WO2016089000A1 - Method for preparing thermoplastic resin - Google Patents

Abstract

The present invention relates to a method for preparing a thermoplastic resin and, more specifically, to a method for preparing a thermoplastic resin, a thermoplastic resin, a method for preparing a thermoplastic resin composition containing the thermoplastic resin, and a thermoplastic resin composition, wherein the method for preparing a thermoplastic resin comprises the steps of: i) preparing a graft copolymer latex by graft-polymerizing, onto a) a conjugated diene rubber, b) at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, and acrylate-based compounds; and ii) introducing a polymeric antibiotic having a primary, secondary, tertiary, or quaternary amine group to the graft copolymer latex, followed by coagulation. According to the present invention, the graft copolymer latex is prepared, and then coagulated using a specific antibiotic, thereby providing a thermoplastic resin having excellent antibiotic activity and melt-kneadability and a method for preparing a thermoplastic resin to produce a thermoplastic resin composition containing the thermoplastic resin.

Description

Thermoplastic Manufacturing Method

[Reciprocal citation with application (s)]

This application claims the benefit of priority based on Korean Patent Application No. 10-2014-0173861 dated December 05, 2014 and Korean Patent Application No. 10-2015-0138309 dated October 01, 2015. All content disclosed in the literature is included as part of this specification.

The present invention relates to a method for producing a thermoplastic resin, and more particularly, to prepare a graft copolymer latex and agglomerate it with a specific antimicrobial agent, thereby preparing a thermoplastic resin having excellent antibacterial and melt kneading properties and a thermoplastic resin composition comprising the same. It relates to a thermoplastic resin manufacturing method for.

Acrylonitrile-Butadiene-Styrene (hereinafter referred to as ABS) resin is a resin having a good balance of physical properties such as impact resistance, chemical resistance, processability and surface gloss, and is used for office equipment, electrical and electronic products, and automotive interior materials. Widely used in toys, household goods, etc.

In relation to the use of the ABS resin, as the interest in hygiene has recently increased, researches on the development of resins given antimicrobial properties that suppress bacterial contamination and proliferation by contact have been actively conducted. Accordingly, various methods for imparting antimicrobial properties have been introduced. The most common method includes adding an antimicrobial agent to the resin, and the antimicrobial agent used may be classified into organic antimicrobial agents and inorganic antimicrobial agents.

Inorganic antimicrobial agents are mainly made of products made by substituting silver, zinc and copper, which are metal ions that have antimicrobial action on inorganic substances such as zeolite, calcium phosphate, zirconium phosphate and silica gel, and are currently used in various fields such as plastic products, paper and textiles. It is utilized in. However, in order to obtain satisfactory antimicrobial properties from the inorganic antimicrobial agent, an inorganic antimicrobial agent should be added in an excessive amount. In this case, discoloration of the resin and deterioration of physical properties may occur due to the excessive antimicrobial component, and manufacturing costs may increase. .

For example, Korean Patent Laid-Open No. 2006-0076792 discloses a method of adding antimicrobial properties by adding silver nanoparticles, which are inorganic antimicrobial agents, to ABS-based transparent resins, but the manufacturing cost increases greatly by using expensive silver nanoparticles. There is this. In addition, as the toxicity of the metal ions has recently been reported to the human body, efforts have been made to limit their use.

Organic antimicrobial agents are further divided into monomolecular antimicrobial agents having a low molecular weight and antimicrobial agents having a high molecular weight. The monomolecular organic antimicrobial agent having a low molecular weight has excellent short-term antimicrobial properties, but its sustainability of antimicrobial activity is not very good, and its use is limited due to acute human toxicity. On the other hand, the antimicrobial agent in the form of polymer has advantages such as improved antimicrobial activity, reduced human toxicity and longer antimicrobial activity compared to the conventional monomolecular antimicrobial agent having a small molecular weight. However, such a polymer-type antimicrobial agent also has a disadvantage of poor melt kneading with the resin, in particular ABS-based thermoplastic resin. Therefore, when an antimicrobial ABS-based thermoplastic resin is manufactured by melt kneading a polymer-type antimicrobial agent with an ABS-based thermoplastic resin using an extruder, the mechanical properties of the manufactured thermoplastic resin are greatly reduced.

Thus, in order to solve the above problems, the polymer-type antimicrobial agent is evenly dispersed in the thermoplastic resin, and there is a need for research on an ABS-based thermoplastic resin having excellent antibacterial properties without deteriorating mechanical properties.

[Prior art document]

[Patent Documents]

(Patent Document 1) KR2006-0076792 A

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a method for producing a thermoplastic resin excellent in antimicrobial and melt kneading by preparing a graft copolymer latex, and agglomerated with a specific antimicrobial agent.

In addition, an object of the present invention is to provide a method for producing a thermoplastic resin composition, including the thermoplastic resin excellent in mechanical properties, fluidity and antibacterial properties.

In addition, an object of the present invention is to provide a thermoplastic resin comprising the antimicrobial agent and a thermoplastic resin composition comprising the same.

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

In order to achieve the above object, the present invention is graft by graft polymerization including i) a) at least one selected from the group consisting of a) conjugated diene rubber, b) an aromatic vinyl compound, a vinyl cyan compound and an acrylate compound. Preparing a copolymer latex; And ii) incorporating the polymer antimicrobial agent having a primary, secondary, tertiary or quaternary amine group into the graft copolymer latex to agglomerate it.

The present invention also provides a graft copolymer comprising a) conjugated diene rubber, b) one or more graft copolymers selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds and acrylate compounds; And a polymer antimicrobial agent having a primary, secondary, tertiary or quaternary amine group.

In another aspect, the present invention is to prepare a graft copolymer latex by graft polymerization comprising i) a) at least one selected from the group consisting of a) conjugated diene rubber, b) an aromatic vinyl compound, a vinyl cyan compound and an acrylate compound. step; ii) aggregating a polymer antimicrobial agent having a primary, secondary, tertiary or quaternary amine group into the graft copolymer latex; iii) obtaining a thermoplastic resin from the aggregated graft copolymer; And iv) 20 to 80% by weight of the thermoplastic resin and 20 to 80% by weight of the copolymer resin polymerized with at least one polymer selected from the group consisting of B) aromatic vinyl compounds, vinyl cyan compounds and acrylate compounds. It provides a method for producing a thermoplastic resin composition comprising a.

In another aspect, the present invention comprises 20 to 80% by weight of the thermoplastic resin and B) 20 to 80% by weight of the copolymer resin polymerized at least one selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound and an acrylate compound. It provides a thermoplastic resin composition.

According to the present invention by preparing a graft copolymer latex, and agglomerated with a specific antimicrobial agent, there is an effect of providing a thermoplastic resin excellent for antimicrobial and melt kneading and a thermoplastic resin manufacturing method for producing a thermoplastic resin composition comprising the same. .

Hereinafter, the present invention will be described in detail.

The present inventors have continued to study the method of evenly dispersing the polymer type antimicrobial agent in the thermoplastic resin so as not to deteriorate the mechanical properties. As a result, the polymer antimicrobial agent having a graft copolymer latex having a primary, secondary, tertiary or quaternary amine group When agglomerated using, the thermoplastic resin having excellent antimicrobial and melt kneading properties can be prepared, and from this, the thermoplastic resin composition having excellent mechanical properties, fluidity and antimicrobial properties can be prepared, thereby completing the present invention. Was done.

Looking at the thermoplastic resin manufacturing method of the present invention in detail.

The thermoplastic resin manufacturing method comprises graft polymerized latex by graft polymerization comprising i) a) at least one selected from the group consisting of a) conjugated diene rubber, b) an aromatic vinyl compound, a vinyl cyan compound and an acrylate compound. Manufacturing; And ii) aggregating the graft copolymer latex by adding a polymer antimicrobial agent having a primary, secondary, tertiary or quaternary amine group.

The graft polymerization of step i) may be, for example, an emulsion polymerization method. The emulsion polymerization may be polymerized by, for example, a batch, semi-batch, or continuous process. The method of adding each component during the emulsion polymerization of the graft copolymer may be, for example, a graft addition method in which a batch is added or a whole or a part is continuously added.

The emulsifier used in the emulsion polymerization of the graft copolymer of step i) is not particularly limited, but specific examples include alkylaryl sulfonate; Alkali methylalkyl sulfates; Sulfonated alkyl esters; And general adsorbent emulsifiers such as soaps of fatty acids or alkali salts of rosin acid.

In step ii), the polymer antimicrobial agent having the amine group may be used as a flocculant.

Aggregation of the step ii) may be carried out at pH 2 to 6, for example, and there is no problem that the thermal stability of the resin is lowered due to residual acidic substances within this range, and the binding of the polymer type antimicrobial agent is made well. The antibacterial property is excellent effect.

As another example, the polymer antimicrobial agent of step ii) may be dissolved in an acid solution having a pH of 2 to 5 in an amount of 0.1 to 10% by weight, or 0.1 to 5% by weight, or 0.5 to 3% by weight, and the pH range is Excellent coagulation characteristics in the inside, do not occur deterioration of the polymer due to acid during long-term storage has excellent stability effect. In addition, when the polymer antimicrobial agent is dissolved in an acid solution in the range of 0.1 to 10% by weight, the aggregation property is excellent and no coagulation occurs, and the viscosity of the acid solution is suitable for the aggregation process.

The acid aqueous solution of pH 2 to 5 may be, for example, an acid aqueous solution containing an organic acid or an inorganic acid, and specific examples include acetic acid, formic acid, citric acid, butyric acid, palmitic acid, oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, and boric acid. It may be at least one selected from the group consisting of.

The method of coagulation in step ii) is not particularly limited, but specific examples include a batch coagulation method in which a coagulant is added first and a latex is added later, a continuous coagulation method in which coagulant and latex are continuously added, and mechanical shear May be a mechanical coagulation method or a slow coagulation method.

The a) conjugated diene rubber may be added in 20 to 70% by weight, 30 to 60% by weight, or 35 to 50% by weight with respect to the graft copolymer, for example, excellent in impact strength within this range, The graft proceeds completely during the polymerization, and the mechanical properties are very good.

The conjugated diene rubber is, for example, a polymer of a conjugated diene compound, butadiene polymer, butadiene-styrene copolymer (SBR), butadiene-acrylonitrile copolymer (NBR), ethylene-propylene copolymer (EPDM) or a polymer derived therefrom Can be.

The conjugated diene rubber latex may have, for example, an average particle diameter of 800 to 6,000 mm 3, or 1,500 to 4,500 mm 3, or 2,000 to 4,000 mm 3, and excellent impact strength within this average particle diameter range.

As another example, the conjugated diene rubber latex may have a gel content of 60 to 95%, or 65 to 90%, and excellent impact strength within the gel content range.

As another example, the conjugated diene rubber latex may have a swelling index of 12 to 40, or 15 to 30, and excellent impact strength within the swelling index range.

At least one selected from the group consisting of the aromatic vinyl compound, the vinyl cyan compound, and the acrylate compound may be added at 30 to 80 wt%, 40 to 70, or 50 to 75 wt% based on the graft copolymer. It can be, and within this range there is an effect of excellent mechanical and physical properties balance.

For example, the aromatic vinyl compound may be added in an amount of 5 to 60% by weight, 15 to 55% by weight, or 30 to 50% by weight based on the graft copolymer, and has excellent workability and physical property balance within this range.

The aromatic vinyl compound may be at least one selected from the group consisting of styrene, α-methyl styrene, ο-ethyl styrene, p-ethyl styrene, and vinyltoluene, for example.

The vinyl cyan compound may be added, for example, in an amount of 0 to 20 wt%, or 10 to 20 wt% with respect to the graft copolymer, and within this range, no coagulum is produced during the graft polymerization, thereby improving productivity. This improves and there is an effect of maintaining the natural color without changing the color of the resin composition yellow.

The vinyl cyan compound may be at least one selected from the group consisting of, for example, acrylonitrile, methacrylonitrile, and ethacrylonitrile.

For example, the acrylate compound may be added in an amount of 0 to 60% by weight, or 0 to 40% by weight based on the graft copolymer, and has excellent workability and physical property balance within this range.

The acrylate compound may be, for example, a (meth) acrylic acid alkyl ester compound, and specific examples include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, and (meth) acrylic acid 2-ethylhexyl. It may be at least one selected from the group consisting of esters, (meth) acrylic acid decyl esters, and (meth) acrylic acid lauryl esters.

The polymer antimicrobial agent having the amine group may be added in an amount of 1 to 20 parts by weight, or 1 to 10 parts by weight, or 3 to 8 parts by weight, based on 100 parts by weight of the graft copolymer, for example. And excellent cohesive properties, there is an excellent impact strength.

The polymer antimicrobial agent having an amine group is, for example, a monomer constituting the monomer, preferably a main monomer, more preferably, at least 50% of the monomer constituting the main chain includes monomers containing primary, secondary, tertiary or quaternary amine groups. Can be.

For example, the polymer antimicrobial agent having an amine group may have solubility in an acid aqueous solution having a pH of 1 to 5 and insoluble in an aqueous solution having a pH of 6 to 12. The solubility means, for example, a property of dissolving 0.1 g or more in 100 g of a solvent at 23 ° C. and atmospheric pressure, and the insolubility means a property of not dissolving 0.1 g or more under the same conditions and criteria.

As another example, the polymer antimicrobial agent having the amine group may be dissolved at least 1 g at 23 ° C. and atmospheric pressure with respect to 100 g of an acid solution having a pH of 1 to 5.

The polymer antimicrobial agent having the amine group is not particularly limited as long as it is a polymer antimicrobial agent that satisfies the solubility according to the pH and the constituents, and specific examples thereof include polydiallyldimethyl ammonium chloride) and polydiciandiamide. (polydicyandiamide), polyN-vinylpyrrolidone (poly (N-vinylpyrrolidone)}, polyethyleneimine (polyethyleneimine), chitosan (chitosan), chitosan derivatives (modified chitosan) and polyvinylpyridine (polyvinylpyridine) It may be one or more.

The thermoplastic resin according to the present invention comprises a graft copolymer in which at least one graft copolymer selected from the group consisting of a) conjugated diene rubber, b) an aromatic vinyl compound, a vinyl cyan compound and an acrylate compound; And a polymer antimicrobial agent having a primary, secondary, tertiary or quaternary amine group.

The method for producing a thermoplastic resin composition according to the present invention comprises graft polymerization by graft polymerization comprising i) a) at least one selected from the group consisting of a) conjugated diene rubber, b) an aromatic vinyl compound, a vinyl cyan compound and an acrylate compound. Preparing a copolymer latex; ii) aggregating a polymer antimicrobial agent having a primary, secondary, tertiary or quaternary amine group into the graft copolymer latex; iii) obtaining a thermoplastic resin from the aggregated graft copolymer; And iv) 20 to 80% by weight of the thermoplastic resin and 20 to 80% by weight of the copolymer resin polymerized with at least one polymer selected from the group consisting of B) aromatic vinyl compounds, vinyl cyan compounds and acrylate compounds. To make; characterized in that it comprises a.

The method of polymerizing the copolymer resin polymerized with one or more selected from the group consisting of the aromatic vinyl compound, the vinyl cyan compound, and the acrylate compound is not particularly limited, but specific examples thereof include suspension polymerization, block polymerization or continuous block polymerization. May be polymerized.

The manufacturing process of the copolymer resin B) may be, for example, a continuous process consisting of a raw material input pump, a continuous stirring tank, a preheating tank, a volatilization tank, a copolymer transfer pump, and an extrusion processor.

As the kneading apparatus of the A) thermoplastic resin and B) copolymer resin, for example, a banbury mixer, a single screw extruder, a twin screw extruder, a buss kneader, and the like may be used. have.

The aromatic vinyl compound included in the B) copolymer resin may be at least one selected from the group consisting of styrene, α-methyl styrene, ο-ethyl styrene, p-ethyl styrene, and vinyltoluene, for example. 10 to 90% by weight, or 30 to 80% by weight, or 50 to 80% by weight relative to the resin may be included.

The vinyl cyan compound included in the B) copolymer resin may be, for example, one or more selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile, and 10 to 70 based on the B) copolymer resin. Wt%, or 20 to 60% by weight, or 20 to 40% by weight.

The acrylate compound contained in the said B) copolymer resin is (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid 2ethylhexyl ester, (meth) acrylic acid, for example. It may be at least one selected from the group consisting of decyl ester and (meth) acrylic acid lauryl ester, and may be included in 0 to 20% by weight, or 0 to 10% by weight based on the B) copolymer resin.

The thermoplastic resin composition according to the present invention comprises: A) 20 to 80% by weight of the thermoplastic resin and B) at least one copolymerized polymer resin 20 to 80 selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound and an acrylate compound. It comprises a weight percent.

The thermoplastic resin composition may be, for example, 5 to 35% by weight, 5 to 25% by weight, or 10 to 20% by weight of the conjugated diene rubber. Within the range of the conjugated diene rubber content, the impact strength is excellent, the workability is improved and the rigidity is excellent.

As another example, the thermoplastic resin composition may have a content of a monomer mixed compound including at least one selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an acrylate compound, in an amount of 60 to 95 wt%, or 75 to 95 wt%, Or 80 to 90% by weight, it is excellent in the physical property balance within the above range.

For example, the thermoplastic resin composition may have an impact strength of 10 kg · cm / cm or more, 15 kg · cm / cm or more, or 20 kg · cm / cm or more.

As another example, the thermoplastic resin composition may have a fluidity of 13 g / 10 min (220 ° C., 10 kg) or more, or 15 g / 10 min (220 ° C., 10 kg) or more.

The thermoplastic resin composition may optionally include additives such as heat stabilizers, light stabilizers, antioxidants, antistatic agents, antibacterial agents or lubricants within a range that does not affect the physical properties.

The present invention also provides a molded article prepared from the thermoplastic resin composition. The molded article may be, for example, office equipment, electrical and electronic products, automotive interior materials, toys or household goods.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

EXAMPLE

Example  One

A) Graft  Copolymer preparation

40 parts by weight (based on solids) of butadiene rubber latex (gel content of 80%, average particle diameter of 0.3 µm) prepared by emulsion polymerization in a nitrogen-filled polymerization reactor, 120 parts by weight of ion-exchanged water, 0.5 parts by weight of potassium rosinate, and acryl 5.0 parts by weight of ronitrile, 10 parts by weight of styrene and 0.1 parts by weight of tertiary dodecyl mercaptan were added at once, and the reaction temperature was raised to 50 ° C. At the time when the temperature inside the reactor reached 50 ° C., 0.1 parts by weight of tertiary butyl hydroperoxide, 0.1 parts by weight of dextrose, 0.1 parts by weight of sodium pyrolate, and 0.002 parts by weight of ferrous sulfate were collectively added to the reactor. After initiation, the reaction temperature was raised to 70 ° C. for 30 minutes. Thereafter, the monomer emulsion prepared by mixing 12.6 parts by weight of acrylonitrile, 32.4 parts by weight of styrene, 25 parts by weight of ion-exchanged water and 1.0 part by weight of potassium rosinate was continuously added to the reactor for 2 hours. At the same time, 0.15 parts by weight of tert-butylhydroperoxide was continuously added to the reactor for 2 hours through a separate inlet. At the time when the addition of the monomer emulsion was completed, 0.05 part by weight of tertiary butyl hydroperoxide, 0.05 part by weight of dextrose, 0.05 part by weight of sodium pyrolate, and 0.001 part by weight of ferrous sulfate were collectively added, and then the reaction temperature was 80 ° C. After mixing for 30 minutes, the mixture was aged for 30 minutes and the reaction was terminated to prepare an ABS graft copolymer latex.

Coagulation and Aging

5 parts by weight of chitosan solution (based on chitosan solids) in which 2% by weight of chitosan was dissolved in a 2% by weight aqueous solution of sulfuric acid as a polymer antimicrobial agent was added to the prepared ABS graft copolymer latex to agglomerate at 70 ° C. It was. After coagulation, the mixture was aged at 90 ° C., dehydrated and dried to obtain an ABS graft copolymer powder. The filtrate generated at this time was analyzed by liquid chromatography, and chitosan was not detected.

B) Copolymer (SAN) Resin Preparation

Into a nitrogen-filled polymerization reactor, 25 parts by weight of acrylonitrile and 75 parts by weight of styrene were continuously added with a raw material obtained by mixing 30 parts by weight of toluene as a solvent and 0.15 parts by weight of tertiary dodecyl mercaptan as a molecular weight regulator to react the reaction temperature. It maintained at 148 degreeC, and made average reaction time into 3 hours. The polymerization liquid discharged from the reaction tank was heated in a preheating bath, the unreacted monomer was volatilized in the volatilization tank, and the copolymer resin was pelleted using a copolymer transfer pump and an extrusion process to maintain the temperature of the copolymer at 210 ° C. Processed into the form.

C) Preparation of the thermoplastic resin composition (A) + B) Melting Kneading )

40 parts by weight of the obtained A) ABS graft copolymer powder and 60 parts by weight of the B) copolymer (SAN) resin were mixed in a conventional mixer, 1.0 part by weight of lubricant and 0.2 part by weight of antioxidant were added, and a biaxial extruder was used. Melting and kneading at 200 ° C to prepare a resin composition in the form of pellets, the resin composition of the pellets prepared by injection was prepared as a specimen for measuring the physical properties.

Example  2

5 weight parts of polydiallyldimethyl ammonium chloride solution in which 2 weight% of polydiallyldimethyl ammonium chloride was dissolved in 2 weight% aqueous solution of sulfuric acid instead of 5 parts by weight of chitosan solution (based on chitosan solids) as a polymer antimicrobial agent during the aggregation and aging process of Example 1. It was prepared in the same manner as in Example 1 except that parts (based on polydiallyldimethylammonium chloride solids) were used. The filtrate generated during the flocculation and aging process was analyzed by liquid chromatography, and polydiallyldimethylammonium chloride was not detected.

Example  3

PolyN-vinylpyrrolidone aqueous solution 5 in which 2% by weight of polyN-vinylpyrrolidone was dissolved in 2% by weight aqueous solution of sulfuric acid instead of 5 parts by weight of aqueous chitosan solution (based on solids) as a polymer antimicrobial agent during the aggregation and aging process of Example 1. It was prepared in the same manner as in Example 1 except that parts by weight (based on poly N-vinylpyrrolidone solid content) were used. The filtrate generated during the flocculation and aging process was analyzed by liquid chromatography. No polyN-vinylpyrrolidone was detected.

Example  4

Except for using 10 parts by weight (based on chitosan solids) chitosan aqueous solution in the aggregation and aging process of Example 1 was prepared in the same manner as in Example 1. The filtrate generated during the aggregation and aging process was analyzed by liquid chromatography, and chitosan was not detected.

Example  5

Except for using the chitosan aqueous solution 2 parts by weight (based on chitosan solids) in the aggregation and aging process of Example 1 was prepared in the same manner as in Example 1. The filtrate generated during the aggregation and aging process was analyzed by liquid chromatography, and chitosan was not detected.

Comparative example  One

Except that 5 parts by weight of aqueous solution of chitosan (based on chitosan solid content) instead of 5 parts by weight of aqueous solution of chitosan as a polymer antimicrobial agent in the aggregation and aging process of Example 1 was prepared in the same manner as in Example 1.

Comparative example  2

Except for using 1 part by weight of chitosan aqueous solution (based on chitosan solids) in the aggregation and aging process of Example 1 was prepared in the same manner as in Example 1.

Comparative example  3

A) + B) of the Comparative Example 1 was prepared in the same manner as in Comparative Example 1 except that 20 parts by weight of chitosan dry powder was added together with the lubricant and additives as additives.

[Test Example]

The physical properties of the thermoplastic resin composition specimens obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were measured by the following method, and the results are shown in Table 1 below.

How to measure

* Antimicrobial activity: Staphylococcus bacterium reduction rate was measured after 24 hours at 35 ℃ using Staphylococcus aureus according to the antimicrobial activity test method KICM-FIR-1003 using a specimen.

* Impact strength (Notched Izod, kg · cm / cm): Measured according to standard measurement ASTM D256 using a 1/4 "specimen.

* Melt Index (Melt Index, g / 10 min): Measured according to the standard measurement ASTM D1238 (220 ℃, 10 kg conditions) using the specimen.

* Gel content and swelling index: Butadiene rubber latex is coagulated with dilute acid or metal salt, washed, dried in a vacuum oven at 60 ° C for 24 hours, chopped rubber mass with scissors and 1 g of rubber sections 100 g of toluene was stored in a dark room at room temperature for 48 hours, and then separated into sol and gel and dried, respectively, and the gel content was expressed by Equation 1 below, and the swelling index was measured by Equation 2 below.

* Average particle size: Dynamic laser light was measured by 370 HPL of Nicomp, USA.

division	Example					Comparative example
	One	2	3	4	5	One	2	3
Impact strength (kgcm / cm)	33.0	32.7	29.2	28.0	33.0	32.0	32.5	7.1
Melt Index (g / 10 min)	23	20	22	19	22	24	23	12
Antimicrobial activity	◎	◎	◎	◎	○	×	×	○
* Antibacterial: Based on bacteria reduction rate, it was divided into three stages (◎-very good, ○-good, ×-bad).

As shown in Table 1, the impact strength of all of Examples 1 to 5 using chitosan, polydiallyldimethylammonium chloride and polyN-vinylpyrrolidone, which are polymer antimicrobial agents having amine groups, as a coagulant, was 10 kg It was confirmed that the mechanical properties are excellent in the cm / cm or more, excellent fluidity from the melt index of 13 g / 10 min or more and excellent melt kneading of the thermoplastic resin contained in the composition of the above embodiment, and also excellent antibacterial activity I could confirm that.

On the other hand, Comparative Example 1 in which the polymer antimicrobial agent having an amine group was not added during the coagulation and aging process and Comparative Example 2 in which 1 part by weight of chitosan, which is a polymer antimicrobial agent having an amine group, were not very good. In Comparative Example 3 in which the antimicrobial agent was added by 20 parts by weight during melt kneading, the antimicrobial activity was shown, but the impact strength and the melt index were found to be very low.

In conclusion, the thermoplastic resin manufacturing method of the present invention, when the graft copolymer latex is agglomerated using a polymer antimicrobial agent having a primary, secondary, tertiary or quaternary amine group, the antibacterial and melt kneading of the thermoplastic resin produced It is to use the excellent properties, it can be seen that due to the invention as described above to produce a thermoplastic resin excellent in antimicrobial and melt kneading properties, it can be implemented a thermoplastic resin composition excellent in both mechanical properties, fluidity and antibacterial properties.

Claims (16)

1. i) graft polymerization comprising a) conjugated diene rubber, b) at least one selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound and an acrylate compound to produce a graft copolymer latex; And

   ii) injecting the polymer antimicrobial agent having a primary, secondary, tertiary or quaternary amine group into the graft copolymer latex to agglomerate the thermoplastic resin.
2. The method of claim 1,

   The aggregation of step ii) is a thermoplastic resin manufacturing method, characterized in that carried out at pH 2 to 6.
3. The method of claim 1,

   The polymer antimicrobial agent of step ii) is dissolved in 0.1 to 10% by weight in an acid solution having a pH of 2 to 5 thermoplastic resin production method characterized in that the input.
4. The method of claim 1,

   The polymer antimicrobial agent having the amine group is a thermoplastic resin production method, characterized in that added to less than 20 parts by weight based on 100 parts by weight of the graft copolymer total.
5. The method of claim 1,

   The polymer antimicrobial agent having an amine group is a method for producing a thermoplastic resin, characterized in that at least 50% of the monomer constituting the monomer containing a primary, secondary, tertiary or quaternary amine group.
6. The method of claim 1,

   The polymer antimicrobial agent having an amine group is polydiallyldimethyl ammonium chloride {poly (diallyldimethyl ammonium chloride)}, polydicyandiamide, polyN-vinylpyrrolidone {poly (N-vinylpyrrolidone)}, polyethyleneimine ), Chitosan (chitosan), chitosan derivatives (modified chitosan) and polyvinylpyridine (polyvinylpyridine) is at least one member selected from the group consisting of thermoplastic resins.
7. The method of claim 1,

   The polymer antimicrobial agent having an amine group is a thermoplastic resin production method characterized in that at least 1 g at 23 ℃ to 100 g of an acid solution having a pH of 1 to 5.
8. The method of claim 1,

   The a) conjugated diene rubber is added to 20 to 70% by weight, b) at least one selected from the group consisting of aromatic vinyl compound, vinyl cyan compound and acrylate compound is added to 30 to 80% by weight Thermoplastic resin manufacturing method.
9. The method of claim 1,

   The acrylate compound is one selected from the group consisting of (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid 2-ethylhexyl ester, and (meth) acrylic acid decyl ester The thermoplastic resin manufacturing method characterized by the above.
10. The method of claim 1,

    The aromatic vinyl compound is at least one member selected from the group consisting of styrene, α-methyl styrene, ο-ethyl styrene, p-ethyl styrene and vinyl toluene.
11. The method of claim 1,

    The vinyl cyan compound is at least one member selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile.
12. a graft copolymer obtained by a) conjugated diene rubber, b) at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds and acrylate compounds; And a polymer antimicrobial agent having a primary, secondary, tertiary or quaternary amine group.
13. i) graft polymerization comprising a) conjugated diene rubber, b) at least one selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound and an acrylate compound to produce a graft copolymer latex;

    ii) aggregating a polymer antimicrobial agent having a primary, secondary, tertiary or quaternary amine group into the graft copolymer latex;

    iii) obtaining a thermoplastic resin from the aggregated graft copolymer; And

    iv) 20 to 80% by weight of the thermoplastic resin and B) 20 to 80% by weight of at least one polymerized copolymer resin selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds and acrylate compounds. Step; thermoplastic resin composition manufacturing method comprising a.
14. A) 20 to 80% by weight of the thermoplastic resin of claim 12 and B) at least one member selected from the group consisting of aromatic vinyl compound, vinyl cyan compound and acrylate compound comprises 20 to 80% by weight polymerized copolymer resin The thermoplastic resin composition characterized by the above-mentioned.
15. The method of claim 14,

    The thermoplastic resin composition has a conjugated diene rubber content of 5 to 35% by weight.
16. The method of claim 14,

    The thermoplastic resin composition is characterized in that the impact strength is 10 kg · cm / cm or more.