KR20100009277A - Antibacterial resin composition for injection molding of natural ventilating device and antibacterial natural ventilating device using the composition - Google Patents

Abstract

PURPOSE: An antibacterial resin composition is provided to improve antibacterial property for bacteria and mold, and antibacterial durability while not lowering shock resistance and thermal stability of a thermoplastic resin due to the stability of organic biocide. CONSTITUTION: An antibacterial resin composition for injection molding of a natural ventilation device comprises (A) a thermoplastic resin 100.0 parts by weight selected from acrylonitrile-butadiene-styrene resin, polycarbonate resin, or their mixture, (B) an inorganic antimicrobial agent 0.1-1.0 parts by weight, and (C) an organic antimicrobial agent 0.1-1.0 parts by weight selected from 2,4,4'-trichloro-2'-hydroxy diphenyl ether, 4,5-dichloro-2-(n-octyl)-isothiazolin-3-one, or their mixture.

Description

ANTIBACTERIAL RESIN COMPOSITION FOR INJECTION MOLDING OF NATURAL VENTILATING DEVICE AND ANTIBACTERIAL NATURAL VENTILATING DEVICE USING THE COMPOSITION}

The present invention does not lower the overall physical properties of the thermoplastic resin itself when injection molding at a high temperature, and the antibacterial resin composition for injection of a natural ventilation device that can improve the antimicrobial and antimicrobial sustainability of the mold as well as bacteria and antimicrobial natural ventilation prepared therefrom Relates to a device.

Recently, as a method for ventilating indoor air of a building, there is a growing interest in a natural ventilation device using only simple operation without opening a window.

The natural ventilation device is a device for ventilating air by using the difference between the outdoor natural wind and the indoor temperature and air pressure, and is designed in a geometric structure to maintain a constant ventilation amount. In addition, the outdoor air inlet passage of the natural ventilation device is provided with a filter for preventing the introduction of various pollutants, such a filter is convenient to clean and replace.

As such, when the natural ventilation device is used, it is not necessary to open the window, thereby reducing the amount of energy used and the cost thereof, and preventing the invasion of outsiders.

However, due to the temperature difference between indoor and outdoor air, condensation, and rainwater introduced in the rainy season, water is generated in the structure of the natural ventilation system. As a result of this moisture, various bacteria and fungi multiply and the air enters the room. There is a problem of polluting. This phenomenon has become more serious recently when the interior of the house is extended by extending the balcony of the house.

On the other hand, the natural ventilation device is made of aluminum or polyvinyl chloride (PVC), polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polyolefin (PO), acrylonitrile-butadiene-styrene (ABS) And a plastic material such as polycarbonate (PC) resin.

In general, plastic is considered to be a material that is difficult to be contaminated by microorganisms, but when an additive used in processing or a contaminant attached to the surface of the plastic becomes a nutrient to the microorganism, the microorganism grows and the plastic itself deteriorates and Mold will develop. In particular, recently, due to the encapsulation of the residential environment and the optimization of the indoor temperature, an environment that is well-matched with the growth conditions of bacteria and fungi has been created.

In order to solve the above problems, a method of antimicrobial coating treatment on the surface after molding the plastic or a method of kneading by incorporating an antimicrobial agent during molding of the plastic has been proposed, of which kneading is mainly used.

Antimicrobial agents used to impart antimicrobial properties to plastics are largely divided into inorganic and organic antimicrobials. Inorganic antimicrobial agents have a continuous antimicrobial effect against bacteria, but require a relatively high amount of antimicrobial activity.As the amount of the antimicrobial agent increases, the dissolution of metal ions occurs during molding, resulting in discoloration of the resin and antimicrobial activity against mold. It has the disadvantage of being weak. On the other hand, the organic antimicrobial agent has an excellent antimicrobial effect against bacteria and fungi, but it is difficult to maintain stability at high temperature, so that the antimicrobial persistence is lowered because it is easily eluted during the molding process of plastics.

In addition, in order to maintain a good shape or shape of the product during injection molding, the plastic must increase the molding temperature to improve fluidity, but the molding temperatures are different depending on the type of resin. In particular, ABS or PC resins are more preferable for application to natural ventilation devices because of their excellent impact resistance, processability, and mechanical strength, but they are more suitable for the application of antimicrobial agents, especially organic antimicrobial agents, because the molding temperature is higher than other resins. There was a difficulty.

Accordingly, there is a need for an injection resin composition that is suitable for injection molding of a natural ventilation device using ABS or PC resin, and has excellent antimicrobial and antimicrobial sustainability, which can simultaneously prevent bacteria and mold without deteriorating the overall physical properties of the resin.

The present invention does not deteriorate the physical properties of the thermoplastic resin itself by adding a specific antimicrobial agent that is stable even when injected at a high temperature, and antibacterial resin composition and natural ventilation for injection of natural ventilation device excellent in antimicrobial and antimicrobial sustainability for mold as well as bacteria. It is an object to provide an antimicrobial masterbatch for device injection.

It is another object of the present invention to provide an antimicrobial compound prepared from the antimicrobial resin composition or the antimicrobial masterbatch.

In addition, another object of the present invention is to provide an antimicrobial natural ventilation device prepared from the antimicrobial resin composition or the antimicrobial masterbatch and a method of manufacturing the same.

The present invention comprises 100 parts by weight of a thermoplastic resin selected from (A) acrylonitrile-butadiene-styrene resin, polycarbonate resin or mixtures thereof, (B) 0.1-1.0 part by weight of inorganic antibacterial agent, and (C) 2,4,4 0.1-1.0 parts by weight of an organic antibacterial agent selected from ´-trichloro-2´-hydroxy diphenyl ether, 4,5-dichloro-2- (n-octyl) -isothiazolin-3-one or mixtures thereof It provides an antibacterial resin composition for natural ventilation device injection, characterized in that made.

In addition, the present invention provides a composition comprising (a) 50-99% by weight of a thermoplastic resin selected from acrylonitrile-butadiene-styrene resin, polycarbonate resin or mixtures thereof, (b) inorganic antibacterial agent, and 2,4,4′-trichloro 1-50% by weight of an organic antimicrobial agent selected from -2'-hydroxy diphenyl ether, 4,5-dichloro-2- (n-octyl) -isothiazolin-3-one or mixtures thereof It provides an antibacterial masterbatch for natural ventilation device injection.

In addition, the present invention provides an antimicrobial compound and antimicrobial natural ventilation device prepared from the antimicrobial resin composition.

In addition, the present invention provides a method for producing an antimicrobial natural ventilation device comprising the step of injection at 280-350 ℃ using the antimicrobial resin composition.

The antimicrobial resin composition for natural ventilation device injection of the present invention does not reduce the overall physical properties such as impact resistance and thermal stability of the thermoplastic resin itself due to the stability of the organic antimicrobial agent even when injection molding at a high temperature. It is effective in improving (short-term antimicrobial) and antimicrobial persistence (long-term antimicrobial). In addition, by preventing bacteria and mold to minimize the change in color, physical properties and shape of the natural ventilation device component, thereby preventing indoor air pollution.

The present invention relates to an antibacterial resin composition for natural ventilation device injection and an antibacterial natural ventilation device prepared therefrom.

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

As used herein, the term “antibacterial” means antibacterial activity against both “bacteria” and “fungus,” and “resin” includes both resins such as liquid, solid or powder.

The antimicrobial resin composition for natural ventilation device injection of the present invention comprises (A) 100 parts by weight of thermoplastic resin, (B) 0.1-1.0 parts by weight of inorganic antibacterial agent, and (C) 2,4,4'-trichloro-2'-hydride. 0.1-1.0 parts by weight of an organic antimicrobial agent selected from oxydiphenyl ether, 4,5-dichloro-2- (n-octyl) -isothiazolin-3-one or mixtures thereof.

The thermoplastic resin (A) of the present invention may be a resin selected from an ABS resin, a PC resin, or a mixture thereof, and the type thereof is not particularly limited as long as it is commonly used in the art.

As the thermoplastic resin, an ABS resin is preferable, and the ABS resin and the PC resin are 5: 5-7: 3 to simultaneously combine excellent properties such as processability and impact resistance of the ABS resin with excellent properties such as heat resistance and mechanical strength of the PC resin. It is also preferable to mix by weight ratio of.

The ABS resin is preferably a resin composed of 20-80 wt% of a matrix copolymer having a weight average molecular weight of 2 × 10 ⁵ or more and 20-80 wt% of a graft copolymer.

The matrix copolymer is preferably 35-70% by weight of the styrene monomer and 30-65% by weight of one or more monomers selected from acrylic monomers or acrylonitrile monomers can be maintained because the heat resistance. In addition, the graft copolymer is excellent in containing 20-60% by weight of rubbery polymer, 20-60% by weight of styrene monomer and 20-60% by weight of at least one monomer selected from acrylic monomer or acrylonitrile monomer. Since impact and workability can be provided, it is preferable.

The acrylic monomer may be a (meth) acrylic acid or a (meth) acrylic acid alkyl ester monomer, and specific examples thereof include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, and (meth) acrylic acid butyl ester , (Meth) acrylic acid hexyl ester, (meth) acrylic acid 2-ethylhexyl ester, and the like, and among these, methacrylic acid methyl ester is preferable.

Specific examples of the rubbery polymer include polybutadiene, butadiene-styrene copolymer, polyisoprene, butadiene-acrylonitrile copolymer, isobutylene-isoprene copolymer, ethylene-propylene rubber, acrylic rubber, urethane rubber or silicone rubber. Can be mentioned.

As the PC resin, a resin having an aromatic group in the main chain and having a viscosity average molecular weight of 1.8 × 10 ⁴ -3.0 × 10 ⁴ or more is preferable for balancing physical properties such as mechanical strength.

Inorganic antibacterial agent (B) of the present invention is an antimicrobial agent that exhibits excellent antimicrobial activity against bacteria in thermoplastic resins, and is silver, which is a metal ion that has an antimicrobial effect on at least one inorganic material selected from the group consisting of zeolite, calcium phosphate and zirconium phosphate. And antibacterial agents substituted with zinc, copper, and the like, and nano-silver.

The inorganic antimicrobial agent is preferably included in 0.1 to 1.0 parts by weight based on 100 parts by weight of the thermoplastic resin. If the content is less than 0.1 parts by weight, it is difficult to obtain the desired antimicrobial effect, and if it exceeds 1.0 parts by weight, it is possible to change the overall physical properties of the thermoplastic resin and to increase the cost.

The (C) organic antimicrobial agent of the present invention is an antimicrobial agent for inhibiting mold growth that is difficult to solve only by an inorganic antimicrobial agent, and is stable at high temperatures, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether (TCHDE), Preference is given to 4,5-dichloro-2- (n-octyl) -isothiazolin-3-one (DCOIT) or mixtures thereof. The TCHDE or DCOIT is stable even at a high temperature of 280 ° C. or higher, preferably 280-350 ° C. during extrusion or injection of an ABS resin or a PC resin, thereby improving antimicrobial and antimicrobial sustainability without lowering overall physical properties of the thermoplastic resin itself. have.

As the organic antimicrobial agent, 2,4,4'-trichloro-2'-hydroxydiphenyl ether (TCHDE) is more preferable because it has better stability at high temperature, and 2,4,4'-trichloro-2 --Hydroxydiphenyl ether and 4,5-dichloro-2- (n-octyl) -isothiazolin-3-one in a 6: 4-9: 1 mixture not only maintains physical properties but also It is most preferable in that it is economical because it improves antimicrobial sustainability due to stability.

The organic antimicrobial agent is preferably included in 0.1 to 1.0 parts by weight of 100 parts by weight of the thermoplastic composition. If the content is less than 0.1 parts by weight, it is difficult to obtain the desired antimicrobial effect, and if it exceeds 1.0 parts by weight, the stability of the antimicrobial agent is reduced during extrusion or injection, resulting in deterioration phenomenon, thereby causing discoloration and gas generation problems of the thermoplastic resin. Is induced.

In the present invention, the weight ratio of the inorganic antimicrobial agent and the organic antimicrobial agent is preferably 1: 1-5: 1. When the weight ratio is included in the above range, it is possible to maintain the complementary antimicrobial and antimicrobial persistence against bacteria or fungi of the inorganic antimicrobial agent and the organic antimicrobial agent.

The antimicrobial resin composition of the present invention may further include calcium stearate to improve the antimicrobial and antimicrobial retention by maintaining the organic antimicrobial agent stable even at a high temperature, and to prevent thermal deformation of the thermoplastic resin.

The calcium stearate is preferably included in an amount of 0.03-1.5 parts by weight based on 100 parts by weight of the thermoplastic resin. If the content is less than 0.03 parts by weight, the effect of imparting stability of the organic antimicrobial agent may be insignificant. If the content exceeds 1.5 parts by weight, the overall physical properties of the thermoplastic resin may be lowered, and further effects are uneconomical.

In addition, the antimicrobial resin composition may further include a wax to smoothly mix the thermoplastic resin and the inorganic and organic antimicrobial agents.

The wax may be included in an amount of 0.15-1.5 parts by weight with respect to 100 parts by weight of the thermoplastic resin so that the antimicrobial agent may be sufficiently dispersed without lowering the physical properties of the thermoplastic resin.

The antimicrobial resin composition comprising the above components is a mixture of talc and barium sulfate to complement the mechanical properties such as heat resistance, dimensional stability, rigidity, and also to sound-absorbing sound from the outside of the natural ventilation device. It may include. Compared with talc, barium sulfate is somewhat better in sound absorption, but it is difficult to mold when used alone because of its high hygroscopicity, and talc has better heat resistance than barium sulfate, but may cause appearance defects in molded products.

The talc and barium sulfate are preferably used in a weight ratio of 4: 6-6: 4, and may be included in an amount of 0.1-20 parts by weight based on 100 parts by weight of the thermoplastic resin of the present invention.

The talc is preferably used having an average particle diameter of 1-20 μm, specific gravity of 2.5-3.0 g / cm 3 and water content of 2000 ppm or less.

In addition to the above components, the antimicrobial resin composition of the present invention may further include additives such as dyes, pigments, antioxidants, heat stabilizers, lubricants, and flame retardants.

The antimicrobial resin composition of the present invention can be applied not only to injection molding of a natural ventilation device, but also to products manufactured by injection molding as other products susceptible to bacteria and molds, for example, flooring.

The present invention provides an antimicrobial masterbatch for natural ventilation device injection.

Masterbatch is a pellet-shaped raw material in which inorganic and organic antimicrobial agents are concentrated and dispersed in a thermoplastic resin, and effectively induces dispersion of inorganic and organic antimicrobial agents to improve antimicrobial sustainability without lowering impact resistance and thermal stability. have.

The masterbatch comprises (a) 50-99% by weight of a thermoplastic resin, (b) 1-50% by weight of an inorganic antimicrobial agent and an organic antimicrobial agent.

The thermoplastic resin, the inorganic antimicrobial agent and the organic antimicrobial agent may be the same as in the antimicrobial resin composition.

The inorganic antimicrobial agent and the organic antimicrobial agent are included in the total amount of the masterbatch 1-50% by weight, preferably 1-30% by weight, more preferably 3-15% by weight, and their weight ratio is 1: 1-6: It is preferable that it is four. If the content of the organic and inorganic antimicrobial agent is less than 1% by weight, the antimicrobial persistence is lowered, and if the content of the organic and inorganic antimicrobial agent exceeds 50% by weight, discoloration problems may occur due to an increase in the metal ion content of the inorganic antimicrobial agent and deterioration of the organic antimicrobial agent.

The masterbatch is prepared by a method comprising (i) a first step of mixing a thermoplastic resin with an inorganic and organic antimicrobial agent, and (ii) a second step of pelletizing the mixture by introducing it into an extruder. In detail, an inorganic antimicrobial agent and an organic antimicrobial agent are added and mixed in a tumbler or a mixer, and a thermoplastic resin is added thereto and stirred at a speed of about 1000 rpm to prepare a mixture. At this time, calcium stearate may be added by spraying at the same time as the organic antimicrobial agent is added, and after adding the thermoplastic resin, wax may be further added. The mixture is then introduced into an extruder and heated to melt and forced kneaded to pelletize. In this case, when cooling by water cooling, dissolved oxygen in the cooling water and ions contained in the inorganic antimicrobial agent may be chemically combined to discolor the color of the masterbatch. Thus, chlorine and sulfide ions which cause discoloration among the anions in the cooling water are activated carbon. It is preferable to adsorb | suck and remove using.

The antimicrobial masterbatches prepared as described above can effectively induce the dispersion of inorganic and organic antimicrobial agents to prevent mechanical properties deterioration and discoloration during injection molding of natural ventilation devices, and improve the antimicrobial and antimicrobial persistence of fungi as well as bacteria. Can be.

The present invention provides an antimicrobial compound prepared from the antimicrobial resin composition.

The compound may be prepared by a method commonly used in the art.

In addition, the present invention provides an antimicrobial natural ventilation device prepared from the antimicrobial resin composition.

The natural ventilation device is a device used for the window of the building, as well as the body of the natural ventilation device parts such as end caps, flaps can be made of an antimicrobial resin composition.

The natural ventilation device may be prepared using an extrusion and injection molding method commonly used in the art, in particular a method comprising the step of injecting the antimicrobial resin composition at 280-350 ℃, preferably 350 ℃ Are manufactured.

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  One

60 parts by weight of an ABS resin prepared by emulsion polymerization and having a rubber content of 42% by weight, 25 parts by weight of acrylonitrile-styrene copolymer prepared by bulk polymerization, and 25 parts by weight of a PC resin having a viscosity average molecular weight of 2.55 × 10 ⁴ A thermoplastic resin made up was prepared. 0.8 parts by weight of an inorganic antibacterial zeolite was added to the mixer, 0.5 parts by weight of calcium stearate, and 0.5 parts by weight of 2,4,4'-trichloro-2'-hydroxydiphenyl ether (TCHDE), which was an organic antimicrobial, Mixed. Subsequently, 0.3 parts by weight of the thermoplastic resin and the wax were added to the mixer and mixed to prepare an antimicrobial resin composition.

The prepared antimicrobial resin composition was melt extruded in an extruder to prepare pellets, and the prepared pellets were injection molded at 350 ° C. with an injection molding machine to prepare specimens.

Example  2

The same procedure as in Example 1 was conducted except that 4,5-dichloro-2- (n-octyl) -isothiazolin-3-one (DCOIT) was used as the organic antibacterial agent.

Example  3

Organic antimicrobial agents were treated with 2,4,4'-trichloro-2'-hydroxy diphenyl ether (TCHDE) and 4,5-dichloro-2- (n-octyl) -isothiazolin-3-one 7: 3. The mixing was carried out in the same manner as in Example 1, except that the mixture was used in a weight ratio of.

Example  4

The organic antimicrobial agent 2,4,4'-trichloro-2'-hydroxy diphenyl ether (TCHDE) was used in the same manner as in Example 1 except that 0.2 parts by weight.

Example  5

The organic antimicrobial agent was used in the same manner as in Example 1, except that 0.8 parts by weight of 2,4,4′-trichloro-2′-hydroxy diphenyl ether (TCHDE) was used.

Comparative example  One

The same procedure as in Example 1 was conducted except that no organic antimicrobial agent was used.

Comparative example  2

The same procedure as in Example 1 was conducted except that 1.2 parts by weight of 2,4,4'-trichloro-2'-hydroxy diphenyl ether (TCHDE), which was an organic antibacterial agent, was used.

Comparative example  3

Except for using 0.5 parts by weight of 2-n-octyl-isothiazolin-3-one (OIT) as an organic antimicrobial agent was carried out in the same manner as in Example 1.

Comparative example  4

Except for using 0.5 parts by weight of polyhexyl methyleneguanidine phosphite as the organic antibacterial agent was carried out in the same manner as in Example 1.

Comparative example  5

10,10'-Oxybisphenoxyarsine (OBPA) was used in the same manner as in Example 1 except that 0.5 parts by weight of the organic antimicrobial agent was used.

Comparative example  6

Zinc 2-pyridinethiol-1-oxide (Z-PTO) was used in the same manner as in Example 1 except that 0.5 parts by weight of the organic antibacterial agent was used.

division Thermoplastic resin Calcium Stearate Wax Inorganic antibacterial agents Organic antibacterial ABS PC TCHDE DCOIT OIT Guanine OBPA Z-PTO Example 1 75 25 0.5 0.3 0.8 0.5 - - - - - Example 2 75 25 0.5 0.3 0.8 - 0.5 - - - - Example 3 75 25 0.5 0.3 0.8 0.35 0.15 - - - - Example 4 75 25 0.5 0.3 0.8 0.2 - - - - - Example 5 75 25 0.5 0.3 0.8 0.8 - - - - - Comparative Example 1 75 25 0.5 0.3 0.8 - - - - - - Comparative Example 2 75 25 0.5 0.3 0.8 1.2 - - - - - Comparative Example 3 75 25 0.5 0.3 0.8 - - 0.5 - - - Comparative Example 4 75 25 0.5 0.3 0.8 - - - 0.5 - - Comparative Example 5 75 25 0.5 0.3 0.8 - - - - 0.5 - Comparative Example 6 75 25 0.5 0.3 0.8 - - - - - 0.5

Test Example

The overall physical properties, antimicrobial and antimicrobial persistence of the specimens prepared in Examples and Comparative Examples were tested in the following manner.

(1) IZOD impact strength (kgcm / cm)

It measured according to ASTM D256 method. At this time, the thickness of the specimen was 1/4.

(2) thermal instability (injection retention thermal stability, ΔE)

Molded one molded article by inserting the antimicrobial resin composition processed in pellet form while maintaining the cylinder temperature of the injection machine at 350 ℃, and maintained for 20 minutes in a stagnant state, and then re-inject the molded article and After the second 20 minutes stay, the degree of color change of the molded article was compared and represented by ΔE. If the difference of △ E is small, discoloration due to instability of the antimicrobial agent is low, and the thermal stability of the product is excellent, and it is widely used as a comparative evaluation method. Generally, when △ E is less than 1.0, it is a very good level, and △ E is If it is 2.0 or higher, a problem is expected in the thermal stability of the product. At this time, the measurement of ΔE, the degree of color change, was measured according to the ASTM D1925 method.

(3) Antimicrobial activity against Escherichia coli (decay rate (%))

Measurement standard: Shaking flask test based on SIAA standard was applied and Escherichia coli ATCC 8739 was used as the used strain.

-Method of measurement: Shake incubator at 30 ° C after cutting 2 g / 10 ml of the specimen in 50 ml of phosphate buffer (pH 6.8) in which bacteria were diluted to a concentration of 1 × 10 ⁴ -10 ⁵ . Rotate incubate for 24 hours at. At this time, the culture bacteria were collected at the beginning of the specimen administration and 24 hours, the number of viable cells was measured, and the decay rate was calculated.

(4) antimicrobial activity against bacteria (% loss)

-Measurement standard: Applied pressure bonding method, and used strains were Bacillus Megaterium ATCC 10778), Pseudomonas Aeruginosa ATCC 15442), bacteria jangtipeuseu (Salonella Typhimyriym KCTC 1925) and the like four or more were used.

-Method of measurement: Inoculate test specimen and control specimen with test specimen, and inoculate a certain amount of inoculum between test specimen and specimen, and extract cultured bacteria. When the number of bacteria present in the extract is measured, the rate of bacterial reduction between the antimicrobial test specimen and the control specimen is measured. The size of the test piece is a rectangle of 5 cm × 6 cm in width and length, respectively, with N number of three pairs or more. In addition, the control piece is also prepared in the same size as the test piece.

For inoculum preparation, dilute the broth broth cultured for 24 hours so that the number of bacteria regenerated from the test specimen or the control specimen at 0 hour contact time is 1-2 × 10 ⁶ , and use 0.1 ml of the bacterial solution as the inoculum. At this time, the dilution of the culture solution using physiological saline.

The control specimen is the same kind and structure as the test specimen, but is used as a control means for the test specimen inoculated with bacteria and the non-inoculated specimen, which is obtained from a product which does not perform antimicrobial processing.

Inoculation of test specimens and control specimens is shaken for 24 hours when using E. coli and allowed to stand for 15 minutes before preparing the inoculum. Using a pipette, 0.1 ml of inoculum is evenly adhered on the test piece and the control piece. Sampling at contact time 0 is carried out as soon as possible after inoculation with a pipette dish inoculated with a neutralized solution of phosphate buffer (pH 7.2). In addition, uninoculated test pieces are also placed in a pipette dish and washed with a neutralizing solution (20 ml). Shake slowly for exactly 1 minute, then dilute continuously. 0.2 ml of each of them is harvested and inoculated in a thin plate of Tryptone glucose extract agar medium. At this time, 10-fold, 100-fold dilution is usually suitable. Neutralization solution should be neutralized by special antibacterial treatment and suitable for the required pH conditions. Sampling from the culture through a constant contact time, place the inoculated specimens and control pieces in a pipette dish, wash with neutralizing solution, shake slowly for exactly 1 minute, and continue diluting. Incubate in a plate incubator at 30 ° C. for 48 hours.

(5) short-term antimicrobial activity against mold

-Measurement standard: It was measured according to ASTM G-21 method. The strains used were Aspergillus niger and Penicillium. citrinum and the like were used. The growth of the fungus is assessed according to the grading criteria set as follows after incubating the test specimens for 3 weeks, and in the case of 0 grade, the antifungal effect is evaluated.

Grade 0: Unrecognized growth of fungal strains

Grade 1: growth of fungal strains is less than 10%

Grade 2: Growth of fungal strains was 10-30%

Grade 3: growth of fungal strains was 30-60%

Class 4: Over 60% of Specimen Area

-Method of measurement: After inoculating the specimen and the control specimen with a mixed spore suspension and incubating for a certain period of time, the growth status of the cultured mold was compared between the test specimen and the control specimen. It is a qualitative indication of the degree of moldiness. The size of the test piece is prepared by 3 cm × 3 cm to prepare three, and the control piece is also prepared in the same way. For inoculum preparation, 50 ml of sterile water to which 0.005% of dioctyl sodium sulfosuccinate was added was placed in a 100 ml Erlenmeyer flask, and each mold spores were collected and sufficiently dispersed. The contents were filtered with gauze to make the filtrate a mixed spore suspension. Test pieces and control pieces were prepared by placing them on a prepared medium in a glass container of 9 cm × 9 cm. The size of the test piece and the control piece into the container is prepared to be 3 cm × 3 cm, and the container containing the sample is prepared three pieces each for the test piece and the control piece.

The medium used is Potato dextrose dextrose agar (PDA), which is sterilized in a high pressure sterilizer at a steam pressure of 1,055 g / cm 2 and 120 ± 2 ° C for 20 minutes. The control piece is used as a control means for the control and inoculated test pieces inoculated with fungus, using the same type and structure as the test piece, but taken from a product that has not been processed. Inoculation of test specimens and control specimens should be prepared in advance the day before the use of the mixed spores and sprayed on the sample with a sterilized sprayer on the day of the test. Incubate the specimens and control specimens in a plate incubator for 3 weeks at 25 ± 2 ° C and 75% relative humidity.

(6) long-term antimicrobial activity against mold (antibacterial retention)

After keeping the prepared specimens for 6 months at 0 ℃ and 80 ℃ temperature (external temperature available for natural ventilation) for 1 month each time, the growth of fungal strains was measured and graded by the same measuring method as above. Was evaluated.

division Impact Strength (㎏ · cm / ㎝) Thermal instability (△ E) Escherichia coli attenuation rate (%) Bacterial Decay Rate (%) Short-term mold antibacterial (3 weeks) Long-term mold antibacterial (6 months) Example 1 55 0.8 99.99 99 0 0 Example 2 54 0.8 99.70 97 0 0 Example 3 53 0.8 99.99 98 0 0 Example 4 54 0.8 98.50 97 0 0 Example 5 53 0.9 99.97 99 0 0 Comparative Example 1 55 0.8 98.50 98 One 3 Comparative Example 2 47 1.1 99.80 99 0 One Comparative Example 3 43 2.0 98.90 97 One 3 Comparative Example 4 46 1.8 98.55 97 One 2 Comparative Example 5 45 1.9 98.60 96 One 2 Comparative Example 6 51 1.5 98.90 98 One 2

As shown in Table 2, the specimens of Examples 1 to 5 prepared from the antimicrobial resin composition according to the present invention have short-term and long-term antimicrobial activity against bacteria decay rate and mold without deteriorating physical properties such as impact resistance and thermal stability. This excellent thing was confirmed. In addition, Figure 1 shows the results of the decay rate test for E. coli according to Example 1 of the present invention, Figure 2 and Figure 3 shows the antimicrobial test results for the fungus of the specimens according to Examples 1 and 3, respectively. As a result, the specimen of Example 1 was significantly attenuated E. coli compared to the control group without using it, the specimens of Examples 1 and 3 is the most widely formed in the clean area with the mold removed around the bacteria and fungi The antimicrobial activity was the best.

On the other hand, the specimen of Comparative Example 1 containing only an inorganic antimicrobial agent did not have good antimicrobial activity against the fungus, the specimen of Comparative Example 2 containing an excessive amount of the organic antimicrobial was lowered the impact strength and thermal stability. In addition, Comparative Examples 3 (FIG. 3) to 6 containing other types of organic antimicrobial agents that do not fall within the scope of the present invention do not maintain stability at high temperatures during injection molding at a high temperature of 350 ℃ antibacterial properties over time As a result, the long-term antimicrobial properties were poor.

1 is a photograph showing the E. coli test results of the specimen prepared from the antimicrobial resin composition according to Example 1 of the present invention,

Figure 2 is a photograph showing the mold test results of the specimen prepared from the antimicrobial resin composition according to Example 1 of the present invention,

Figure 3 is a photograph showing the mold test results of the specimen prepared from the antimicrobial resin composition according to Example 3 of the present invention,

Figure 4 is a photograph showing the mold test results of the specimen prepared from the antimicrobial resin composition according to Comparative Example 3 of the present invention.

Claims (12)

(A) 100 parts by weight of a thermoplastic resin selected from acrylonitrile-butadiene-styrene resin, polycarbonate resin or mixtures thereof, (B) 0.1-1.0 parts by weight of an inorganic antibacterial agent, and (C) 2,4,4'-trichloro-2'-hydroxy diphenyl ether, 4,5-dichloro-2- (n-octyl) -isothiazolin-3-one or mixtures thereof Antibacterial resin composition for natural ventilation device injection, characterized in that comprises 0.1 to 1.0 parts by weight of organic antibacterial agent. The antimicrobial resin composition for natural ventilation device injection according to claim 1, further comprising 0.03-1.15 parts by weight of calcium stearate. The antimicrobial resin composition for natural ventilation device injection according to claim 1, further comprising 0.15-1.50 parts by weight of wax. The antimicrobial resin composition for natural ventilation device injection according to claim 1, wherein the inorganic antimicrobial agent is at least one selected from the group consisting of zeolite, calcium phosphate and zirconium phosphate. The antimicrobial resin composition according to claim 1, wherein the organic antimicrobial agent is 2,4,4'-trichloro-2'-hydroxydiphenyl ether. The method of claim 1, wherein the organic antimicrobial agent is 2,4,4′-trichloro-2′-hydroxy diphenyl ether and 4,5-dichloro-2- (n-octyl) -isothiazolin-3-one The antimicrobial resin composition for natural ventilation device injection, characterized in that the mixture is 6: 4-9: 1. The antimicrobial resin composition for natural ventilation device injection according to claim 1, wherein the weight ratio of the inorganic antimicrobial agent and the organic antimicrobial agent is 1: 1-6: 4. (a) 50-99% by weight of a thermoplastic resin selected from acrylonitrile-butadiene-styrene resin, polycarbonate resin or mixtures thereof, (b) an inorganic antimicrobial agent, 2,4,4'-trichloro-2'-hydroxy diphenyl ether, 4,5-dichloro-2- (n-octyl) -isothiazolin-3-one or theirs An antimicrobial masterbatch for natural ventilation device injection, characterized in that it comprises 1-50% by weight of an organic antimicrobial agent selected from the mixture. 9. The antimicrobial masterbatch for natural ventilation device according to claim 8, wherein the weight ratio of the inorganic antimicrobial agent and the organic antimicrobial agent is 1: 1-5: 1. An antimicrobial compound prepared from the antimicrobial resin composition according to any one of claims 1 to 7. An antimicrobial natural ventilation device prepared from the antimicrobial resin composition according to any one of claims 1 to 7. Method for producing an antimicrobial natural ventilation device comprising the step of injecting at 280-350 ℃ using the antimicrobial resin composition according to claim 1.

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