KR20040110322A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE: Provided is a thermoplastic resin composition, which has excellent heat resistance, surface gloss, weather resistance, discoloration resistance and impact strength as well as shows good appearance and post-processability such as heat fusion property. CONSTITUTION: The thermoplastic resin composition comprises: (a) 20-40 parts by weight of acrylate-styrene-acrylonitrile polymer comprising (i) 4-20 parts by weight of an acrylate-styrene-acrylonitrile resin containing small-diameter alkyl acrylate rubbery polymer having an average particle diameter of 500-2000 angstroms, and (ii) 10-32 parts by weight of acrylate-styrene-acrylonitrile polymer comprising (i) 4-20 parts by weight of an acrylate-styrene-acrylonitrile resin containing large-diameter alkyl acrylate rubbery polymer having an average particle diameter of 2500-5000 angstroms; (b) 40-80 parts by weight of a heat resistant copolymer comprising (i) 50-80 parts by weight of alpha-methylstyrene monomer, and (ii) 20-50 parts by weigh of acrylonitrile; and (c) 1-20 parts by weight of an acrylic polymer containing polybutadiene rubbery polymer having an average particle diameter of 2500-5000 angstroms, gel content of 60-95% and a swelling index of 12-40.

Description

Thermoplastic Resin Composition {THERMOPLASTIC RESIN COMPOSITION}

The present invention relates to a thermoplastic resin composition, and more particularly, a thermoplastic resin composition having not only excellent heat resistance, surface gloss, weathering discoloration, and impact strength, but also good appearance characteristics, and excellent post-processability, in particular heat sealing property. It is about.

The acrylate-styrene-acrylonitrile (ASA) -based thermoplastic resin has excellent weather resistance, chemical resistance, and thermal stability, and is widely used in outdoor electrical and electronic parts, construction materials, and sporting goods. . In recent years, it is also used in a side mirror housing or a large air conditioner outdoor unit housing in the automotive field that requires lightweight. However, to be used in exterior materials in these automotive fields, they must be excellent in heat resistance, surface gloss, and weathering discoloration.

As a method of imparting heat resistance to the acrylate-styrene-acrylonitrile resin, a method of preparing a heat resistant acrylate-styrene-acrylonitrile resin by kneading a heat resistant copolymer to an acrylate-styrene-acrylonitrile polymer is used. have.

Japanese Laid-Open Patent Publication No. 2001-253990, Japanese Laid-Open Patent Publication No. 2001-2881, and Japanese Laid-Open Patent Publication No. 2001-253990 are kneaded as a method for producing the above heat resistant acrylate-styrene-acrylonitrile resin. Disclosed is a method for producing a part or all of the styrene used in the production of a heat resistant copolymer for containing a good heat resistance α-methylstyrene or maleimide compound, Japanese Patent Laid-Open No. 2002-96394 is filled with inorganic Japanese Patent Laid-Open No. 2001-207000 discloses a method of kneading with a polycarbonate resin. However, the above-described prior arts have a problem in that weathering resistance or low temperature impact resistance is low, and surface gloss is lowered according to the addition of additives, and the price and processability are bad.

In addition, in order to be applied to automobile parts, etc., it is necessary to have excellent post-processing properties such as heat fusion, and accordingly, there is a demand for acrylate-styrene-acrylonitrile resin having good post-processing property, particularly heat fusion property, and excellent heat resistance and color change resistance. Is rising.

In accordance with such a requirement, US Pat. No. 3,944,631 discloses a process for adding PMMA resin, an acrylic polymer, to an acrylate-styrene-acrylonitrile polymer via multistage polymerization. However, this polymer has the disadvantage of being easily broken due to the low impact strength of PMMA. In order to compensate for this, U.S. Patent No. 4,731,414 discloses a method of using an impact modifier, but this also has a problem in that impact strength is lowered and product surface gloss is relatively lowered.

Therefore, there is a need for further studies on thermoplastic resin compositions having excellent heat resistance, surface gloss, weathering discoloration, impact strength, and post-processing properties.

In order to solve the problems of the prior art as described above, the present invention is not only excellent in heat resistance, surface gloss, weathering discoloration, and impact strength, but also good appearance characteristics, excellent post-processability, particularly heat-sealing properties The purpose is to provide.

In order to achieve the above object, the present invention is a thermoplastic resin composition,

a) i) Small-diameter alkyl acrylates having an average particle diameter of 500 to 2,000 kPa

Acrylate-styrene-acrylonitrile containing rubber polymer

4 to 20 parts by weight of the resin; And

Ii) Large-diameter alkyl acrylates with an average particle diameter of 2,500 to 5,000 mm 3

Styrene-acrylonitrile containing crumb rubber polymer

10 to 32 parts by weight of reel resin

Acrylate-styrene-acrylonitrile polymer 20 to include

40 parts by weight;

b) iv) 50 to 80 parts by weight of α-methylstyrene (AMS) monomer; And

Ii) 20 to 50 parts by weight of acrylonitrile (AN) monomer

40 to 80 parts by weight of a heat resistant copolymer comprising a; And

c) Paul with an average particle diameter of 2500 to 5000 Å, gel content of 60 to 95% and swelling index of 12 to 40

Of acrylic polymers 1 to 20 containing ributadiene rubber polymer

Part

It provides a thermoplastic resin composition comprising a.

Hereinafter, the present invention will be described in detail.

The inventors of the present invention, while studying a thermoplastic resin composition having excellent heat resistance, surface gloss, weathering discoloration, impact strength, and post-processing properties, and acrylate-styrene-acrylonitrile resin containing a small diameter alkyl acrylate rubber polymer and a large diameter A thermoplastic resin was prepared by adding a heat-resistant copolymer and an acrylic polymer to an acrylate-styrene-acrylonitrile polymer containing an acrylate-styrene-acrylonitrile resin containing an alkyl acrylate rubber polymer, resulting in heat resistance and surface gloss. In addition, the weather discoloration, and excellent impact strength, as well as at the same time good appearance characteristics, it was confirmed that the post-processability, in particular heat fusion properties significantly improved, based on this, to complete the present invention.

The thermoplastic resin composition of the present invention comprises an acrylate-styrene-acrylonitrile resin containing a small diameter alkyl acrylate rubber polymer having an average particle diameter of 500 to 2,000 mm 3 and a large diameter alkyl acrylate rubber polymer having an average particle diameter of 2,500 to 5,000 mm 3 Heat-resistant air containing 20 to 40 parts by weight of an acrylate-styrene-acrylonitrile polymer containing an acrylate-styrene-acrylonitrile resin, an α-methylstyrene (AMS) monomer and an acrylonitrile (AN) monomer. It is characterized in that it comprises 1 to 20 parts by weight of an acrylic polymer containing 40 to 80 parts by weight of a copolymer, and an average particle diameter of 2500 to 5000 mm 3, a gel content of 60 to 95%, and a polybutadiene rubber polymer having a swelling index of 12 to 40.

The thermoplastic resin composition of the present invention can be produced by the following method.

a) acrylate-styrene-acrylonitrile copolymer preparation

Iii) ASA resin containing small diameter alkyl acrylate rubber polymer

(Manufacture of small diameter alkyl acrylate rubber polymer)

The small diameter alkyl acrylate rubber polymer of this step is prepared by emulsion polymerization of an alkyl acrylate monomer.

Specifically, the small diameter alkyl acrylate rubber polymer is a) 5 to 50 parts by weight of the alkyl acrylate monomer, b) 1 to 4 parts by weight of the emulsifier, c) 0.05 to 0.2 parts by weight of the initiator, d ) 0.01 to 0.07 parts by weight of the grafting agent, ㅁ) 0.05 to 0.3 parts by weight of the crosslinking agent, and iii) 0.05 to 0.4 parts by weight of the electrolyte material.

As the alkyl acrylate monomer of a), butyl acrylate or ethyl hexyl acrylate may be used, and preferably butyl acrylate is used.

The alkyl acrylate monomer is preferably included 5 to 50 parts by weight based on 100 parts by weight of the total monomer.

The emulsifier of b) may be a derivative of an alkyl sulfur succinate metal salt having 12 to 18 carbon atoms having a pH of 3 to 9, or an alkyl sulfate ester or sulfonic acid metal salt having 12 to 20 carbon atoms. Examples thereof include alkyl sulfur succinate metal salt derivatives having 12 to 18 carbon atoms such as sodium salt, potassium salt, or lithium salt of dicyclohexyl sulfur succinate, dihexyl sulfur succinate, di 2-ethyl hexyl sulfur succinate; Or sulfuric acid having 12 to 20 carbon atoms, an alkyl sulfate metal salt such as sodium lauric sulfate, sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleate sulfate, potassium dodecyl sulfate, or potassium octadecyl sulfate Esters or sulfonic acid metal salts. In particular, it is preferable to use the sodium salt of di 2-ethylhexyl sulfur succinate.

The emulsifier is preferably included 1 to 4 parts by weight, more preferably 1.5 to 3 parts by weight based on 100 parts by weight of the total monomer.

The initiator of c) may use an inorganic or organic peroxide compound, and examples thereof include water-soluble initiators such as potassium persulfate, sodium persulfate, or ammonium persulfate, or oil-soluble initiators such as cumene hydroperoxide or benzoyl peroxide. There is this.

The initiator is preferably included in 0.05 to 0.2 parts by weight based on 100 parts by weight of the total monomer.

The grafting agent of d) may be aryl methacrylate (AMA), triaryl isocyanurate (TAIC), triaryl amine (TAA), or diaryl amine (DAA).

The grafting agent is preferably included in 0.01 to 0.07 parts by weight based on 100 parts by weight of the total monomer.

The cross-linking agent of ㅁ) ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, Neopentyl glycol dimethacrylate, trimethylol propane trimethacrylate, trimethylol methane triacrylate, or the like can be used.

The crosslinking agent is preferably included in 0.05 to 0.3 parts by weight based on 100 parts by weight of the total monomer.

As the electrolyte material of _iii) , NaHCO ₃ , Na ₂ S ₂ O _7, or K ₂ CO ₃ may be used, and preferably NaHCO ₃ is used.

The electrolyte material is preferably contained in 0.05 to 0.4 parts by weight based on 100 parts by weight of the total monomer.

In the preparation of the small-diameter alkyl acrylate rubber polymer of this step, the monomer is preferably administered continuously, or a mixture of continuous administration and batch administration is preferably added.

The small diameter alkyl acrylate rubber polymer prepared as described above is preferably pH 5-9, more preferably pH 6-8. In addition, the particle size (measured using Nicomp 370 HPL by the Dynamic Laser Light Scattering method) of the small-diameter alkyl acrylate rubber polymer is preferably 500 to 2,000 mm 3, more preferably 700 to That's 1,500 km3.

(Manufacture of ASA resin containing small diameter alkyl acrylate rubber polymer)

The ASA resin of this step is prepared by graft polymerization of an aromatic vinyl compound and a vinyl cyan compound on the small-diameter alkyl acrylate rubber polymer prepared above.

Specifically, the ASA resin in the prepared small-diameter alkyl acrylate rubber polymer is a) 10 to 50 parts by weight of aromatic vinyl compound, b) 1 to 20 parts by weight of vinyl cyan compound, c) 1 to 2 parts by weight of an emulsifier, d) 0.05 to 0.3 parts by weight of a polymerization initiator, and ㅁ) up to 0.2 parts by weight of a molecular weight regulator can be prepared by polymerization.

As the aromatic vinyl compound of a), styrene, alpha methyl styrene, para methyl styrene, or the like may be used as the styrene monomer derivative.

The aromatic vinyl compound is preferably included in 10 to 50 parts by weight based on 100 parts by weight of the total resin composition.

The vinyl cyan compound of b) preferably uses acrylonitrile, and the content thereof is preferably included in an amount of 1 to 20 parts by weight based on 100 parts by weight of the total resin composition.

The emulsifier of c) may be a derivative of a carboxylic acid metal salt such as fatty acid metal salt of 12 to 20 carbon atoms having 9 to 13 carbon atoms, or rosin acid metal salt of 12 to 20 carbon atoms. Specifically, there are fatty acid metal salts such as sodium thiarate, lauryl acid, sodium or potassium of oleic acid, or metal rosin salts such as sodium rosin and potassium rosin.

The emulsifier is preferably contained in 1 to 2 parts by weight based on 100 parts by weight of the total resin composition.

The polymerization initiator of d) may be a water-soluble initiator such as potassium persulfate, sodium persulfate, or ammonium persulfate, or an oil-soluble initiator such as cumene hydroperoxide or benzoyl peroxide.

The polymerization initiator is preferably contained in 0.05 to 0.3 parts by weight based on 100 parts by weight of the total resin composition.

The molecular weight regulator of ㅁ) is preferably used tertiary dodecyl mercaptan, the content is preferably included in a maximum of 0.2 parts by weight. If the content exceeds 0.2 parts by weight, there is a problem that the rate of decrease of the impact strength increases.

In the case of batch administration of the entire amount of the mixed monomer including the emulsifier in the preparation of the ASA resin in this step, it is difficult to grafting by temporarily raising the pH of the polymerization system, and because the stability of the particles is reduced, the internal structure of the particles is not uniform. It is preferable that the mixed monomer containing an emulsifier is added by a continuous dosing method during the reaction.

The ASA resin containing the small diameter alkyl acrylate rubber polymer prepared as described above is preferably pH 8-11, more preferably pH 9-10.5.

The small diameter alkyl acrylate rubber polymer is preferably included in an amount of 4 to 20 parts by weight based on 100 parts by weight of the total acrylate-styrene-acrylonitrile polymer. If the content is less than 4 parts by weight, there is a problem that the colorability is lowered, and if it exceeds 20 parts by weight, there is a problem that the impact strength is lowered.

Ii) Preparation of ASA Resin Containing Large Diameter Alkyl Acrylate Rubber Polymers

(Manufacture of large diameter alkyl acrylate rubber polymer)

The large diameter alkyl acrylate rubber polymer of this step is prepared by emulsion polymerization of an alkyl acrylate monomer.

Specifically, the large-diameter alkyl acrylate rubber polymer is a) 10 to 60 parts by weight of the alkyl acrylate monomer, b) 0.1 to 1.0 parts by weight of the emulsifier, c) 0.05 to 0.2 parts by weight of the initiator, d) 0.01 to 0.07 parts by weight of the grafting agent, k) 0.05 to 0.3 parts by weight of the crosslinking agent, and iii) 0.05 to 0.4 parts by weight of the electrolyte material.

As the alkyl acrylate monomer of a), butyl acrylate or ethyl hexyl acrylate may be used, and preferably butyl acrylate is used.

The alkyl acrylate monomer is preferably included in 10 to 60 parts by weight based on 100 parts by weight of the total monomer.

The emulsifier of b) may use the same materials as those used in the preparation of the small diameter alkyl acrylate rubber polymer. The emulsifier is preferably included 0.1 to 1.0 parts by weight based on 100 parts by weight of the total monomer.

In addition, the polymerization initiator, the grafting agent, the crosslinking agent, and the electrolyte material used in the preparation of the large-diameter alkyl acrylate rubber polymer may use the same materials as those used in the preparation of the small-diameter alkyl acrylate rubber polymer.

The large-diameter alkyl acrylate rubber polymer prepared as described above is preferably pH 5-9, more preferably pH 6-8. In addition, the particle size of the large-diameter alkyl acrylate rubber polymer is preferably 2,500 to 5,000 mm 3, more preferably 3,000 to 4,500 mm 3.

(Manufacture of ASA resin containing large diameter alkyl acrylate rubber polymer)

The ASA resin of this step is prepared by graft polymerization of an aromatic vinyl compound and a vinyl cyan compound on the prepared large diameter alkyl acrylate rubber polymer.

Specifically, the ASA resin in the prepared large-diameter alkyl acrylate rubber polymer is a) 10 to 40 parts by weight of aromatic vinyl compound, b) 1 to 20 parts by weight of vinyl cyan compound, c) emulsifier based on 100 parts by weight of the total resin composition. 0.1 to 2.0 parts by weight, d) 0.05 to 0.3 parts by weight of the polymerization initiator, and ㅁ) a maximum of 0.2 parts by weight of the molecular weight regulator can be prepared by polymerization.

As the aromatic vinyl compound of a), styrene, alpha methyl styrene, para methyl styrene, or the like may be used as the styrene monomer derivative.

The aromatic vinyl compound is preferably included in 10 to 40 parts by weight based on 100 parts by weight of the total resin composition.

The vinyl cyan compound of b) preferably uses acrylonitrile, and the content thereof is preferably included in an amount of 1 to 20 parts by weight based on 100 parts by weight of the total resin composition.

In addition, emulsifiers, polymerization initiators, grafting agents, crosslinking agents, and electrolyte materials used in the preparation of ASA resins containing large diameter alkyl acrylate rubber polymers are those used in the preparation of ASA resins containing the small diameter alkyl acrylate rubber polymers. The same material as can be used.

The large-diameter alkyl acrylate rubber polymer is preferably included in 10 to 32 parts by weight based on 100 parts by weight of the total acrylate-styrene-acrylonitrile polymer. If the content is less than 10 parts by weight, there is a problem that the impact strength is lowered.

In particular, the ASA resin containing the small diameter alkyl acrylate copolymer prepared as described above and the ASA resin containing the large diameter alkyl acrylate copolymer are preferably mixed in a ratio of 1: 1 to 1: 4. If the mixing ratio is out of the range, the impact strength is significantly lowered, there is a problem that the coloring and gloss is lowered.

After mixing and stirring the ASA resin containing the small-diameter alkyl acrylate copolymer and the ASA resin containing the large-diameter alkyl acrylate copolymer in a ratio as described above, it was subjected to atmospheric condensation at 85 ° C. using an aqueous calcium chloride solution, 95 Aged at 占 폚, dehydrated, washed, and then dried for 30 minutes by hot air at 90 占 폚 to obtain final acrylate-styrene-acrylonitrile polymer powder particles.

The acrylate-styrene-acrylonitrile polymer prepared as described above is preferably included in an amount of 20 to 40 parts by weight based on 100 parts by weight of the total thermoplastic resin composition. If the content is less than 20 parts by weight, there is a problem that the impact strength is lowered, if it exceeds 40 parts by weight there is a problem that the gloss is worse, the colorability is lowered.

b) heat resistant copolymer

The heat resistant copolymer of this step is prepared by polymerizing 50 to 80 parts by weight of α-methylstyrene (AMS) monomer and 20 to 50 parts by weight of acrylonitrile (AN) monomer.

The heat-resistant copolymer is 50 to 80 parts by weight of α-methylstyrene (AMS) monomer, 20 to 50 parts by weight of acrylonitrile (AN) monomer, up to 10 parts by weight of styrene monomer, and up to 10 parts of acrylic monomer based on 100 parts by weight of monomer. It is prepared by copolymerizing parts by weight, 26 to 30 parts by weight of solvent, and 0.1 to 1.0 parts by weight of molecular weight modifier.

The solvent is preferably toluene, and the molecular weight regulator is preferably di-t-dodecyl mercaptan.

The polymerization is preferably carried out by bulk polymerization, the reaction time is preferably 2 to 4 hours, the reaction temperature is 140 ~ 170 ℃.

The heat-resistant copolymer manufacturing process is a continuous process consisting of a raw material input pump, a continuous stirring tank, a preheating tank and a volatilization tank, a polymer transfer pump, and an extrusion process.

The molecular chain structure distribution of the heat resistant copolymer prepared in this step is analyzed using a ¹³ C NMR analyzer. At this time, the analytical method was dissolved in deuterated chloroform and measured using tetramethylsilane as an internal standard, the peak appearing in the range of 141 ~ 144 ppm of the measured 140 ~ 150 ppm peak {AMS-AN-AN } In the chain structure, the peaks in the range of 144.5 to 147 ppm are taken as the {AMS-AMS-AN} chain structure, and the peaks in the range of 147.5 to 150 ppm are taken as the {AMS-AMS-AMS} chain structure, respectively. Measure the area of the peaks.

In the present invention, it is preferable that the [AMS-AMS-AMS] chain structure in the molecular chain structure of the copolymer is at most 14%, and the [AMS-AN-AN] chain structure is at most 39%. If the [AMS-AMS-AMS] chain structure exceeds 14% of the molecular chain structure of the copolymer, there is a problem that thermal stability is lowered due to thermal decomposition of the [AMS-AMS-AMS] chain structure during processing. -AN-AN] If the chain structure exceeds 39% there is a problem that the heat resistance is not good.

The heat resistant copolymer is preferably included in 40 to 80 parts by weight, more preferably 50 to 70 parts by weight based on 100 parts by weight of the total thermoplastic resin composition. If the content is less than 40 parts by weight, there is a problem that the heat resistance of the resin is lowered, and if it exceeds 80 parts by weight, there is a problem that the impact strength is significantly reduced.

c) acrylic polymer preparation

(Polybutadiene rubber polymer production)

The polybutadiene rubber polymer of this step is iii) 100 parts by weight of 1,3-butadiene, ii) 1 to 4 parts by weight of emulsifier, iii) 0.2 to 1.5 parts by weight of polymerization initiator, iii) 0.5 parts by weight of electrolyte, iv) molecular weight regulator 0.1 To 0.5 parts by weight, and iii) 75 parts by weight of ion-exchanged water in a batch to react at 65 to 85 ° C. for 25 to 50 hours to prepare a polybutadiene rubber latex.

The emulsifier of ii) may be alkyl aryl sulfonate, alkali methyl alkyl sulfate, sulfonated alkyl ester, fatty acid soap, or rosin acid alkali salt. The said emulsifier can be used individually or in mixture of 2 or more types.

The polymerization initiator of (i) may be a water-soluble persulfate, a peroxy compound, an oxidation-reduction system, or a fat-soluble polymerization initiator. Examples of the water-soluble persulfate include sodium persulfate or potassium persulfate, and the fat-soluble polymerization initiators include cumene hydroperoxide, diisopropyl benzenehydroperoxide, azobis isobutylnitrile and tertiary butyl hydroperoxide. , Paramethane hydroperoxide, or benzoyl peroxide.

The electrolyte of vi) KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ HPO ₄ , or Na ₂ HPO ₄ and the like can be used.

It is preferable to use mercaptans as a molecular weight modifier of said i).

In the preparation of the polybutadiene rubber polymer, the polymerization temperature is very important for adjusting the gel content and swelling index of the rubber latex, and is preferably performed at 65 to 85 ° C. In addition, the selection of a polymerization initiator should also be considered when adjusting the gel content and swelling index of the polybutadiene rubber polymer.

The polybutadiene rubber polymer prepared as described above has an average particle diameter of 2500 to 5000 mm 3, a gel content of 60 to 95%, and a swelling index of 12 to 40.

(Acrylic polymer production)

The acrylic polymer of this step is 8 to 25 parts by weight of the polybutadiene rubber latex prepared above, ii) 40 to 70 parts by weight of the alkyl methacrylate compound or acrylic acid alkyl ester compound, i) 15 to 30 parts by weight of the aromatic vinyl compound Iii) 1 to 20 parts by weight of a vinyl cyan compound, iii) 0.2 to 0.6 parts by weight of an emulsifier, iii) 0.2 to 0.6 parts by weight of a molecular weight modifier, and iii) 0.05 to 0.3 parts by weight of a polymerization initiator at 4 to 80 ° C. Prepared by graft copolymerization for 7 hours.

As the aromatic vinyl compound of iii), styrene, α-methylstyrene, or ρ-methylstyrene may be used as the styrene derivative, and in particular, styrene is preferably used.

It is preferable that acrylonitrile is used for the vinyl cyan compound of said (i).

The emulsifier of i) may be alkylaryl sulfonate, alkali methylalkyl sulfate, sulfonated alkyl ester, fatty acid soap, alkali rosin salt or the like. The said emulsifier can be used individually or in mixture of 2 or more types.

It is preferable to use the tertiary dodecyl mercaptan for the molecular weight modifier of said i).

The polymerization initiator of iii) may be a peroxide such as cumene hydroperoxide, diisopropylbenzenehydroperoxide, or peranthate; An oxidation-reduction catalyst system mixed with a reducing agent such as sodium formaldehyde succilate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, or sodium sulfite can be used.

The polymerization conversion rate of the latex obtained by polymerizing the above components is 98% or more, and an antioxidant and a stabilizer are administered to the latex to agglomerate with calcium chloride aqueous solution at a temperature of 80 ° C. or higher, and then dehydrated and dried to give final acrylic polymer powder particles. Can be obtained.

The acrylic polymer is preferably included in 1 to 20 parts by weight based on 100 parts by weight of the total thermoplastic resin composition. If the content is less than 1 part by weight, there is a problem that gloss is lowered, and if it exceeds 20 parts by weight, there is a problem that the impact strength is significantly reduced.

The thermoplastic resin composition of the present invention is an acrylate-styrene-acrylonitrile resin containing a small diameter alkyl acrylate rubber polymer prepared as described above and an acrylate-styrene-acrylonitrile resin containing a large diameter alkyl acrylate rubber polymer. It is prepared by mixing an acrylate-styrene-acrylonitrile polymer, a heat resistant copolymer, and an acrylic polymer comprising a.

In addition, the thermoplastic resin composition of the present invention may further include a lubricant and an antioxidant as necessary.

The lubricant may use ethylene bis stearamide, oxidized polyethylene wax, magnesium stearate, mixtures thereof, and the like.

The lubricant is preferably included in an amount of 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the thermoplastic resin composition.

The thermoplastic resin of the present invention prepared as described above has the advantage of not only excellent heat resistance, surface gloss, weathering discoloration, and impact strength, but also good appearance characteristics and remarkable improvement in post-processing properties, particularly heat fusion.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Example 1

(Graft ASA copolymer)

① Preparation of ASA resin containing small diameter alkyl acrylate rubber polymer

Manufacture of Small Diameter Alkyl Acrylate Rubber Polymers

70 parts by weight of distilled water, 10 parts by weight of butyl acrylate, 1.5 parts by weight of di 2-ethylhexyl sulfur succinate sodium salt, 0.02 parts by weight of ethylene glycol dimethacrylate, 0.1 parts by weight of sodium bicarbonate, and 0.04 parts by weight of potassium persulfate. Into a reactor of 10 L, the temperature was raised to 70 ℃, and reacted for 1 hour to prepare a seed. Here, a mixture of 34 parts by weight of distilled water, 0.5 parts by weight of di 2-ethylhexyl sulfur succinate, 30 parts by weight of butyl acrylate, and 0.1 parts by weight of sodium bicarbonate and 0.06 parts by weight of catalyst potassium persulfate were mixed at 70 ° C. for 3 hours. The polymerization was carried out while continuously administered to prepare a small diameter alkyl acrylate rubber polymer having an average particle diameter of 800 to 1,000 mm 3.

Preparation of ASA Resin Containing Small Diameter Alkyl Acrylate Rubber Polymer

63 parts by weight of distilled water, 1.4 parts by weight of potassium rosinate, 0.042 parts by weight of potassium hydroxide (KOH), 40 parts by weight of styrene (ST), and 20 parts of acrylonitrile (AN) in the prepared small diameter alkyl acrylate rubber polymer. Part, and a mixture of 0.05 parts by weight of tertiary dodecyl mercaptan (TDDM) and 0.1 parts by weight of potassium persulfate (KPS), which is a catalyst, were respectively polymerized with continuous administration at 70 ° C. for 5 hours to increase the polymerization conversion rate. After further reacting at 80 ° C. for 1 hour, the reaction mixture was cooled to 60 ° C.

The particle size of the small diameter alkyl acrylate rubber polymer-containing ASA resin prepared as described above was 1200 GPa, the polymerization conversion rate was 98%, the pH was 9.5, and the graft rate was 40%.

② Preparation of ASA resin containing large diameter alkyl acrylate rubber polymer

Manufacture of large diameter alkyl acrylate rubber polymers

70 parts by weight of distilled water, 5 parts by weight of butyl acrylate, 0.015 parts by weight of di 2-ethylhexyl sulfur succinate sodium salt, 0.02 parts by weight of ethylene glycol dimethacrylate, 0.1 parts by weight of sodium bicarbonate, and 0.04 parts by weight of potassium persulfate Into a reactor of 10 L, the temperature was raised to 70 ℃, and reacted for 1 hour to prepare a seed. Here, a mixture of 34 parts by weight of distilled water, 0.285 parts by weight of di 2-ethylhexyl sulfur succinate sodium salt, 45 parts by weight of butyl acrylate, and 0.1 parts by weight of sodium bicarbonate and 0.06 parts by weight of potassium persulfate as a catalyst were mixed at 70 ° C. Polymerization was carried out with continuous administration for 3 hours to prepare a large diameter alkyl acrylate rubber polymer having an average particle diameter of 3,000 to 4,000 mm 3.

Manufacture of large diameter alkyl acrylate rubber polymer-containing ASA resin

63 parts by weight of distilled water, 1.4 parts by weight of potassium rosinate, 0.042 parts by weight of potassium hydroxide (KOH), 35 parts by weight of styrene (ST), and 15 parts by weight of acrylonitrile (AN) in the prepared large diameter alkyl acrylate rubber polymer. , And a mixture of 0.05 parts by weight of tertiary dodecyl mercaptan (TDDM) and 0.1 parts by weight of a catalyst, potassium persulfate (KPS), were polymerized with continuous dosing at 70 ° C. for 5 hours, and then 80 ° C. to increase the polymerization conversion rate. After further reacting for 1 hour at, it was cooled to 60 ° C.

The particle size of the large-diameter alkyl acrylate rubber polymer-containing ASA resin prepared as described above was 4,500 mm 3, the polymerization conversion rate was 99%, the pH was 9.5, and the graft rate was 45%.

The acrylate-styrene-acrylonitrile resin containing the small diameter alkyl acrylate rubber polymer prepared as described above and the acrylate-styrene-acrylonitrile resin containing the large diameter alkyl acrylate rubber polymer are 1: 3 mixing ratio. After mixing and stirring in a latex state, the mixture was subjected to atmospheric condensation at 85 ° C. using an aqueous calcium chloride solution, aged at 95 ° C., dehydrated and washed, and dried for 30 minutes by hot air at 90 ° C. to obtain final acrylate-. Styrene-acrylonitrile powder particles were obtained.

(Heat-resistant copolymer production)

70 parts by weight of α-methylstyrene, 30 parts by weight of acrylonitrile, 30 parts by weight of toluene as a solvent, and 0.15 parts by weight of di-t-dodecylmercaptan with a molecular weight regulator were added to the reactor so that the average reaction time was 3 hours. The reaction temperature was maintained at 148 ° C. during continuous administration. The polymerization liquid discharged from the reaction tank is heated in a preheating tank, the unreacted monomer is volatilized in a volatilization tank, and the temperature of the polymer is maintained at 210 ° C. Processed in pellet form.

(Acrylic copolymer production)

In a nitrogen-substituted polymerization reactor (autoclave), 80 parts by weight of ion-exchanged water, 100 parts by weight of 1,3-butadiene, 1.2 parts by weight of potassium rosin salt as emulsifier, 1.5 parts by weight of potassium oleate salt, sodium carbonate (Na ₂ CO) as an electrolyte ₃ ) 0.7 parts by weight, 0.8 parts by weight of potassium hydrogen carbonate (KHCO ₃ ), and 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) were used as a molecular weight regulator, and the reaction temperature was raised to 65 ° C. Then, 0.3 parts by weight of potassium persulfate was added as a polymerization initiator to initiate the reaction, and the reaction temperature was continuously raised to 85 ° C. for 35 hours, and then the reaction was terminated to prepare a polybutadiene rubber polymer.

10 parts by weight of polybutadiene rubber latex prepared above, 90 parts by weight of ion-exchanged water, 0.2 parts by weight of sodium oleate emulsifier, 14.38 parts by weight of methyl methacrylate, 5.62 parts by weight of styrene, 2.5 parts by weight of acrylonitrile. Parts, 0.2 parts by weight of tertiary dodecyl mercaptan, 0.048 parts by weight of sodium pyrophosphate, 0.012 parts by weight of dextrose, 0.001 parts by weight of ferrous sulfide, and 0.04 parts by weight of cumene hydroperoxide at 50 ° C. The reaction was carried out while the temperature was raised to 73 ° C. over 2 hours. Here, 70 parts by weight of ion-exchanged water, 0.4 parts by weight of sodium oleate, 43.12 parts by weight of methyl methacrylate, 16.88 parts by weight of styrene, 7.5 parts by weight of acrylonitrile, 0.25 parts by weight of tertiary dodecyl mercaptan, and 0.048 parts by weight of sodium pyrophosphate , 0.012 parts by weight of dextrose, 0.001 parts by weight of ferrous sulfide, and 0.1 parts by weight of cumene hydroperoxide were continuously administered for 4 hours, and then heated to 76 ° C. again, and aged for 1 hour. Finished. At this time, the polymerization conversion rate was 99.5% and solid coagulation content was 0.1%. The acrylic copolymer prepared above was coagulated with an aqueous calcium chloride solution and washed to obtain a rubber-containing acrylic polymer powder.

(Thermoplastic resin manufacture)

20 parts by weight of the acrylate-styrene-acrylonitrile copolymer prepared as described above, 70 parts by weight of the heat resistant copolymer, 10 parts by weight of the acrylic copolymer, 1 part by weight of EBA (ethylene bis stearamide) as a lubricant, and 0.3 antioxidants The pellets were prepared by mixing the parts by weight at 230 ° C. using a twin screw extruder.

Example 2

A pellet was prepared in the same manner as in Example 1, except that 25 parts by weight of the acrylate-styrene-acrylonitrile copolymer and 5 parts by weight of the acrylic copolymer were used.

Example 3

Except that 30 parts by weight of the acrylate-styrene-acrylonitrile copolymer, and 60 parts by weight of the heat resistant copolymer in Example 1 was carried out in the same manner as in Example 1 to prepare a pellet.

Example 4

A pellet was manufactured in the same manner as in Example 1, except that 50 parts by weight of the heat resistant copolymer, 20 parts by weight of the acrylic copolymer, and 1 part by weight of polyethylene wax were used as the lubricant.

Comparative Example 1

30 parts by weight of the acrylate-styrene-acrylonitrile copolymer prepared in Example 1, 70 parts by weight of the heat resistant copolymer prepared in Example 1, 1 part by weight of EBA (ethylene bis stearamide) as a lubricant, and oxidation 0.3 parts by weight of the inhibitor was mixed to prepare pellets using a twin screw extruder at 230 ° C.

Comparative Example 2

20 parts by weight of the acrylate-styrene-acrylonitrile copolymer prepared in Example 1, 70 parts by weight of the heat resistant copolymer prepared in Example 1, 10 parts by weight of the acrylic copolymer (PMMA resin, LG MMA IH830), 1 part by weight of EBA (ethylene bis stearamide) and 0.3 part by weight of antioxidant were mixed with a lubricant to prepare pellets at 230 ° C. using a twin screw extruder.

The pellets prepared in Examples 1 to 4 and Comparative Examples 1 or 2 were again injected to measure impact strength, tensile strength, fluidity, heat deformation temperature, glossiness, and heat fusion strength by the following method. It is shown in Table 1 below.

A) impact strength-measured by ASTM D256.

B) Tensile strength-measured by ASTM D638.

C) Flowability-measured by ASTM D1238.

D) Heat Deflection Temperature (HDT)-measured by ASTM D648.

ㅁ) glossiness-measured by ASTM D523.

Iii) Thermal welding strength-After the injection specimen was melted for 60 seconds at 320 ℃ for 5 seconds, the weld strength between the resin and the metal surface was evaluated. That is, the thermal fusion property was evaluated by the length and the generation | strength degree of the strand which generate | occur | produce after resin contacts a metal surface. At this time, if the length of the strand is long and occurs a lot under the same heat fusion conditions, the heat fusion strength is lowered. Here, the thermal fusion strength was classified into three stages, and judged as A, B, and C. A good case, A bad case and C medium were B, and thermal fusion was evaluated by relative visual judgment.

division Example Comparative example One 2 3 4 One 2 Impact strength 16.0 15.4 16.5 16.2 16.3 14.5 Tensile Strength (㎏ / ㎠) 520 550 470 490 490 570 Fluidity (g / 10min) 8.6 7.8 6.7 7.3 7.5 7.7 Heat Deflection Temperature (1/4 ", ℃) 99.5 99.2 97.6 95.3 99.9 98.9 Glossiness 92 90 93 95 83 88 Heat Fusion Strength A A A A C B

Through Table 1, it can be seen that the thermoplastic resin composition of Examples 1 to 4 according to the present invention improves the surface gloss of the product without deteriorating heat resistance compared to Comparative Examples 1 and 2, and excellent heat fusion strength, heat The fusion strength was found to be a measure of post-processability, in particular heat fusion, and thus it was confirmed that heat fusion was excellent.

The thermoplastic resin composition according to the present invention is not only excellent in heat resistance, surface gloss, weathering discoloration, and impact strength, but also good in appearance characteristics, and excellent in post-processing property, particularly heat fusion property.

Claims (14)

In the thermoplastic resin composition, a) i) Small-diameter alkyl acrylates having an average particle diameter of 500 to 2,000 kPa Acrylate-styrene-acrylonitrile containing rubber polymer 4 to 20 parts by weight of the resin; And Ii) Large-diameter alkyl acrylates with an average particle diameter of 2,500 to 5,000 mm 3 Styrene-acrylonitrile containing crumb rubber polymer 10 to 32 parts by weight of reel resin Acrylate-styrene-acrylonitrile polymer 20 to include 40 parts by weight; b) iv) 50 to 80 parts by weight of α-methylstyrene (AMS) monomer; And Ii) 20 to 50 parts by weight of acrylonitrile (AN) monomer 40 to 80 parts by weight of a heat resistant copolymer comprising a; And c) Paul with an average particle diameter of 2500 to 5000 Å, gel content of 60 to 95% and swelling index of 12 to 40 Of acrylic polymers 1 to 20 containing ributadiene rubber polymer Part Thermoplastic resin composition comprising a. The method of claim 1, A thermoplastic resin composition prepared by polymerizing 5-50 parts by weight of an alkyl acrylate monomer with respect to 100 parts by weight of the total monomer of a) i) the small diameter alkyl acrylate rubber polymer. The method of claim 2, The alkyl acrylate monomer is at least one member selected from the group consisting of butyl acrylate and ethyl hexyl acrylate. The method of claim 1, 10 to 50 parts by weight of the acrylate-styrene-acrylonitrile resin containing the small-diameter alkyl acrylate rubber polymer of a) iii) to 100 parts by weight of the total resin composition in the small-diameter alkyl acrylate rubber polymer , And a thermoplastic resin composition prepared by polymerizing 1 to 20 parts by weight of a vinyl cyan compound. The method of claim 4, wherein The thermoplastic resin composition in which the said aromatic vinyl compound is selected from the group which consists of styrene, alpha methyl styrene, and para methyl styrene. The method of claim 4, wherein The thermoplastic cyan compound is acrylonitrile. The method of claim 1, A thermoplastic resin composition prepared by polymerizing an alkyl acrylate monomer in the large-diameter alkyl acrylate rubber polymer of a) ii). The method of claim 1, 10 to 40 parts by weight of an acrylate-styrene-acrylonitrile resin containing the large diameter alkyl acrylate rubber polymer of a) ii) to 100 parts by weight of the total resin composition in the large diameter alkyl acrylate rubber polymer, and A thermoplastic resin composition prepared by polymerizing 1 to 20 parts by weight of a vinyl cyan compound. The method of claim 1, ASA resin wherein said acrylate-styrene-acrylonitrile polymer of a) contains a small diameter alkyl acrylate copolymer of a) i): ASA resin containing a large diameter alkyl acrylate copolymer of a) ii) is 1: A thermoplastic resin composition mixed in a ratio of 1 to 1: 4. The method of claim 1, The thermoplastic resin composition of the b) is a thermoplastic resin composition further comprises up to 10 parts by weight of the styrene monomer, and up to 10 parts by weight of the acrylic monomer. The method of claim 1, [AMS-AMS-AMS] chain structure of the molecular chain structure of the heat resistant copolymer of b) is up to 14%, [AMS-AN-AN] chain structure is up to 39% thermoplastic resin composition. The method of claim 1, A thermoplastic resin composition prepared by polymerizing the polybutadiene rubber polymer of c) 100 parts by weight of 1,3-butadiene. The method of claim 1, The acrylic polymer of c) is polybutadiene rubber latex 8 to 25 parts by weight, methacrylic acid alkyl ester compound or acrylic acid alkyl ester compound 40 to 70 parts by weight, aromatic vinyl compound 15 to 30 parts by weight, and vinyl cyan compound 1 to 20 A thermoplastic resin composition prepared by polymerizing parts by weight. The method of claim 1, The thermoplastic resin composition further comprises a lubricant or an antioxidant.