KR100974995B1 - Ecofriendly pvc composition, method for preparing the same and construction material made from the same - Google Patents
Ecofriendly pvc composition, method for preparing the same and construction material made from the same Download PDFInfo
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- KR100974995B1 KR100974995B1 KR1020100019295A KR20100019295A KR100974995B1 KR 100974995 B1 KR100974995 B1 KR 100974995B1 KR 1020100019295 A KR1020100019295 A KR 1020100019295A KR 20100019295 A KR20100019295 A KR 20100019295A KR 100974995 B1 KR100974995 B1 KR 100974995B1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
- E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
- E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
- E04C2/10—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of wood, fibres, chips, vegetable stems, or the like; of plastics; of foamed products
- E04C2/20—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of wood, fibres, chips, vegetable stems, or the like; of plastics; of foamed products of plastics
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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Abstract
The present invention relates to an environmentally friendly PVC composition, a method for manufacturing the same, and a building material including the same, and more particularly, comprising a PVC resin, a lead-free thermal stabilizer, and a clay powder of 250 to 6000 mesh having a water content of 7.0% or less. It relates to an environmentally friendly PVC resin composition, a manufacturing method thereof and a building material comprising the same.
According to the present invention, compared to the building material made of the conventional PVC composition, harmful substances, especially harmful heavy metals do not occur, more environmentally friendly, health promotion, antibacterial and anti-fungal effects due to the generation of far infrared rays and anions, and loess The texture and color of the excellent, no or no discoloration by ultraviolet light, and has an effect of providing an environmentally friendly PVC resin composition, a method of manufacturing the same and a building material comprising the same to maintain the properties consistent with the KS standard.
Description
The present invention relates to an environmentally friendly PVC composition, a method for manufacturing the same, and a building material comprising the same, and more particularly, compared to a building material made of a conventional PVC composition, no harmful substances, especially harmful heavy metals, are more environmentally friendly and far-infrared. Eco-friendly PVC resin that has health promotion, antibacterial and antifungal effects due to the generation of negative ions, excellent texture and color of ocher, no or no discoloration by UV light, and maintains physical properties consistent with KS standard. It relates to a composition, a method for producing the same, and a building material comprising the same.
In general, a building material manufactured from a PVC resin composition (hereinafter referred to as a 'PVC building material') is cheaper than other building materials, has excellent chemical resistance, weather resistance, and flame retardancy, and is widely used as a building material because of excellent mechanical properties. .
The PVC building material tends to be decomposed by heat during processing of the PVC resin, so that lead-based heat stabilizers containing lead, which is one of the six major heavy metals (lead, mercury, cadmium, hexavalent chromium, and brominated flame retardants, PBBs and PBDEs) are commonly used. These lead-based thermal stabilizers are inexpensive (reduced production costs) and have an excellent effect on suppressing thermal decomposition reactions (processability).
However, the PVC building material containing the lead-based heat stabilizer is a problem such as environmental pollution and human heavy metal poisoning.
Therefore, some domestic companies are trying to develop PVC construction materials that do not contain harmful heavy metals by using non-lead heat stabilizers, but they still do not have sufficient processability in blending and extrusion molding.
Ocher emits far-infrared rays, thus insulates heat, forms an electric field similar to the electromagnetic waves of the human body, and is not only beneficial to the human body, but also excellent in blocking effects such as moisture, and is applied to PVC building materials, resulting in dispersibility, light stability, and processability. It matters.
In order to solve the problems of the prior art as described above, the present invention is more environmentally friendly due to the generation of harmful substances, especially harmful heavy metals compared to the building materials made of conventional PVC composition, health promotion, antibacterial due to the generation of far infrared rays and anions And it has an anti-fungal effect, excellent texture and color of ocher, no or no discoloration by UV, eco-friendly PVC resin composition to maintain the properties consistent with the KS standard, the manufacturing method and the same It aims to provide building materials.
Moreover, an object of this invention is to provide the method of manufacturing the said building material.
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 an environmentally friendly PVC resin composition comprising a PVC resin, a lead-free thermal stabilizer and a 250 to 6000 mesh loess powder having a water content of 7.0% or less, and a method for manufacturing the same. Provide building materials, including
The present invention also provides a method of manufacturing the building material.
As described above, according to the present invention, it is more environmentally friendly because no harmful substances, in particular, no harmful heavy metals are generated, compared to conventional building materials made of PVC composition, and health promotion, antibacterial and antifungal properties due to the generation of far infrared rays and anions It is effective, and has excellent texture and color of ocher, no or no discoloration by ultraviolet rays, and provides eco-friendly PVC resin composition which maintains physical properties consistent with KS standard, its manufacturing method and building materials including the same. It is effective.
1 is a graph schematically showing the change in temperature, pressure and porosity (condition) of each location in an extruder during the extrusion process of PVC building material according to the present invention, a device diagram schematically showing the inside and outside of the extruder used, and the area inside the extruder This is a combination of the function and the state of the PVC composition.
Hereinafter, the present invention will be described in detail.
Eco-friendly PVC resin composition of the present invention is characterized in that it comprises a PVC resin, a lead-free thermal stabilizer and 250 to 6000 mesh loess powder having a water content of 7.0% or less.
The ocher powder has a water content of 7.0% or less, preferably 3.0% or less, more preferably 1.5% or less, and most preferably 1.0% or less. There is a problem in that dispersibility and processability are poor, such as agglomeration with each other or sticking to the mixing vessel.
The ocher powder is 250 to 6000 mesh (mesh), preferably 2000 to 4000 mesh (mesh), when applied to the PVC building material within this range has the effect of greatly improving the dispersibility and product properties of the composition.
The ocher powder is preferably prepared by processing the ocher particles to a size of 250 to 6000 mesh, and then rapidly drying at a high temperature of 200 ° C. or higher, preferably 280 to 320 ° C., more preferably 300 ° C.
The lead-free thermal stabilizer is calcium magnesium zinc thermal stabilizer, calcium zinc thermal stabilizer, organotin thermal stabilizer, metal tin metal thermal stabilizer, barium zinc thermal stabilizer, epoxy zinc thermal stabilizer, magnesium aluminum carbonate thermal stabilizer and It may be preferable that it is at least one selected from the group consisting of a linked heat stabilizer, more preferably a calcium zinc-based heat stabilizer.
The PVC resin is 100 to 130 parts by weight, preferably 116 to 119 parts by weight, the lead-free thermal stabilizer is 3 to 10 parts by weight, preferably 5.5 to 6.5 parts by weight, the ocher powder is 5 to 15 parts by weight Part, preferably 7 to 12 parts by weight, there is an effect of maintaining the functionality of the loess and the physical properties of the product within this range.
It is preferable that the PVC resin composition further comprises at least one member selected from the group consisting of an impact modifier, a filler, and a colorant.
Preferably, the impact modifier is an acrylic impact modifier, and may be used in an amount of 5 to 10 parts by weight based on a total of 150 parts by weight of the eco-friendly PVC resin composition.
The filler is not particularly limited as long as it can be commonly used in PVC building materials, preferably calcium carbonate, and may be used in 3 to 6 parts by weight based on 150 parts by weight of the total environmentally friendly PVC resin composition.
The colorant is not particularly limited as long as it can be commonly used in PVC building materials, but it is preferable that the colorant can be used, 0.5 to 3.5 parts by weight based on the total 150 parts by weight of the environmentally friendly PVC resin composition.
It may be preferable that the PVC resin composition further comprises an auxiliary lubricant, a sunscreen or a mixture thereof.
The auxiliary lubricant is used to improve the dispersibility and processability of the PVC resin composition, and is not particularly limited as long as it can be commonly used in PVC building materials, 2 to 4 parts by weight based on the total 150 parts by weight of the environmentally friendly PVC resin composition. It is preferred to be used, which has the effect of having the most stable dispersibility and excellent processability within this range.
The sunscreen has an effect of suppressing the color change by oxidizing the PVC resin composition by ultraviolet rays, preferably from 1.1 to 1.3 parts by weight based on the total 150 parts by weight of the environmentally friendly PVC resin composition.
The eco-friendly PVC construction material of the present invention is characterized by being made of the above-mentioned PVC resin composition.
The eco-friendly PVC building material may be preferably a building interior material or exterior material such as windows, moldings, door frames.
The manufacturing method of the eco-friendly PVC resin composition of the present invention includes the steps of: i) blending PVC resin, lead-free thermal stabilizer, impact modifier, filler and colorant using a mixer; Ii) mixing the mixture by adding 250 to 6000 mesh loess powder having a water content of 7.0% or less at the time of reaching 95 to 105 ° C .; And iii) terminating the mixture at 110 to 123 ° C. and cooling after adding the loess powder; Characterized in that comprises a.
The mixer is not particularly limited as long as it is usually used for the production of the PVC resin composition.
The ocher powder is preferably added at 95 to 105 ° C, more preferably at about 100 ° C, and when blended in this temperature range, the agglomeration of the ocher powder itself is prevented and the dispersibility is excellent.
The blending is preferably terminated at 110 to 123 ° C, more preferably terminated at 118 ° C, the compound compounded in this range is effective to reduce the load of the extruder during processing to the extruder.
Ii) 95 to 105 ℃ in the blending can be reached by self-heating by the raw material blending without a separate heating device.
Step iii) may be preferably added by adding a supplemental lubricant, a sunscreen or a mixture thereof when or after the ocher powder is added.
The manufacturing method of the eco-friendly PVC building material of the present invention includes: i) blending a PVC resin, a lead-free thermal stabilizer, an impact modifier, a filler and a colorant using a mixer; Ii) mixing the mixture by adding 250 to 6000 mesh loess powder having a water content of 7.0% or less at the time of reaching 95 to 105 ° C .; Iii) terminating the mixture at 110 to 123 ° C. and then cooling the loess powder to prepare a PVC resin composition; And iii) melt kneading and extruding the prepared PVC resin composition at a constant temperature and 12 to 22 rpm using an extruder; Characterized in that comprises a.
Extrusion of step iii) is preferably carried out at a temperature of 180 to 195 ° C. of the raw material input part, a temperature of 150 to 185 ° C. of the melt kneading part, and a temperature of 190 to 198 ° C. at the die. Although it is carried out at the temperature of 155 degreeC-175 degreeC of the melt-kneading part, and the temperature of 190-192 degreeC in die | dye in and out of degreeC, it is excellent in thermal stability within this range, and there exists an effect which suppresses a sudden temperature and pressure rise.
The temperature condition at the time of extrusion relates to the setting temperature of the heater attached to the extruder at the time of extrusion of the PVC resin composition.
In the extrusion, the temperature of the resin in the cylinder and the die (mold) is preferably controlled so as not to exceed 195 ° C, more preferably, so as not to exceed 190 ° C, in particular when the resin exceeds 195 ° C. While boiling, a large amount of bubbles are formed, there is a problem that the impact strength drops sharply.
For reference, the graph shown in FIG. 1 schematically shows the relative pressure, temperature, and porosity change of the PVC resin composition melted and kneaded in the extruder. It falls sharply and then increases again.
The extrusion of iii) is preferably carried out at 12 to 22 rpm in the case of 150 to 280 kg of extrusion per hour based on a 92mm twin parallel extruder, and the extrusion amount per hour depends on the type of mold (die). Preferred rpm ranges may vary.
For reference, in case of small die (die), the amount of extrusion per hour is low, so the rpm is relatively low (but it may vary depending on the production line speed), and in the case of large die (die), the area of the drilled hole is high. Since the amount of discharge increases, the rpm increases.
More specifically, the melt kneading unit may be divided into a compression zone and a metering zone. Preferably, the compression section is 175 to 185 ° C., and the metering section is 150 to 175 ° C. .
The extruder used for the extrusion is not particularly limited as long as it can be used for the production of PVC building materials, but may be preferably a twin parallel type.
1 is a graph showing the temperature, pressure and porosity change (condition) of each location in the extruder during the extrusion process of the environmentally friendly PVC building material, the device diagram schematically showing the inside and outside of the extruder used, and the function and PVC by area inside the extruder The diagram showing the state of the composition is combined.
In the graph, the Y axis shows the relative magnitudes of temperature, pressure and porosity, and the X axis corresponds to the position of the extruder shown below the graph.
Extruder in the above device diagram is composed of a hopper (Hopper), heater (H1 ~ H5), cylinder, screw and die (DIE), etc., the adapter (Adapter) installed between the heater H5 and the die to control the pressure inside the extruder Pressure generators and the like are omitted, and the blended PVC resin composition in the solid state is indicated on the hopper and a part of the cylinder.
The chart shows a feeding zone corresponding to the extruder in position, a feeding zone where the compounded PVC resin composition is put in a solid state, a compression unit where kneading and melting occurs, a kneading of the melted plasticized PVC resin composition It is divided into a metering zone for controlling the extrusion flow rate by controlling the temperature and pressure, and a die for extruding the melt-kneaded PVC resin composition into a desired shape.
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]
<Mixing stage>
116.5 kg of PVC resin (manufactured by LG Chemical), 6.4 kg of calcium-zinc-based heat stabilizer (manufactured by Baerlocher), 8.16 kg of acrylate-based impact modifier (manufactured by LG Chemical, IM809), 5.24 kg of calcium carbonate, 0.58 kg per branch, other auxiliary 3.26 kg of lubricant and 1.16 kg of a sunscreen (manufactured by CIBA, XT833) were added to a mixer, and then compounding was started at 1750 rpm. 8.73 kg of 2000 mesh loess powder dried at 3% or less after the start of the mixing, the mixing was continued, and then the mixing was stopped when reaching 118 ° C and cooled to 35 ° C in a cooler. PVC resin composition was prepared.
<Extrusion Step>
150.03 kg of the blended PVC resin composition was added to a hopper of a twin parallel screw extruder (90 mm), and 13.6 rpm, a raw material input part 180 ° C., a compression part 162 ° C., a metering part 175 ° C., a die 190 ° C. , Melted, kneaded and extruded under the resin temperature (the temperature of the resin measured at the moment of ejecting from the mold and exiting the machine) and the extrusion loads of 51A to 53A to finally form a synthetic resin window and door member (PVC window material). .
[Comparative Example]
Synthetic resin window and door member made by conventional PVC resin composition containing lead-based heat stabilizer (preparation of SKP210DD) and not containing ocher (manufactured by Daedong Eloy Sash).
[Test Example]
The properties of the PVC resin composition products prepared or obtained in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Tables 1 and 2 below.
* Dispersibility: It was measured based on the apparent specific gravity and shape of the compound of the compound before extrusion processing after the completion of the compounding, and was evaluated to have excellent dispersibility when the spherical particle shape had a high apparent specific gravity.
* Far-infrared generation: It was measured by KICM-FIR-1005: 2006 by the Construction Materials Testing Laboratory (accession number: KWR107002, sample name: synthetic resin window and window member (SF90P loess)). This is a result of measuring the black body using the FT-IR Spectrometer, it was measured at a temperature of 40 ℃ and a wavelength of 5 ~ 20 ㎛.
* Antimicrobial activity: Measured by KICM-FIR-1003: 2009 by the KICM-FIR-1003: 2009 (Accession No .: KWR112002, Sample name: Mold for plastic windows and doors (SF09P loess), inoculated bacteria bacterial concentration (CFU / mL): Escherichia coli 3.3 × 10 5 , Pseudomonas aeruginosa: 3.6 × 10 5 , CFU: Colony Forming Unit, strain used: Eschericha coli ATCC 8739, Pseudomonas aeruginosa ATCC 15442, Specimen: 5 × 5 cm, Control: Stomacher film 5 × 5 cm).
* Antifungal properties: measured by the method according to ASTM G-21: 2002 by the Institute of Building Materials Testing (accession number: KWR107004, sample name: plastic window and window mold (SF90P loess), the duration of the culture test: 4 weeks or more).
* Hazardous heavy metals: measured by the method according to USEPA 3052: 1996 at the Institute of Building Materials Testing (Accession No .: KWR125003 (Comparative Example), KWR125004 (Example), Sample name: Synthetic resin window and window (SF90P general)).
Example
Great
Cd: not detected
Hg: not detected
(W / ㎡)
Comparative example
Cd: 52
Hg: not detected
(Antibacterial)
Test Methods
(CFU / mL)
(CFU / mL)
2009
As shown in Tables 1 and 2, the PVC product (example) according to the present invention has excellent dispersibility, far-infrared rays generated, excellent antibacterial and antifungal properties, and can be confirmed that it does not contain harmful heavy metals. there was.
In addition, it was confirmed that the conventional PVC building material (Comparative Example) containing no ocher powder and containing a lead-based heat stabilizer contained a large amount of harmful heavy metals.
For reference, although lead was not detected as a constituent of the ingredients blended in the example, the lead component was detected as 36.3 mg / kg in Table 1, which was performed in the same extruder. Accordingly, it is determined that the lead component remaining in the extruder after the comparative example was buried in the following example.
Claims (12)
Environmentally friendly PVC resin composition.
The PVC resin composition is characterized in that it further comprises one or more selected from the group consisting of fillers and colorants.
Environmentally friendly PVC resin composition.
The PVC resin composition, characterized in that further comprises an auxiliary lubricant, a sunscreen or a mixture thereof.
Environmentally friendly PVC resin composition.
The lead-free thermal stabilizer is calcium magnesium zinc thermal stabilizer, calcium zinc thermal stabilizer, organotin thermal stabilizer, metal tin metal thermal stabilizer, barium zinc thermal stabilizer, epoxy zinc thermal stabilizer, magnesium aluminum carbonate thermal stabilizer and At least one member selected from the group consisting of zinc-based heat stabilizers
Environmentally friendly PVC resin composition.
The colorant is fat sugar
Environmentally friendly PVC resin composition.
The PVC resin is 100 to 130 parts by weight, the lead-free thermal stabilizer is 3 to 10 parts by weight, the ocher powder is characterized in that 5 to 15 parts by weight.
Environmentally friendly PVC resin composition.
Eco-friendly PVC Building Material.
A method for producing environmentally friendly PVC resin composition.
In step iii), at the time of or after the addition of the ocher powder, an auxiliary lubricant, a sunscreen, or a mixture thereof is further added.
A method for producing environmentally friendly PVC resin composition.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100019295A KR100974995B1 (en) | 2010-03-04 | 2010-03-04 | Ecofriendly pvc composition, method for preparing the same and construction material made from the same |
| PCT/KR2011/001512 WO2011108887A2 (en) | 2010-03-04 | 2011-03-04 | Environmentally friendly pvc composition, preparation method thereof, and construction material comprising same |
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| KR1020100019295A KR100974995B1 (en) | 2010-03-04 | 2010-03-04 | Ecofriendly pvc composition, method for preparing the same and construction material made from the same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20200073072A (en) * | 2018-12-13 | 2020-06-23 | 주식회사 케이씨씨 | Composition for decoration sheet and decoration sheet prepared therefrom |
| KR20200100952A (en) | 2019-02-19 | 2020-08-27 | 주식회사 대건케미칼 | Eco-friendly composition for pipe making |
| KR102165524B1 (en) | 2020-03-30 | 2020-10-14 | 주식회사 대건케미칼 | The pigment composition for the plastic moldings having water-borne prevention effect |
| KR20220087715A (en) | 2020-12-18 | 2022-06-27 | 프로켐 주식회사 | Method for manufacturing hybrid type PVC stabilizer including liquid stabilizer and powder stabilizer |
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| KR20200073072A (en) * | 2018-12-13 | 2020-06-23 | 주식회사 케이씨씨 | Composition for decoration sheet and decoration sheet prepared therefrom |
| KR102167904B1 (en) * | 2018-12-13 | 2020-10-20 | 주식회사 케이씨씨 | Composition for decoration sheet and decoration sheet prepared therefrom |
| KR20200100952A (en) | 2019-02-19 | 2020-08-27 | 주식회사 대건케미칼 | Eco-friendly composition for pipe making |
| KR102165524B1 (en) | 2020-03-30 | 2020-10-14 | 주식회사 대건케미칼 | The pigment composition for the plastic moldings having water-borne prevention effect |
| KR20220087715A (en) | 2020-12-18 | 2022-06-27 | 프로켐 주식회사 | Method for manufacturing hybrid type PVC stabilizer including liquid stabilizer and powder stabilizer |
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