KR100508142B1 - Thermoplastic Resin Composition Having Excellent Antistatic Property - Google Patents

Abstract

The present invention relates to an acrylate-styrene-acrylonitrile (ASA) -based thermoplastic resin composition having excellent antistatic properties, and in particular, an alkyl sulfur succinate salt as a surface-active agent. Small and large diameter graft acrylate-styrene-acrylonitrile (ASA) resins containing 4 parts by weight to 4 parts by weight, including styrene-acrylonitrile (SAN) resins, and general antistatic agents to be excellent in basic physical properties and weather resistance In addition, at the same time provides an acrylate-styrene-acrylonitrile-based thermoplastic resin composition significantly improved long-term antistatic properties compared to the conventional general antistatic resin composition.

Description

Thermoplastic Resin Composition Having Excellent Antistatic Property

The present invention relates to a thermoplastic resin composition excellent in antistatic properties. More specifically, the present invention relates to an acrylate-styrene-acrylonitrile-based thermoplastic resin composition which not only has excellent physical properties and weather resistance, but also significantly improved antistatic properties.

The acrylate-styrene-acrylonitrile (ASA, ternary copolymer consisting of acrylate-styrene-acrylonitrile) resin has excellent weather resistance, chemical resistance, and thermal stability, and is used for outdoor electrical and electronic parts, construction materials, and sporting goods. It is used a lot. However, due to the intrinsic insulation characteristics of resins, static charges are formed due to external friction and contact, and as a result, foreign matters such as dust in the air are attached, which degrades the appearance quality, and in particular, malfunctions of precision electronic components, etc. As a cause, much effort has been made in the industry to improve this.

In order to improve the charging characteristics of such a resin, the following several methods have been proposed, and the first method is a method of coating an antistatic agent on the resin surface. As the antistatic agent, a surface-active agent having good hygroscopicity with water is used.

However, this method has a disadvantage in that the antistatic effect is lowered in a low atmospheric humidity condition, the coated antistatic agent is desorbed from the resin surface to contaminate the product, and in the manufacturing process, there is a disadvantage that the economic efficiency of the additional coating process.

As a second method, there is a method of incorporating a small amount of a low molecular weight antistatic agent having a property of shifting to the resin surface in the resin manufacturing process. This is the principle that the antistatic agent present in the resin matrix migrates to the resin surface over time, and the hydrophilic groups in the antistatic agent combine with moisture in the air to form a moisture layer and release the charged static charge through the moisture layer. Many of these methods have been proposed in the existing patents. US Pat. No. US3,575,903 using oxyethylate allyl amine, US Pat. No. US3,625,915 using alkanoamine and polyethylene glycol and Lauric diethanolamide US Pat. No. US3,873,645 and the like are the patents that proposed the method.

However, the method requires an induction time until the antistatic agent transitions to the surface, so the antistatic effect is insufficient immediately after the resin processing such as injection, and when the resin is washed or wiped with a cloth, the antistatic property is drastically deteriorated. There is a disadvantage in that long-term persistence is lowered because the sex is gradually reduced.

In a third method, a polymer type antistatic agent is used. In this method, the antistatic agent forms a network structure in the resin matrix, which acts as a charge carrier, and thus exhibits an antistatic effect immediately after processing, less antistatic effect due to external friction, and an excellent antistatic effect over time. There is this. Japanese Patent No. 4-33734 and US Patent No. US5,338,795 using polyether ester amides have proposed the above method. However, the above method may cause compatibility problems with the matrix resin to be used, and has a disadvantage in that it is economically poor due to relatively high cost as compared to the low molecular weight antistatic agent. In addition, US Patent No. US5.714,534 suggested that polystyrene resin is used as a matrix, and sulfonic acid salt is mixed with polyethylene oxide, acrylate copolymer, and surface active agent to show excellent long-term antistatic effect. It may cause compatibility problems.

An object of the present invention is to improve the long-term antistatic properties by devising a method using an alkyl sulfo succinate metal salt emulsifier that exhibits an antistatic effect among emulsifiers commonly used in emulsion polymerization, rather than blending and mixing low molecular weight antistatic agents. It is to provide an acrylate-styrene-acrylonitrile-based thermoplastic resin composition.

The above and other objects of the present invention can be achieved by the present invention described below.

The thermoplastic resin composition according to the present invention comprises (1) 10 to 45 parts by weight of small-diameter graft acrylate-styrene-acrylonitrile containing an alkyl sulfo succinate metal salt as an emulsifier; (2) 10 to 40 parts by weight of large-diameter graft acrylate-styrene-acrylonitrile containing an alkyl sulfo succinate metal salt as an emulsifier; (3) 10 to 80 parts by weight of styrene acrylonitrile (SAN) resin; And (4) 0.1 to 2.0 parts by weight of an antistatic agent based on 100 parts by weight of the sum of the above (1), (2) and (3).

The small-diameter graft acrylate-styrene-acrylonitrile polymer containing the (1) emulsifier may comprise 5 to 50 parts by weight of small-diameter alkyl acrylate rubber polymer; 10 to 50 parts by weight of an aromatic vinyl compound; 1 to 20 parts by weight of a vinyl cyan compound; And 1 to 2 parts by weight of potassium rosin acid as an emulsifier.

The small diameter alkyl acrylate rubber polymer may include 5 to 50 parts by weight of an alkyl acrylate monomer based on 100 parts by weight of the total monomers; And derivatives of alkyl sulfosuccinate metal salts having 12 to 18 carbon atoms having a pH of 3 to 9 or alkyl sulfate esters or sulfonic acid metal salt derivatives having from 12 to 20 carbon atoms, and in consideration of antistatic properties, It comprises 1 to 4 parts by weight of di 2-ethyl hexyl sulfur succinate sodium salt.

The alkyl acrylate monomer is butyl acrylate or ethyl hexyl acrylate.

The aromatic vinyl compound is selected from the group consisting of styrene, alpha methyl styrene and paramethyl styrene.

The vinyl cyan compound is acrylonitrile.

The large diameter graft acrylate-styrene-acrylonitrile polymer containing the emulsifier may comprise 10 to 60 parts by weight of the large diameter alkyl acrylate rubber polymer; 10 to 40 parts by weight of an aromatic vinyl compound; 1 to 20 parts by weight of a vinyl cyan compound; And 1 to 2 parts by weight of potassium rosin acid as an emulsifier.

The large-diameter alkyl acrylate rubber polymer is a derivative of an alkyl sulfosuccinate metal salt having 12 to 18 carbon atoms having a pH of 3 to 9 as an emulsifier, and 10 to 60 parts by weight of an alkyl acrylate monomer with respect to 100 parts by weight of the total monomer, or 12 carbon atoms. Derivatives of alkyl sulphate esters or sulfonic acid metal salts of ˜20 can be used, and preferably 0.1 to 1 parts by weight of di 2-ethylhexyl sulfur succinate sodium salt.

The alkyl acrylate monomer is butyl acrylate or ethyl hexyl acrylate.

The aromatic vinyl compound is selected from the group consisting of styrene, alpha methyl styrene and paramethyl styrene. The vinyl cyan compound is acrylonitrile.

The antistatic agent is cationic, anionic or nonionic.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

While the present inventors are studying a method for improving the antistatic property of an acrylate-styrene-acrylonitrile resin, most of the emulsifiers used in the emulsion polymerization have hydrophilic groups and lipophilic groups. Since it has the same structure as that of the emulsifier in some alkyl acrylate rubber polymers, it is possible to contribute to the antistatic property by using a principle that selects a specific emulsifier with good reactivity with moisture and adjusts the proper content. It was confirmed that it shows an excellent effect, and when using an alcohol amine cationic general antistatic agent is added to further show an excellent antistatic effect and there is no degradation in physical properties and weather resistance to complete the present invention.

The present invention relates to acrylate-styrene-acrylonitrile (ASA) resins, styrene-acrylonitrile (SAN) resins containing large diameter alkyl acrylate rubber polymers and small diameter alkyl acrylate rubber polymers, and alcohol amine cationic antistatic agents. It relates to an acrylate-styrene-acrylonitrile-based thermoplastic resin composition comprising a.

(A) Preparation of Small Diameter Graft Acrylate-Styrene-Acrylonitrile Polymer

A) preparation of small diameter alkyl acrylate rubber polymers

The small diameter alkyl acrylate rubber polymer is prepared by emulsion polymerization of an alkyl acrylate monomer. Butyl acrylate, ethyl hexyl acrylate may be used as the alkyl acrylate monomer used in the rubber polymer, but it is preferable to use butyl acrylate, the content of which is 5 to 50 parts by weight based on 100 parts by weight of the total monomers. It is preferable.

Emulsifiers, initiators, grafting agents, crosslinking agents, electrolyte materials and the like may be used as additives in the preparation of the small-diameter alkyl acrylate rubber polymers.

The emulsifier may be a derivative of an alkyl sulfo succinate metal salt having 12 to 18 carbon atoms having a pH of 3 to 9, or a derivative of an alkyl sulfate or sulfonic acid metal salt having 12 to 20 carbon atoms. Examples of the alkyl sulfo succinate metal salt derivative having 12 to 18 carbon atoms include dicyclohexyl sulfo succinate, dihexyl sulfo succinate, sodium or potassium salt of di 2-ethylhexyl sulfo succinate, lithium salt, and the like. Sulfuric acid esters or sulfonic acid metal salts having 12 to 20 carbon atoms include sodium lauric sulfate, sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleate sulfate, potassium dodecyl sulfate, or potassium octadecyl sulfate. Alkyl sulfate metal salts, such as these, can be used. In consideration of the antistatic contribution of the crosslinked alkyl acrylate rubber polymer as a whole, it is most preferable to use a sodium salt of di 2-ethylhexyl sulfur succinate having high reactivity with water, and the content thereof is 100 wt% of the total monomers. It is 1-4 weight part with respect to a part, Most preferably, it is 1.5-3 weight part. The required antistatic property is not expected at 1.0 parts by weight or less of the di 2-ethylhexyl sulfur succinate salt, and at 4.0 parts by weight or more, the thermal stability of the final acrylonitrile-styrene-acrylate (ASA) resin is rapidly lowered and discolored. It causes problems such as silver.

The initiator may be 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 of cumene hydroperoxide, or benzoyl peroxide. The content is preferably contained in 0.05 to 0.2 parts by weight based on 100 parts by weight of the total monomers.

The grafting agent may use aryl methacrylate (AMA), triaryl isocyanurate (TAIC), triaryl amine (TAA), or diaryl amine (DAA), the content of which is 100 parts by weight of the total monomer It is preferably contained in 0.01 to 0.07 parts by weight relative to.

The crosslinking agent is ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3 butanediol dimethacrylate, 1,6hexanediol dimethacrylate, neopentyl Grichol dimethacrylate, trimethylol propane trimethacrylate, trimethylol methane triacrylate, and the like can be used, and the content thereof is preferably contained in 0.05 to 0.3 parts by weight based on 100 parts by weight of the total monomers. .

As the electrolyte material, NaHCO ₃ , Na ₂ S ₂ O _7, or K ₂ CO ₃ may be used, and preferably NaHCO ₃ is used. The content is preferably contained in 0.05 to 0.4 parts by weight based on 100 parts by weight of the total monomers.

The addition of the monomer when polymerizing the alkyl acrylate rubber polymer may be performed by adding the continuous addition method alone or by mixing the continuous addition method and the batch addition method.

The pH of the alkyl acrylate rubber polymer is preferably in the range of 5 to 9, more preferably in the range of 6 to 8.

The particle size of the polymerized small-diameter alkyl acrylate rubber polymer is preferably 500 to 2000 mm 3, more preferably 700 to 1500 mm 3.

B) graft acrylate-styrene-acrylonitrile resin preparation

In the graft reaction, the aromatic vinyl compound may use styrene, alpha methyl styrene, para methyl styrene, or the like as the styrene monomer derivative, and preferably styrene. The content is preferably contained in 10 to 50 parts by weight based on the total resin composition.

As the vinyl cyan compound, acrylonitrile is preferably used, and the content thereof is preferably contained in an amount of 1 to 20 parts by weight based on the total resin composition.

The emulsifier used in the preparation of the acrylate-styrene-acrylonitrile resin has a pH of 9 to 13 in the aqueous solution, and uses derivatives of carboxylic acid metal salts such as fatty acid metal salts and rosin acid metal salts having 12 to 20 carbon atoms. It is preferable. As examples of the fatty acid metal salts, sodium or potassium of waste thiic acid, lauryl acid, and oleic acid can be used, and sodium or potassium rosin salt can be used as the rosin acid metal salt.

The polymerization initiator used in the production of the acrylate-styrene-acrylonitrile resin 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. Can be used. The content is preferably contained in 0.05 to 0.3 parts by weight based on the total resin composition.

In the batch addition method, the pH of the polymerization system is raised temporarily to make grafting difficult, and the stability of the particles is poor, so that the internal structure of the particles is not uniform. Therefore, the addition of mixed monomers including an emulsifier during the graft reaction uses a continuous addition method. It is desirable to.

It is preferable to use a tertiary dodecyl mercaptan, and the content of the molecular weight modifier added to adjust the molecular weight of the graft polymer is preferably contained in 0.2 parts by weight or less. If the content exceeds 0.2 parts by weight, there is a problem that the rate of decrease of the impact strength increases.

The pH of the acrylate-styrene-acrylonitrile resin having the above-described small diameter alkyl acrylate rubber is preferably in the range of 8 to 11, more preferably in the range of 9 to 10.5.

Latex particle size was measured using a Nicomp 370 HPL by Dynamic Laser Light Scattering.

(B) Preparation of Large Diameter Graft Acrylate-Styrene-Acrylonitrile Polymers

A) preparation of large diameter alkyl acrylate rubber polymers

Large diameter alkyl acrylate rubber polymers are prepared by emulsion polymerization of alkyl acrylate monomers. Butyl acrylate, ethyl hexyl acrylate may be used as the alkyl acrylate monomer used in the rubber polymer, but preferably butyl acrylate is used, the content of which is 10 to 60 parts by weight based on 100 parts by weight of the total monomers. It is preferable to be.

Emulsifiers, initiators, grafting agents, crosslinking agents, electrolyte materials and the like may be used as additives in the preparation of the large-diameter alkyl acrylate rubber polymers.

The emulsifier may be a derivative of an alkyl sulfo succinate metal salt having 12 to 18 carbon atoms having a pH of 3 to 9, or a derivative of an alkyl sulfate or sulfonic acid metal salt having 12 to 20 carbon atoms. Examples of the alkyl sulfo succinate metal salt derivative having 12 to 18 carbon atoms include dicyclohexyl sulfo succinate, dihexyl sulfo succinate, sodium or potassium salt of di 2-ethylhexyl sulfo succinate, lithium salt and the like. Most preferably it is best to use the sodium salt of di 2-ethylhexyl sulfur succinate, the content of which is 0.1 to 1.0 parts by weight based on 100 parts by weight of the total monomers.

The initiator may be 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 of cumene hydroperoxide, or benzoyl peroxide. The content is preferably contained in 0.05 to 0.2 parts by weight based on 100 parts by weight of the total monomers.

The grafting agent may use aryl methacrylate (AMA), triaryl isocyanurate (TAIC), triaryl amine (TAA), or diaryl amine (DAA), the content of which is 100 parts by weight of the total monomer It is preferably contained in 0.01 to 0.07 parts by weight relative to.

The crosslinking agent is ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3 butanediol dimethacrylate, 1,6hexanediol dimethacrylate, neopentyl Grichol dimethacrylate, trimethylol propane trimethacrylate or trimethylol methane triacrylate and the like can be used, the content of which is preferably included in 0.05 to 0.3 parts by weight based on 100 parts by weight of the total monomers.

As the electrolyte material, NaHCO ₃ , Na ₂ S ₂ O _7, or K ₂ CO ₃ may be used, and preferably NaHCO ₃ is used. The content is preferably contained in 0.05 to 0.4 parts by weight based on 100 parts by weight of the total monomers.

The pH of the alkyl acrylate rubber polymer is preferably in the range of 5 to 9, more preferably in the range of 6 to 8.

The particle size of the polymerized large-diameter alkyl acrylate rubber polymer is preferably 2500 to 5000 mm 3, more preferably 3000 to 4500 mm 3.

B) graft acrylate-styrene-acrylonitrile resin preparation

In the grafting reaction, the aromatic vinyl compound may use styrene, alpha methyl styrene, para methyl styrene, or the like as the styrene monomer derivative. Preferably, styrene is used. The content is preferably contained in 10 to 40 parts by weight based on the total resin composition.

As the vinyl cyan compound, acrylonitrile is preferably used, and the content thereof is preferably contained in an amount of 1 to 20 parts by weight based on the total resin composition.

The emulsifier used in the preparation of the graft acrylate-styrene-acrylonitrile resin has a pH of 9-13 in the aqueous solution, and a derivative of carboxylic acid metal salts such as fatty acid metal salts having 12 to 20 carbon atoms and metal rosin acid salts. It is preferable to use. As examples of the fatty acid metal salts, sodium or potassium of waste thiic acid, lauryl acid, and oleic acid may be used, and sodium or potassium rosin salt may be used as the metal rosin acid salt, and the content thereof is preferably 1 to 2 parts by weight.

The polymerization initiator used in the production of the acrylate-styrene-acrylonitrile resin 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. Can be used. The content is preferably contained in 0.05 to 0.3 parts by weight based on the total resin composition.

(C) general antistatic agents

A resin composition having excellent long-term antistatic properties is prepared by the acrylate-styrene-acrylonitrile polymer, and a low molecular weight general antistatic agent is used to further improve the antistatic property. The antistatic agent used may be a cationic, anionic or nonionic antistatic agent, but the use of a cationic antistatic agent is preferred. In the present invention, alcohol amine cationic antistatic agent 125B manufactured by MIYOSHI, Japan is used.

The acrylate-styrene-agrylonitrile thermoplastic resin (ASA) composition excellent in the antistatic property of this invention,

1) 10 to 45 parts by weight of the small-diameter graft acrylate-styrene-acrylonitrile polymer prepared by the method (A);

2) 10 to 40 parts by weight of the large diameter graft acrylate-styrene-acrylonitrile polymer prepared by the method (B);

3) 15 to 80 parts by weight of styrene-acrylonitrile (SAN) resin; And

To 100 parts by weight of acrylate-styrene-acrylonitrile thermoplastic resin (ASA) prepared by the above 1), 2), 3),

4) 0.1 to 2 parts by weight of alcohol amine cationic antistatic agent.

It comprises a small diameter ASA polymer of 1), a large diameter ASA polymer of 2) and a SAN resin of 3), an antistatic agent of 4) and a thermal stabilizer, a lubricant, a light stabilizer is added thereto, and then mixed and mixed to 210 ℃ to 230 Pellet was prepared by using a twin screw extruder at ℃ and the pellet was injected again to measure the antistatic properties and physical properties, weather resistance. The antistatic property was measured half life using a HONESTOMETER, and the physical properties were measured by the ASTM method. The weather resistance was tested by ATLAS Ci35A accelerated weathering test equipment for 2,000 hours to measure the color difference (ΔE) of the specimen before and after the test.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to Examples.

Example 1

Manufacture of small diameter graft acrylate-styrene-acrylonitrile resin

(1) Preparation 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 feeding continuously. The particle size of the rubber polymer obtained after completion of the reaction showed a range of 800 to 1000 mm 3.

(2) Preparation of Small Diameter Graft Acrylate-Styrene-Acrylonitrile 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), 20 parts by weight of acrylonitrile (AN), and 3 to the alkyl acrylate rubber polymer. A mixture of 0.05 parts by weight of grade dodecyl mercaptan (TDDM) and 0.1 parts by weight of potassium persulfate (KPS) as a catalyst were continuously added at 70 ° C. for 5 hours, followed by a polymerization reaction at 80 ° C. to increase the polymerization conversion rate. After further reacting for 1 hour, the mixture was cooled to 60 ° C.

The particle size of the small diameter graft acrylate-styrene-acrylonitrile resin prepared as described above was 1200 mm 3, the polymerization conversion rate was 98%, pH was 9.5, and the graft rate was 40%.

The obtained acrylate-styrene-acrylonitrile resin was subjected to atmospheric condensation at 85 ° C. using an aqueous calcium chloride solution, and then aged at 95 ° C. for dehydration and washing, followed by drying for 30 minutes with hot air at 90 ° C. to obtain a final acrylic resin. Laterate-styrene-acrylonitrile powder particles were obtained.

Manufacture of large diameter graft acrylate-styrene-acrylonitrile resins

(1) Preparation 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 catalyst potassium persulfate were added at 70 ° C. The polymerization was carried out while being continuously added for a time. The particle size of the rubber polymer obtained after completion of the reaction showed a range of 3000 to 4000 mm 3.

(2) Preparation of large diameter graft acrylate-styrene-acrylonitrile 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), 35 parts by weight of styrene (ST), 15 parts by weight of acrylonitrile (AN), and 3 to the alkyl acrylate rubber polymer. A mixture of 0.05 parts by weight of grade dodecyl mercaptan (TDDM) and 0.1 parts by weight of potassium persulfate (KPS) as a catalyst were continuously added at 70 ° C. for 5 hours, followed by a polymerization reaction at 80 ° C. to increase the polymerization conversion rate. After further reacting for 1 hour, the mixture was cooled to 60 ° C.

The particle size of the large-diameter graft acrylate-styrene-acrylonitrile resin prepared as described above was 4500 kPa, the polymerization conversion rate was 99%, the pH was 9.5, and the graft rate was 45%.

The obtained large-diameter graft acrylate-styrene-acrylonitrile resin was subjected to atmospheric coagulation at 85 ° C. using an aqueous calcium chloride solution, and then aged at 95 ° C. for dehydration and washing, followed by drying for 30 minutes by hot air at 90 ° C. To obtain final acrylate-styrene-acrylonitrile powder particles.

ASA thermoplastic resin manufacturing

35 parts by weight of the small-size acrylate-styrene-acrylonitrile powder particles, 20 parts by weight of large-diameter ASA powder particles, 45 parts by weight of styrene-acrylonitrile (SAN) resin, and a stabilizer, a lubricant, and a light stabilizer were mixed and extrusion kneaded. An acrylate-styrene-acrylonitrile-based thermoplastic resin was prepared.

Example 2

In Example 1, the content of di 2-ethylhexyl sulfo succinate sodium salt was changed to 3.0 parts by weight in the small-diameter rubber polymer manufacturing step of (1) in the small-diameter graft acrylate-styrene-acrylonitrile resin manufacturing process. Except that was carried out in the same manner as in Example 1.

Example 3

The di-ethylhexyl sulfo succinate sodium salt content was changed to 1.3 parts by weight in the small-diameter rubber polymer manufacturing step of (1) in the small-diameter graft acrylate-styrene-acrylonitrile resin manufacturing process in Example 1. Except that was carried out in the same manner as in Example 1.

Example 4

Except for adding 0.5 part by weight of the cationic antistatic agent in Example 1 was carried out in the same manner as in Example 1.

Comparative Example 1

In Example 1, di-ethylhexyl sulfo succinate sodium salt was added to dodecyl sulfur succinate potassium salt in the small-diameter rubber polymer manufacturing step of (1) in the small-diameter graft acrylate-styrene-acrylonitrile resin manufacturing process. The same procedure as in Example 1 was conducted except that the procedure was changed to.

Comparative Example 2

In Example 1, the small-diameter graft acrylate-styrene-acrylonitrile resin was prepared by changing the content of di 2-ethylhexyl sulfo succinate sodium salt in the small-diameter rubber polymer manufacturing step of (1) to 0.8 parts by weight. Except that was carried out in the same manner as in Example 1.

Comparative Example 3

In Example 1, the small-diameter graft acrylate-styrene-acrylonitrile resin was prepared by changing the content of di 2-ethylhexyl sulfo succinate sodium salt in the small-diameter rubber polymer manufacturing step of (1) to 3.5 parts by weight. Except that was carried out in the same manner as in Example 1.

[Comparative Example 4]

The di-ethylhexyl sulfo succinate sodium salt content was changed to 0.8 parts by weight in the small-diameter rubber polymer manufacturing process of (1) in the small-diameter graft acrylate-styrene-acrylonitrile resin manufacturing process in Example 1 The same process as in Example 1 was carried out except that 0.5 parts by weight of the antistatic agent was added.

[Comparative Example 5]

The di-ethylhexyl sulfo succinate sodium salt content was changed to 0.8 parts by weight in the small-diameter rubber polymer manufacturing step of (1) in the small-diameter graft acrylate-styrene-acrylonitrile resin manufacturing process in Example 1, The same process as in Example 1 was conducted except that 1.0 part by weight of the cationic antistatic agent was added.

The ASA thermoplastic resins obtained in Examples 1 to 4 and Comparative Examples 1 to 5 were pelletized using a 30 Φ twin screw extruder, and then obtained by using an injection molding machine. Using this, the antistatic properties were evaluated by measuring the half-life using the following physical properties and the hornistometer, and the weather resistance was measured by the weathering acceleration tester. Thermal stability was evaluated by thermal discoloration (ΔE) and appearance quality through the injection machine stay 250 ℃ / 15 minutes, the results are shown in Table 1 below.

A) Izod impact strength (1/4 notched at 23 ° C., kg · cm / cm) —measured according to ASTM D256.

B) Tensile strength (50 mm / min, kg / cm 2)-measured according to ASTM D638.

C) fluidity (220 ° C./10 Kg, g / 10 min) —measured according to ASTM D1238.

D) antistatic property (sec)-measured at half-life at 23 ° C. and 50% RH over time (4 weeks).

ㅁ) Thermal stability-evaluated by thermal discoloration (ΔE) and appearance quality.

Weather resistance-Atlas Ci35A W-O-M (Xenon Lamp, Energy 0.35 W / ㎡)

After using the test for 2,000 hours, the discoloration was measured by ΔE.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 4 Comparative Example 4 Comparative Example 5 Small Diameter ASA Large Diameter ASASAN Antistatic Agent 352045- 352045- 352045- 352045- 352045- 352045- 3520450.5 3520450.5 3520451.0 Small Diameter Emulsifier A (Diethylhexyl Sulpersuccinate Naturium) 2.0 3.0 1.3 - 0.8 3.5 2.0 0.8 0.8 Small diameter emulsifier B (dodecylsulpersuccinate potassium salt) - - - 2.0 - - - - - Impact strength 19 17.5 20.2 17.1 23.4 13.7 19 19 20.0 The tensile strength 460 465 462 450 444 477 455 455 454 Flow index 10.5 11.0 9.5 12.5 12.7 9.8 10.8 10.5 11.0 Half-Life Fruit 1 day 7 days 14 days 21 days 28 days 4132302724 3829211818 6963585051 6858554846 ∞∞∞∞∞ 1714101110 2220161515 1218354877 1112224574 (After friction with cloth) 58 43 75 76 ∞ 25 38 125 120 Weather resistance (△ E) 1.85 2.11 1.88 1.88 1.75 2.99 1.98 1.91 2.11 Thermal Stability Thermochromic (△ E) 3.3 4.4 3.1 3.1 3.0 5.7 3.5 3.6 3.9 External visual judgment  × Surface condition: Good, Normal × Bad

As described above, the acrylate-styrene-acrylonitrile resin-based thermoplastic resin composition of the present invention not only has excellent physical properties such as impact strength, tensile strength, fluidity, and weather resistance, but also uses a conventional general antistatic agent. Compared to the case, the antistatic property is excellent in long-term durability and the antistatic property due to external friction (lighting) is very small.

While the invention has been described in detail above with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the invention, and such modifications and variations fall within the scope of the appended claims. It is also natural.

Claims (12)

(1) 10 to 45 parts by weight of a small diameter graft acrylate-styrene-acrylonitrile resin having a particle diameter of 500 to 2000 mm 3 containing an alkyl sulfo succinate metal salt as an emulsifier; (2) 10 to 40 parts by weight of large-diameter graft acrylate-styrene-acrylonitrile-based resin having a particle diameter of 2500 to 5000 mm 3 containing an alkyl sulfo succinate metal salt as an emulsifier; (3) 10 to 80 parts by weight of styrene acrylonitrile (SAN) resin; And (4) 0.1 to 2.0 parts by weight of antistatic agent based on 100 parts by weight of the above (1), (2) and (3) Thermoplastic resin composition comprising a. The method of claim 1, Small-diameter graft acrylate-styrene-acrylonitrile-based resins containing the above-mentioned (1) emulsifier 5 to 50 parts by weight of small diameter alkyl acrylate rubber polymer; 10 to 50 parts by weight of styrene monomer derivative; 1 to 20 parts by weight of acrylonitrile; And 1-2 parts by weight of sodium rosin as an emulsifier Thermoplastic resin composition comprising a. The method of claim 2, The small diameter alkyl acrylate rubber polymer is based on 100 parts by weight of the total monomers, 5 to 50 parts by weight of an alkyl acrylate monomer; And Characterized by alkyl sulfosuccinate metal salt having 8 to 20 carbon atoms of pH 3-9 as emulsifier, the content is 1 to 4 parts by weight based on 100 parts by weight of monomer Alkyl acrylate rubber polymer production method comprising a . The method of claim 3, wherein The alkyl acrylate monomer is a butyl acrylate or ethyl hexyl acrylate, characterized in that the thermoplastic resin composition. The method of claim 2, The styrene monomer derivative is a thermoplastic resin composition, characterized in that selected from the group consisting of styrene, alpha methyl styrene and paramethyl styrene. delete The method of claim 1, The large-diameter graft acrylate-styrene-acrylonitrile-based resin containing the emulsifier (2) 10 to 60 parts by weight of large-diameter alkyl acrylate rubber polymer; 10 to 40 parts by weight of styrene monomer derivatives; 1 to 20 parts by weight of acrylonitrile; And 1-2 parts by weight of potassium rosin as an emulsifier Thermoplastic resin composition comprising a . The method of claim 7, wherein The large diameter alkyl acrylate rubber polymer is based on 100 parts by weight of the total monomers, 10 to 60 parts by weight of alkyl acrylate monomers; And 0.1 to 1 parts by weight of a derivative of alkyl sulfosuccinate metal salt having 12 to 18 carbon atoms having pH of 3 to 9 or an alkyl sulfate ester or sulfonic acid metal salt having 12 to 20 carbon atoms as an emulsifier Thermoplastic resin composition comprising a. The method of claim 8, The alkyl acrylate monomer is a thermoplastic resin composition, characterized in that butyl acrylate or ethyl hexyl acrylate. The method of claim 7, wherein The styrene monomer derivative is a thermoplastic resin composition, characterized in that selected from the group consisting of styrene, alpha methyl styrene and paramethyl styrene. delete The method of claim 1, The antistatic agent is a thermoplastic resin composition, characterized in that selected from the group consisting of cationic, anionic and nonionic.