrylate (Crosslinking agent) 0.02% by weight, sodium bicarbonate (NaHCO ₃ , electrolyte) 0.1% by weight, the reaction mixture containing potassium persulfate (polymerization initiator) 0.04% by weight and water 88.34% by weight, the reaction temperature was 70 The polymer seed was prepared by raising the temperature to ℃ and reacting for 1 hour.

Then again here, 30 wt% butylacrylate, 0.5 wt% di (2-ethylhexyl) sulfosuccinate sodium salt, 0.1 wt% sodium hydrogencarbonate, 0.06 wt% potassium persulfate and 69.34 wt% water While continuously introducing the reaction mixture, the polymerization reaction was performed at 70 ° C. for 3 hours to prepare an acrylic rubber polymer having an average particle diameter of 900 mm 3.

Step 2: Preparation of the First Copolymer

63 parts by weight of distilled water, 1.4 parts by weight of potassium rosinate (emulsifier), 100 parts by weight of the reaction mixture of 40% by weight of the acrylic rubber polymer having an average particle diameter of 900Å, 40% by weight of styrene and 20% by weight of acrylonitrile. 0.05 parts by weight of dodecyl mercaptan (molecular weight regulator) and 0.1 parts by weight of potassium persulfate (polymerization initiator) were continuously added at 70 ° C. for 5 hours to carry out the polymerization reaction, while further increasing the polymerization conversion rate at 80 ° C. for 1 hour. After the reaction, the mixture was cooled to 60 ° C to prepare a first copolymer having a polymerization conversion rate of 98%, an average particle diameter of 1,200 Pa, pH 9.5, and a graft rate of 40%.

Next, the first copolymer was agglomerated at 85 ° C. and 1 atm conditions using an aqueous calcium chloride solution (metal salt flocculant), aged, dehydrated and washed at 95 ° C., and then dried for 30 minutes by hot air at 90 ° C. To prepare a first copolymer powder containing 1,500 ppm CaCl ₂ .

Second Copolymer Preparation

Step 1: preparing acrylic rubber polymer

5 wt% of butylacrylate (acrylate monomer), 1.5 wt% of di (2-ethylhexyl) sulfosuccinate sodium salt (emulsifying agent), ethylene glycol dimethacrylate, in a 10 L reactor (Crosslinking agent) 0.02% by weight, sodium hydrogencarbonate (NaHCO ₃ , electrolyte) 0.1% by weight, the reaction mixture containing potassium persulfate (polymerization initiator) 0.04% by weight and 93.34% by water, the reaction temperature was 70 The polymer seed was prepared by raising the temperature to ℃ and reacting for 1 hour.

Then again here, 45% by weight of butylacrylate, 0.285% by weight of di (2-ethylhexyl) sulfosuccinate sodium salt, 0.1% by weight of sodium bicarbonate, 0.06% by weight of potassium persulfate and 54.555% by weight of water While continuously introducing the reaction mixture, the polymerization reaction was performed at 70 ° C. for 3 hours to prepare an acrylic rubber polymer having an average particle size of 3,500 mm 3.

Step 2: Preparation of Second Copolymer

63 parts by weight of distilled water, 1.4 parts by weight of potassium rosinate (emulsifier), based on 100 parts by weight of the reaction mixture of 50% by weight of the acrylic rubber polymer having an average particle diameter of 3,500 Pa, 35% by weight of styrene and 15% by weight of acrylonitrile. 0.05 parts by weight of t-dodecyl mercaptan (molecular weight regulator) and 0.1 parts by weight of potassium persulfate (polymerization initiator) were continuously added at 70 ° C. for 5 hours to carry out the polymerization reaction, while increasing the polymerization conversion rate at 80 ° C. for 1 hour. After further reacting, the mixture was cooled to 60 ° C to prepare a second copolymer having a polymerization conversion rate of 99%, an average particle size of 4,500 Pa, pH 9.5, and a graft rate of 45%.

Next, the second copolymer was agglomerated at 85 ° C. and 1 atm conditions using an aqueous calcium chloride solution (metal salt flocculant), aged, dehydrated and washed at 95 ° C., and then dried by hot air at 90 ° C. for 30 minutes. Finally, a second copolymer powder including 1,500 ppm of CaCl ₂ was prepared.

Heat resistant copolymer

N-phenyl maleimide copolymer containing 40% by weight of N-phenyl maleide monomer, 7% by weight of acrylonitrile monomer and 53% by weight of styrene (PAS1460 manufactured by Japan Catalyst, Mw = 100,000, glass transition temperature of 165 ° C) It was used as it is.

And alpha-methyl styrene copolymer (980HM of LG Chem, Mw = 150,000) containing 75 weight% of alpha-methyl styrene monomers and 25 weight% of acrylonitrile monomers was used as it was.

Silicone Coloring Enhancer

As a silicone type color improving agent, the phenyl silicone type color improving agent (X-22-1821 by Shin-Etus) of viscosity 1000CS was used as it was.

Preparation of resin composition

The first copolymer, the second copolymer, the heat resistant copolymer, and the silicone-based color improving agent prepared above were mixed in the composition ratios of Table 1 below. Then, based on the total weight of the mixture, 0.5 parts by weight of ethylene bisteaamide (lubricant), stearyl-β- (3,5-di-t-butyl-4-hydrocyphenyl) propionate (antioxidant) ) 0.5 parts by weight, (2,2,6,6-tetramethyl-4-piperidyl) sebacate (weather stabilizer) and 1 part by weight of quencher (B-Mat manufactured by Chemtura), 240 parts The thermoplastic resin composition was manufactured using the twin screw extruder (L / D44, screw diameter 30mm) at degreeC.

[ Example  2]

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that 20 parts by weight of the first copolymer and 20 parts by weight of the second copolymer were used in the composition and content as shown in Table 1 below.

[ Example  3]

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that 20 parts by weight of N-phenyl maleimide copolymer and 44.8 parts by weight of alpha-methyl styrene copolymer were used in the composition and content as shown in Table 1 below. .

[ Comparative example  One]

As shown in Table 1, except that 10 parts by weight of the first copolymer, 30 parts by weight of the second copolymer was carried out in the same manner as in Example 1, the thermoplastic resin composition was molded into pellets.

[ Comparative example  2]

As shown in Table 1, the thermoplastic resin composition was prepared in the same manner as in Example 1 except that the first copolymer was not used and 40 parts by weight of the second copolymer was used.

[ Comparative example  3]

As shown in Table 1, a thermoplastic resin composition was prepared in the same manner as in Example 1, except that 59.8 parts by weight of the alpha-methyl styrene copolymer was used instead of the N-phenyl maleimide copolymer.

[ Comparative example  4]

As shown in Table 1 below, 30 parts by weight of N-phenyl maleimide copolymer and styrene-acrylonitrile copolymer (SAN, 92HR of LG Chem) were used without using an alpha-methyl styrene copolymer. Then, it carried out similarly to Example 1, and manufactured the thermoplastic resin composition.

[ Comparative example  5]

As shown in Table 1 below, 25 parts by weight of ABS graft copolymer including butadiene-based rubbery copolymer, 15 parts by weight of N-phenyl maleimide copolymer and alpha without using the first copolymer and the second copolymer A thermoplastic resin composition was prepared in the same manner as in Example 1 except that 60 parts by weight of the methyl styrene copolymer was used.

[ Comparative example  6]

As shown in Table 1, a thermoplastic resin composition was prepared in the same manner as in Example 1 except that 40 parts by weight of the first copolymer was used and the second copolymer was not used.

division
(Unit: weight part) Example Comparative example One 2 3 One 2 3 4 5 6 First copolymer 25 20 25 10 - 25 25 - 40 Second copolymer 15 20 15 30 40 15 15 - - ABS graft - - - - - - - 25 - PMI ⁽¹⁾ 20 20 15 20 20 - 29.8 14.8 20 AMS ⁽²⁾ 39.8 39.8 44.8 39.8 39.8 59.8 - 60 39.8 SAN ⁽³⁾ - - - - - - 30 - - Silicone
Color Enhancer 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (1) PMI: N-phenyl maleimide copolymer
(2) AMS: alpha-methyl styrene copolymer
(3) SAN: styrene-acrylonitrile copolymer

[ Experimental Example ]

The thermoplastic resin compositions prepared in Examples and Comparative Examples were dried at 80 ° C. for 3 hours, and then injected under conditions of a molding temperature of 240 ° C. and a mold temperature of 40 ° C. to measure their respective physical properties in the following manner. Table 2 shows.

(1) impact strength test Izod impact strength )

Impact strength (IMP, 1/4 ”notched at 23 ° C., kg? Cm / cm) was tested according to ASTM D256.

(2) heat deflection temperature HDT )

It was measured according to ASTM D648.

(3) heat reliability

It was measured whether or not warping occurred by holding in a rotary oven for 95 hours at 95 ℃.

(4) coefficient of linear expansion CLTE )

It measured according to ASTM D696.

(5) Gray  scale

According to the ISO evaluation method 105, the weather resistance test was carried out using the weatherometer specified in the ISO evaluation method 105. The weather resistance test conditions were set at 0.56 W / m ² irradiance of the Xeno-arc beam required by the automotive industry, the black panel temperature was 89 ° C., and the irradiation humidity was 50%, and the specimens were irradiated for 2,000 hours. Was measured.

(6) glossiness

Measurement was made at 45 ° according to ASTM D2457.

(7) CIE  L

According to the CIE standard color observation method, the L value was measured by the SCI method.

division Example Comparative example One 2 3 One 2 3 4 5 6 Impact strength
(kgfcm / cm) 10.5 11.3 10.8 14.8 17.5 18.1 13.3 20.4 8.1 Heat deflection temperature
(℃) 99.5 99.1 97.8 99.8 99 95.1 100.2 100.5 100 Thermal Reliability OK OK OK OK OK NG NG OK OK Coefficient of linear expansion
(Μm / m / ℃) 80.1 80 81.8 80.5 82.1 88.5 86 83.1 80.8 Grayscale
(Rating) 4.5 4.5 4.5 4.5 4.5 4.5 4.5 2.5 4.5 Glossiness
(45 °) 13.7 15.7 14.3 18.6 21.7 13.8 18.5 17.5 14.2 CIE L ⁽¹⁾ 26.8 27.3 28 30.5 31.5 26.8 27.1 25.1 30.5 (1) Heat resistance reliability of oven stay after fastening to Stanchion made of Nylon + GF (Glass Fiber)

As shown in Table 2, it can be confirmed that the plastic molded article made of the thermoplastic resin composition of the present invention is excellent in the complexability and has an excellent blackness. On the other hand, in the case of Comparative Example 1 and Comparative Example 2, the CIE L value was found to exceed 30, through which it can be seen that the colorability is poor.

Since the thermoplastic resin composition of this invention has a low linear expansion coefficient, it can confirm that it is excellent in heat-strain deformation. On the other hand, in the case of Comparative Example 3 and Comparative Example 4, the coefficient of linear expansion was found to be high, through which it can be seen that it can not be used in combination with the nylon resin.

When using an ABS type graft copolymer like the comparative example 5, it can confirm that weather resistance falls remarkably. In addition, when the second copolymer is not used as in Comparative Example 6, it can be confirmed that the impact strength is not very good.

Claims (13)

25 to 70 parts by weight of two kinds of acrylate-styrene-acrylonitrile graft copolymers having different average particle diameters;
20 to 65 parts by weight of a heat resistant copolymer including an N-phenyl maleide copolymer and an alpha-methylene styrene copolymer; And
Thermoplastic resin composition comprising 0.1 to 5 parts by weight of the silicone-based color improving agent. The method of claim 1,
The acrylate-styrene-acrylonitrile graft copolymer is
A first copolymer having an average particle diameter of 500 to 2,000 mm 3; And
A thermoplastic resin composition comprising a second copolymer having an average particle diameter of 2,500 to 5,000 kPa. The method of claim 1,
The acrylate-styrene-acrylonitrile graft copolymer is
20 to 45 parts by weight of the first copolymer; And
5 to 25 parts by weight of the second copolymer thermoplastic resin composition. The method of claim 2, wherein the first copolymer,
10 to 70 parts by weight of an acrylic rubber polymer having an average particle diameter of 500 to 2,500 Pa;
10 to 60 parts by weight of styrene monomer; And
Thermoplastic resin composition which is a copolymer of acrylonitrile-based monomer 1 to 30 parts by weight. The method of claim 2, wherein the second copolymer,
10 to 70 parts by weight of an acrylic rubber polymer having an average particle diameter of 2,500 to 5,000 kPa;
10 to 60 parts by weight of styrene monomer; And
Thermoplastic resin composition which is a copolymer of acrylonitrile-based monomer 1 to 30 parts by weight. The method of claim 1,
The heat resistant copolymer comprises an N-phenyl maleide copolymer and an alpha-methylene styrene copolymer in a 1: 1 to 1: 4 weight ratio. The method of claim 1, wherein the N-phenyl maleide copolymer,
30 to 70 parts by weight of N-phenyl maleide monomer;
1 to 30 parts by weight of acrylonitrile monomers; And
A thermoplastic resin composition which is a copolymer of styrene monomer 25 to 60 parts by weight. The method of claim 7, wherein
N-phenyl maleide copolymer is a thermoplastic resin composition containing 1 to 5 parts by weight of maleic anhydride. The method of claim 1, wherein the alpha-methylene styrene-based copolymer,
50 to 80 parts by weight of alpha-methyl styrene monomer and
A thermoplastic resin composition which is a copolymer of acrylonitrile monomer 20 to 50 parts by weight. The method of claim 1,
The silicone-based color improving agent is at least one member selected from the group consisting of epoxy silicone-based color improving agent, carbonyl-silicon-based color improving agent, amino-silicone-based color improving agent, polyester-based color improving agent and fluoroalkyl silicone-based color improving agent. Acrylic copolymers having an average particle diameter of 200 to 2,000 kPa; Styrene monomers; And grafting the acrylonitrile-based monomer to prepare a first copolymer.
Acrylic copolymer with an average particle diameter of 2,500-5,000 kPa; Styrene monomers; And grafting the acrylonitrile-based monomer to prepare a second copolymer.
N-phenyl maleimide copolymer; And mixing the alpha-methylene styrene-based copolymer to prepare a heat resistant copolymer. And
20 to 45 parts by weight of the first copolymer; 5 to 25 parts by weight of the second copolymer; 20 to 65 parts by weight of the heat resistant copolymer; And preparing a resin composition by mixing 0.1 to 5 parts by weight of the silicone-based color improving agent. The method of claim 11,
Preparing a first copolymer; And the step of preparing the second copolymer, each independently, a styrene-based monomer and an acrylonitrile-based monomer continuously input to the acrylic rubber polymer polymer polymerization method for performing a polymerization reaction. The method of claim 11,
In the step of preparing a resin composition,
The first copolymer and the second copolymer are each independently a method for producing a thermoplastic resin having a pH of 8 to 11.