WO2021020869A1 - Expandable vinyl chloride resin composition - Google Patents

Expandable vinyl chloride resin composition Download PDF

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Publication number
WO2021020869A1
WO2021020869A1 PCT/KR2020/009962 KR2020009962W WO2021020869A1 WO 2021020869 A1 WO2021020869 A1 WO 2021020869A1 KR 2020009962 W KR2020009962 W KR 2020009962W WO 2021020869 A1 WO2021020869 A1 WO 2021020869A1
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Prior art keywords
vinyl chloride
resin composition
weight
chloride resin
parts
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PCT/KR2020/009962
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French (fr)
Korean (ko)
Inventor
김민우
김재송
최용석
Original Assignee
한화솔루션 주식회사
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Priority claimed from KR1020200093870A external-priority patent/KR102539747B1/en
Application filed by 한화솔루션 주식회사 filed Critical 한화솔루션 주식회사
Priority to CN202080052849.7A priority Critical patent/CN114174412A/en
Publication of WO2021020869A1 publication Critical patent/WO2021020869A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
    • C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the present invention relates to an eco-friendly foamable vinyl chloride resin composition having excellent foaming properties.
  • the vinyl chloride resin is a homopolymer of vinyl chloride and a hybrid polymer containing 50% or more of vinyl chloride, and is one of the general-purpose thermoplastic plastic resins produced by suspension polymerization and emulsion polymerization.
  • polyvinyl chloride resins produced by emulsion polymerization are plasticizers, stabilizers, fillers, blowing agents, pigments, viscosity depressants, titanium dioxide (TiO).
  • Mixing and subsidiary materials are processed into a plastisol or granule form, and through coating molding, extrusion molding, injection molding, and calendar molding, flooring, wallpaper, tarpaulin, artificial leather, toys, automobile interior materials , It is used in a wide range of fields such as coatings under automobiles.
  • interior interior products such as wallpaper or flooring are products that are most exposed in residential and office spaces, and more than 60% of them are manufactured using vinyl chloride resin.
  • the main issue of wallpaper and flooring is environment-friendliness, and the criteria for judging eco-friendliness are HB grades (best, excellent, good), which are rated according to the amount of volatile organic compounds (VOCs) emitted by the Air Purification Association. 3) and whether it contains phthalate plasticizers (DEHP, BBP, DBP, DINP, etc.), which are considered suspicious substances for environmental hormones in Korea.
  • plasticizer is a liquid component that occupies the largest amount.
  • plasticizers include phthalate products such as DEHP (Di-2-EthylHexyl Phthalate), DINP (Di-IsoNonyl Phthalate), DIDP (Di- Iso-Decyl Phthalate), BBP (Butyl Benzyl Phthalate), DBP (Di-n-butyl phthalate), and in particular DINP has been widely used.
  • phthalate-based plasticizers are suspicious of environmental hormones as an endocrine disrupter that interferes or disrupts human hormone action socially, and thus regulation is underway. Accordingly, recently, non-phthalate plasticizers such as DOTP (Dioctyl terephthalate) have been used instead of phthalate plasticizers.
  • DOTP Dioctyl terephthalate
  • the foamable vinyl chloride resin composition used for foam mats such as playroom mats, artificial leather, etc.
  • ADCA Azodicarbonamide
  • the ADCA is formamide (Formamide), a kind of volatile organic compound during thermal decomposition. ).
  • OBSH p,p'-Oxybis(benzenesulfonyl hydrazide)
  • a foamable resin composition containing OBSH as a foaming agent and DOTP as a plasticizer is used in consideration of eco-friendliness.
  • OBSH has a relatively small amount of gas emission during foaming and a low decomposition temperature, and has a disadvantage in that it lacks foaming properties such as foaming ratio and foam cell stability compared to ADCA foaming agents under the processing conditions of general vinyl chloride-based resins.
  • the present invention provides an eco-friendly expandable vinyl chloride-based resin composition that has excellent foaming properties such as foaming ratio and foam cell stability, does not contain a phthalate plasticizer, and significantly reduces the generation of volatile organic compounds. It aims to do.
  • an object of the present invention is to provide a molded article comprising the expandable vinyl chloride resin composition.
  • the present invention includes a vinyl chloride resin, di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and p,p'-oxybis(benzenesulfonylhydrazide) It provides a foamable vinyl chloride resin composition.
  • the expandable vinyl chloride-based resin composition may contain 50 to 120 parts by weight of the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate based on 100 parts by weight of the vinyl chloride-based resin.
  • the expandable vinyl chloride-based resin composition may include 0.5 to 12 parts by weight of the p,p'-oxybis (benzenesulfonyl hydrazide) based on 100 parts by weight of the vinyl chloride-based resin.
  • the expandable vinyl chloride resin composition contains the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and p,p'-oxybis(benzenesulfonylhydrazide) from 20:1 to 7 It can be included in a weight ratio of :1.
  • the vinyl chloride-based resin may have a degree of polymerization of 800 or more to less than 1,700.
  • the expandable vinyl chloride-based resin composition is, based on 100 parts by weight of the vinyl chloride-based resin, the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate 70 to 100 parts by weight, and It may contain 5 to 10 parts by weight of the p,p'-oxybis (benzenesulfonyl hydrazide).
  • the foamable vinyl chloride resin composition may further include a stabilizer and/or a filler.
  • the stabilizer is selected from the group consisting of Ca-Zn-based compounds, K-Zn-based compounds, Ba-Zn-based compounds, organic Tin-based compounds, metallic soap-based compounds, phenolic compounds, phosphoric acid ester compounds, and phosphorous acid ester compounds. It can be any one or more.
  • the filler may be at least one selected from the group consisting of calcium carbonate, talc, titanium dioxide, kaolin, silica, alumina, magnesium hydroxide, and clay.
  • the present invention provides a molded article comprising the foamable vinyl chloride resin composition.
  • the molded article may be wallpaper, foam mat, flooring, artificial leather, or automobile interior material.
  • the expandable vinyl chloride resin composition according to the present invention is a vinyl chloride resin, di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and p,p'-oxybis(benzenesulfonylhydrazide) By including together, it shows excellent foaming properties.
  • the foamable vinyl chloride-based resin composition does not contain a phthalate-based plasticizer and ADCA, it is environmentally friendly because there is little concern about the occurrence of environmental hormones and volatile organic compounds.
  • foamable vinyl chloride resin composition of the present invention may be suitably used for wallpaper, foam mat, flooring, artificial leather, or automobile interior materials.
  • the foamable vinyl chloride-based resin composition according to the present invention has the insufficient foaming performance of p,p'-oxybis(benzenesulfonylhydrazide) (OBSH), di(2-ethylhexyl)cyclohexane-1,4-dicar It was conceived that it can be supplemented by using a deoxylate (DEHCH) together.
  • OBSH p,p'-oxybis(benzenesulfonylhydrazide)
  • DEHCH deoxylate
  • the foamable vinyl chloride-based resin composition uses OBSH, an eco-friendly foaming agent, and does not contain a phthalate plasticizer, it can be used as an eco-friendly material that greatly reduces the risk of generation of volatile organic compounds or release of environmental hormones.
  • the expandable vinyl chloride resin composition according to an embodiment of the present invention includes a vinyl chloride resin, di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and p,p'-oxybis(benzenesulfuryl). Phonylhydrazide).
  • the vinyl chloride-based resin refers to a vinyl chloride-based monomer alone or a (co)polymer in which a vinyl chloride-based monomer and a comonomer copolymerizable therewith are copolymerized.
  • it may be prepared by a polymerization method such as suspension polymerization, micro-suspension polymerization, emulsion polymerization, or mini-emulsion polymerization by mixing a suspension agent, a buffer, and a polymerization initiator.
  • the vinyl chloride-based resin is polyvinyl chloride (PVC), and a degree of polymerization of 800 or more to less than 1,700 may be used in consideration of compatibility with an OBSH foaming agent. Alternatively, the degree of polymerization of the vinyl chloride-based resin may be 900 to 1500. If the degree of polymerization of the vinyl chloride-based resin is too high, above 1,700, foam sheets are not formed at the temperature at which the OBSH foaming agent is foamed, and all of the vaporized foaming agent escapes and foaming may not occur smoothly. Conversely, if the degree of polymerization is less than 800, There may be a problem that foaming does not occur because the molding is completed before the foaming agent is evaporated.
  • PVC polyvinyl chloride
  • the degree of polymerization of the vinyl chloride resin can be measured according to JIS K 6720-2.
  • the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate is a compound represented by the following Chemical Formula 1, and is chlorinated in the present invention. It is used as a plasticizer for vinyl resins. DEHCH has low viscosity at room temperature and low temperature, so it can realize excellent coating properties, has a fast gelling speed, and has excellent foaming properties. In addition, it is possible to minimize the generation of volatile organic compounds compared to existing phthalate plasticizers, and unlike DOTP, since it does not contain a benzene ring in the molecular structure, it is possible to reduce the potential risk.
  • the DEHCH may be included in an amount of 50 to 120 parts by weight, or 70 to 100 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content of DEHCH is less than 50 parts by weight based on 100 parts by weight of the vinyl chloride-based resin, the viscosity is too high and processing is difficult, and the effect of supplementing the foaming performance of OBSH cannot be obtained. In addition, if the DEHCH content exceeds 120 parts by weight based on 100 parts by weight of the vinyl chloride resin, the viscosity is too low to process, and the gelling is too slow, so that the gas generated when the foaming agent evaporates does not form a cell and escapes. There is a problem that the foamability is inferior, which is not preferable.
  • the expandable vinyl chloride resin composition of the present invention contains only DEHCH as a plasticizer, and may not further contain a plasticizer other than DEHCH.
  • p,p'-oxybis (benzenesulfonyl hydrazide) (p,p'-Oxybis (benzenesulfonyl hydrazide); OBSH) is a compound represented by the following formula (2), and is used as a blowing agent in the present invention.
  • the OBSH is preferably included in an amount of 0.5 to 12 parts by weight, or 5 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content of OBSH is less than 0.5 parts by weight based on 100 parts by weight of the vinyl chloride-based resin, there is a problem that sufficient foaming does not occur, and if it exceeds 12 parts by weight, there may be a problem that the stability of the foaming cell is poor.
  • OBSH is eco-friendly because it does not generate harmful components such as formamide and ammonia.
  • the amount of gas released from OBSH is about 125 ml/g, which does not reach ADCA (about 220 ml/g), and the decomposition temperature is low at 157 to 160° C., and foaming performance is lower than that of ADCA under the same processing conditions. Accordingly, in the present invention, the insufficient foaming performance of OBSH is supplemented by using the above-described DEHCH as a plasticizer.
  • the weight ratio of the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and p,p'-oxybis(benzenesulfonylhydrazide) is 20:1 to 7 It is preferably in the range of :1, or 10:1 to 7:1. Within a range that satisfies the above weight ratio, a sufficient plasticizing effect and excellent foaming performance can be expected.
  • the foamable vinyl chloride resin composition of the present invention may use only the above OBSH as a foaming agent, and may not further contain a foaming agent other than OBSH.
  • OBSH a foaming agent
  • the foamable vinyl chloride resin composition of the present invention may use only the above OBSH as a foaming agent, and may not further contain a foaming agent other than OBSH.
  • the expandable vinyl chloride resin composition according to an embodiment of the present invention based on 100 parts by weight of the vinyl chloride resin, the di (2-ethylhexyl) cyclohexane-1,4-dicarboxylate 50 to 120 parts by weight, and 0.5 to 12 parts by weight of the p,p'-oxybis (benzenesulfonyl hydrazide) may be included.
  • the expandable vinyl chloride resin composition according to another embodiment of the present invention based on 100 parts by weight of the vinyl chloride resin, the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate 70 To 100 parts by weight, and 5 to 10 parts by weight of the p,p'-oxybis (benzenesulfonyl hydrazide).
  • the vinyl chloride-based resin composition may further include additives such as stabilizers and fillers.
  • the additive may be appropriately selected according to physical properties to be improved in the vinyl chloride resin composition.
  • the stabilizer is added for the purpose of preventing various changes in physical properties caused by cutting and crosslinking of the main chain by separating HCl from the vinyl chloride-based resin to form a polyene structure, which is a chromophore, and Ca-Zn-based compound, K -Zn-based compounds, Ba-Zn-based compounds, organic Tin-based compounds, metallic soap-based compounds, phenolic compounds, phosphoric acid ester compounds and phosphorous acid ester compounds include any one or more selected from the group consisting of.
  • More specific examples as a stabilizer that can be used in the present invention are Ca-Zn-based compounds; K-Zn-based compounds; Ba-Zn-based compounds; Organic Tin-based compounds such as mercaptide-based compounds, maleic acid-based compounds, or carboxylic acid-based compounds; Metallic soap-based compounds such as Mg-stearate, Ca-stearate, Pb-stearate, Cd-stearate, or Ba-stearate; Phenolic compounds; Phosphoric acid ester compounds; Or a phosphorous acid ester compound, and the like, and is optionally included depending on the purpose of use.
  • a K-Zn-based compound preferably a K-Zn-based complex organic compound.
  • the stabilizer is preferably 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content of the stabilizer is less than 0.5 parts by weight, there is a problem that the thermal stability is poor, and if it exceeds 5 parts by weight, there is a problem that the workability is poor.
  • the filler of the present invention is used for the purpose of improving the productivity and dry touch of a vinyl chloride resin composition, and is a group consisting of calcium carbonate, talc, titanium dioxide, kaolin, silica, alumina, magnesium hydroxide, and clay. It includes any one or more selected from.
  • the filler may preferably be 10 to 100 parts by weight, more preferably 20 to 50 parts by weight.
  • the filler is included in an amount of less than 10 parts by weight, there is a problem that dimensional stability and economy are lowered, and when it is included in an amount exceeding 100 parts by weight, the foaming surface is not good, and there is a problem that the workability is deteriorated.
  • the expandable vinyl chloride-based resin composition according to the present invention may be prepared by a method generally known in the art using a vinyl chloride-based resin, DEHCH as a plasticizer, OBSH as a foaming agent, and optionally additives. It is not limited.
  • the foamable vinyl chloride-based resin composition of the present invention includes DEHCH and OBSH together and exhibits excellent foaming properties similar to those of the existing ADCA foaming agent.
  • the foamable vinyl chloride-based resin composition may be used as wallpaper, foam mat, flooring, artificial leather, automobile interior materials, and the like.
  • the expandable vinyl chloride-based resin composition of the present invention does not contain a phthalate plasticizer, and a foaming agent that generates volatile organic compounds such as formamide is greatly reduced, thereby reducing harmful substances such as playroom mats. It can be suitably used in a required field.
  • a molded article including the vinyl chloride-based resin composition is provided.
  • the molded article may be manufactured by additionally adding additives such as a stabilizer, a filler, and/or a foaming agent to the vinyl chloride-based resin composition according to its use.
  • the molded article may be used as wallpaper, foam mat, flooring, artificial leather, automobile interior material, and the like.
  • polymerization degree 1000 90 parts by weight of DEHCH as a plasticizer and 10 parts by weight of OBSH as a foaming agent were weighed and mixed for 15 minutes with a mixer to prepare a foamable vinyl chloride-based resin composition (plastisol).
  • a foamable vinyl chloride resin composition was prepared in the same manner as in Example 1, except that 80 parts by weight of DEHCH was used as a plasticizer.
  • a foamable vinyl chloride resin composition was prepared in the same manner as in Example 1, except that 70 parts by weight of DEHCH was used as a plasticizer.
  • a foamable vinyl chloride resin composition was prepared in the same manner as in Example 1, except that DOTP was used as a plasticizer.
  • Each plastisol of Examples (Ex.) and Comparative Examples (C.Ex.) was coated to a thickness of 1.0 mm on paper using an applicator, and then heated in an oven at 190°C to 230°C for 80 to 160 seconds to foam To prepare a foam sheet.
  • the thickness of the foam sheet was measured, and the uniformity of the foam cell was visually confirmed.
  • 1 is a photograph of a cross section of each foam sheet.
  • Example (Ex.) and Comparative Example (C.Ex.) were measured for gelling rate at 120° C. using SVNC equipment.
  • SVNC equipment As the gelling proceeds, the amplitude decreases, and the gelling speed was compared and measured using the rate at which this value decreases. 2 is a graph of measuring gelling speed.
  • Foam sheets prepared using the plastisols of Examples and Comparative Examples were sampled in a circle shape with a radius of 3 cm, and pretreated at 40° C. for 1 hour. The gas sample generated after that was collected and the amount of formamide released was measured using Gas Chromatography.
  • Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3
  • Foam sheet thickness (mm) 7.0 6.5 6.5 6.0
  • 1.0 (no foam) 5.0
  • Foam cell uniformity ⁇ ⁇ ⁇ ⁇ - ⁇ Gelling speed ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Formamide emission ( ⁇ g / m 3 ) - - - 4031.85 - -
  • Foaming refers to the surface condition of the product, the foaming ratio, the size of the foaming cell and the uniformity of the foaming cell.
  • the foamable vinyl chloride resin composition of Examples 1 to 3 was environmentally friendly, and exhibited equal or higher foaming characteristics while having excellent gelling speed compared to the conventional vinyl chloride resin composition containing the ADCA foaming agent and the DOTP plasticizer. I could confirm. However, when the combination of the DEHCH plasticizer and the OBSH foaming agent is not satisfied as in Comparative Examples 2 and 3, it can be seen that foaming does not occur, foaming property is poor, and the gelling speed is lowered.

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  • Polymers & Plastics (AREA)
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Abstract

The present invention relates to an environmentally friendly expandable vinyl chloride resin composition which is excellent in foaming characteristics such as expansion ratio and cell stability, and from which toxic substances such as formamide are not generated.

Description

발포성 염화비닐계 수지 조성물Expandable vinyl chloride resin composition
관련 출원(들)과의 상호 인용Cross-reference with related application(s)
본 출원은 2019년 7월 31일자 한국 특허 출원 제10-2019-0093425호 및 2020년 7월 28일자 한국 특허 출원 제10-2020-0093870호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0093425 filed July 31, 2019 and Korean Patent Application No. 10-2020-0093870 filed July 28, 2020. All contents disclosed in the literature are included as part of this specification.
본 발명은 발포 특성이 우수하고 친환경적인 발포성 염화비닐계 수지 조성물에 관한 것이다.The present invention relates to an eco-friendly foamable vinyl chloride resin composition having excellent foaming properties.
염화비닐계 수지는 염화비닐의 단독 중합체 및 염화비닐을 50% 이상 함유한 혼성 중합체로서, 현탁중합과 유화 중합으로 제조되는 범용 열가소성 플라스틱 수지 중의 하나이다. 그 중에서 유화중합으로 제조되는 폴리염화비닐계 수지는 가소제(Plasticizer), 안정제(Stabilizer), 충전제(Filler), 발포제(Blowing Agent), 안료(Pigment), 점도 조절제(Viscosity Depressant), 이산화 티타늄(TiO 2) 및 부원료를 혼합하여 플라스티졸(Plastisol) 형태 혹은 그래뉼(Granule) 형태로 가공되며 코팅 성형, 압출 성형, 사출 성형, 카렌다 성형 가공법을 통해 바닥재, 벽지, 타포린, 인조피혁, 장난감, 자동차 내장재, 자동차 하부 코팅재 등의 광범위한 분야에 사용되고 있다.The vinyl chloride resin is a homopolymer of vinyl chloride and a hybrid polymer containing 50% or more of vinyl chloride, and is one of the general-purpose thermoplastic plastic resins produced by suspension polymerization and emulsion polymerization. Among them, polyvinyl chloride resins produced by emulsion polymerization are plasticizers, stabilizers, fillers, blowing agents, pigments, viscosity depressants, titanium dioxide (TiO). 2 ) Mixing and subsidiary materials are processed into a plastisol or granule form, and through coating molding, extrusion molding, injection molding, and calendar molding, flooring, wallpaper, tarpaulin, artificial leather, toys, automobile interior materials , It is used in a wide range of fields such as coatings under automobiles.
특히, 벽지나 바닥재 등의 내부 인테리어 제품은 주거 및 사무 공간에서 가장 많이 노출되는 제품으로서, 60% 이상이 염화비닐계 수지를 이용하여 제조되고 있다. 최근 벽지와 바닥재의 주요 쟁점은 친환경에 관한 것이며, 친환경성에 대한 판단 기준은 공기청정협회에서 시행하고 있는 휘발성 유기 화합물(Volatile Organic Compounds: VOCs)의 방출량에 따라 매겨지는 HB 등급(최우수, 우수, 양호까지 3단계)과 국내에서 환경호르몬 의심물질이라고 여겨지는 프탈레이트계 가소제(DEHP, BBP, DBP, DINP등) 함유여부에 따라 결정되고 있다. In particular, interior interior products such as wallpaper or flooring are products that are most exposed in residential and office spaces, and more than 60% of them are manufactured using vinyl chloride resin. Recently, the main issue of wallpaper and flooring is environment-friendliness, and the criteria for judging eco-friendliness are HB grades (best, excellent, good), which are rated according to the amount of volatile organic compounds (VOCs) emitted by the Air Purification Association. 3) and whether it contains phthalate plasticizers (DEHP, BBP, DBP, DINP, etc.), which are considered suspicious substances for environmental hormones in Korea.
벽지와 바닥재용 염화비닐계 수지 조성물 중에서 가소제는 가장 많은 함량을 차지하는 액상 성분이며, 이러한 가소제의 예로 프탈레이트계 제품인 DEHP(Di-2-EthylHexyl Phthalate), DINP(Di-IsoNonyl Phthalate), DIDP(Di-Iso-Decyl Phthalate), BBP(Butyl Benzyl Phthalate), DBP(Di-n-butyl phthalate)를 들 수 있으며, 특히 DINP가 널리 사용되어 왔다. Among vinyl chloride resin compositions for wallpaper and flooring, plasticizer is a liquid component that occupies the largest amount. Examples of such plasticizers include phthalate products such as DEHP (Di-2-EthylHexyl Phthalate), DINP (Di-IsoNonyl Phthalate), DIDP (Di- Iso-Decyl Phthalate), BBP (Butyl Benzyl Phthalate), DBP (Di-n-butyl phthalate), and in particular DINP has been widely used.
그러나, 프탈레이트계 가소제는 사회적으로 사람의 호르몬 작용을 방해하거나 혼란시키는 내분비계 교란물질(endocrine disrupter)로서 환경호르몬으로 의심받고 있어 규제가 진행 중이다. 이에 최근에는 프탈레이트계 가소제 대신 DOTP(Dioctyl terephthalate) 등 비-프탈레이트계 가소제를 사용하고 있다. However, phthalate-based plasticizers are suspicious of environmental hormones as an endocrine disrupter that interferes or disrupts human hormone action socially, and thus regulation is underway. Accordingly, recently, non-phthalate plasticizers such as DOTP (Dioctyl terephthalate) have been used instead of phthalate plasticizers.
한편, 놀이방 매트와 같은 발포 매트, 인조 피혁 등에 사용되는 발포성 염화비닐계 수지 조성물은 기존에 발포제로 ADCA(Azodicarbonamide)를 주로 사용하였으나, 상기 ADCA는 열 분해 시 휘발성 유기 화합물의 일종인 포름아마이드(Formamide)를 생성하는 문제가 있다. 이에, ADCA를 대체할 발포제로서 OBSH(p,p'-Oxybis(benzenesulfonyl hydrazide))가 사용되고 있으며, 친환경성을 고려하여 OBSH를 발포제로, DOTP를 가소제로 포함하는 발포성 수지 조성물이 사용되고 있다. On the other hand, the foamable vinyl chloride resin composition used for foam mats such as playroom mats, artificial leather, etc., previously mainly used ADCA (Azodicarbonamide) as a foaming agent, but the ADCA is formamide (Formamide), a kind of volatile organic compound during thermal decomposition. ). Accordingly, OBSH(p,p'-Oxybis(benzenesulfonyl hydrazide)) is used as a foaming agent to replace ADCA, and a foamable resin composition containing OBSH as a foaming agent and DOTP as a plasticizer is used in consideration of eco-friendliness.
그러나 OBSH는 발포 시 가스 방출량이 상대적으로 적고 분해 온도가 낮아, 일반적인 염화비닐계 수지의 가공 조건에서 ADCA 발포제 대비 발포 배율, 발포 셀 안정성과 같은 발포 특성이 부족한 단점이 있다. However, OBSH has a relatively small amount of gas emission during foaming and a low decomposition temperature, and has a disadvantage in that it lacks foaming properties such as foaming ratio and foam cell stability compared to ADCA foaming agents under the processing conditions of general vinyl chloride-based resins.
따라서, 우수한 발포 특성을 유지하면서도 친환경적인 발포성 염화비닐계 수지 조성물을 개발할 필요성이 있다.Therefore, there is a need to develop an eco-friendly foamable vinyl chloride resin composition while maintaining excellent foaming properties.
본 발명은 상기 과제를 해결하기 위한 것으로, 발포 배율, 발포 셀 안정성 등 발포 특성이 우수하면서도, 프탈레이트계 가소제를 포함하지 않고, 휘발성 유기 화합물의 발생이 현저히 저감된 친환경 발포성 염화비닐계 수지 조성물을 제공하는 것을 목적으로 한다.The present invention provides an eco-friendly expandable vinyl chloride-based resin composition that has excellent foaming properties such as foaming ratio and foam cell stability, does not contain a phthalate plasticizer, and significantly reduces the generation of volatile organic compounds. It aims to do.
또한, 본 발명은 상기 발포성 염화비닐계 수지 조성물을 포함하는 성형품을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a molded article comprising the expandable vinyl chloride resin composition.
상기 과제를 해결하기 위하여 본 발명은 염화비닐계 수지, 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트, 및 p,p'-옥시비스(벤젠술포닐히드라지드)를 포함하는 발포성 염화비닐계 수지 조성물을 제공한다.In order to solve the above problems, the present invention includes a vinyl chloride resin, di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and p,p'-oxybis(benzenesulfonylhydrazide) It provides a foamable vinyl chloride resin composition.
상기 발포성 염화비닐계 수지 조성물은, 상기 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트를 염화비닐계 수지 100 중량부에 대하여 50 내지 120 중량부로 포함할 수 있다.The expandable vinyl chloride-based resin composition may contain 50 to 120 parts by weight of the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate based on 100 parts by weight of the vinyl chloride-based resin.
상기 발포성 염화비닐계 수지 조성물은, 상기 p,p'-옥시비스(벤젠술포닐히드라지드)를 염화비닐계 수지 100 중량부에 대하여 0.5 내지 12 중량부로 포함할 수 있다.The expandable vinyl chloride-based resin composition may include 0.5 to 12 parts by weight of the p,p'-oxybis (benzenesulfonyl hydrazide) based on 100 parts by weight of the vinyl chloride-based resin.
상기 발포성 염화비닐계 수지 조성물은, 상기 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트, 및 p,p'-옥시비스(벤젠술포닐히드라지드)를 20:1 내지 7:1의 중량비로 포함할 수 있다.The expandable vinyl chloride resin composition contains the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and p,p'-oxybis(benzenesulfonylhydrazide) from 20:1 to 7 It can be included in a weight ratio of :1.
상기 염화비닐계 수지는 중합도가 800 이상 내지 1,700 미만인 것일 수 있다.The vinyl chloride-based resin may have a degree of polymerization of 800 or more to less than 1,700.
바람직하기로, 상기 발포성 염화비닐계 수지 조성물은, 상기 염화비닐계 수지 100 중량부에 대하여, 상기 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트 70 내지 100 중량부, 및 상기 p,p'-옥시비스(벤젠술포닐히드라지드) 5 내지 10 중량부를 포함할 수 있다.Preferably, the expandable vinyl chloride-based resin composition is, based on 100 parts by weight of the vinyl chloride-based resin, the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate 70 to 100 parts by weight, and It may contain 5 to 10 parts by weight of the p,p'-oxybis (benzenesulfonyl hydrazide).
한편, 상기 발포성 염화 비닐계 수지 조성물은 안정제 및/또는 충전제를 더 포함할 수 있다.On the other hand, the foamable vinyl chloride resin composition may further include a stabilizer and/or a filler.
상기 안정제는 Ca-Zn계 화합물, K-Zn계 화합물, Ba-Zn계 화합물, 유기 Tin계 화합물, 메탈릭 비누계 화합물, 페놀계 화합물, 인산 에스테르계 화합물 및 아인산 에스테르계 화합물로 이루어진 군에서 선택되는 어느 하나 이상일 수 있다.The stabilizer is selected from the group consisting of Ca-Zn-based compounds, K-Zn-based compounds, Ba-Zn-based compounds, organic Tin-based compounds, metallic soap-based compounds, phenolic compounds, phosphoric acid ester compounds, and phosphorous acid ester compounds. It can be any one or more.
상기 충전제는 탄산칼슘, 탈크, 이산화티탄, 카올린, 실리카, 알루미나, 수산화마그네슘 및 점토로 이루어진 군에서 선택되는 어느 하나 이상일 수 있다.The filler may be at least one selected from the group consisting of calcium carbonate, talc, titanium dioxide, kaolin, silica, alumina, magnesium hydroxide, and clay.
또, 본 발명은 상기 발포성 염화비닐계 수지 조성물을 포함하는 성형품을 제공한다.In addition, the present invention provides a molded article comprising the foamable vinyl chloride resin composition.
상기 성형품은 벽지, 발포 매트, 바닥재, 인조 피혁, 또는 자동차 내장재일 수 있다.The molded article may be wallpaper, foam mat, flooring, artificial leather, or automobile interior material.
본 발명에 따른 발포성 염화비닐계 수지 조성물은 염화비닐계 수지, 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트, 및 p,p'-옥시비스(벤젠술포닐히드라지드)를 함께 포함하여, 우수한 발포 특성을 나타낸다. 또, 상기 발포성 염화비닐계 수지 조성물은 프탈레이트계 가소제 및 ADCA를 포함하지 않아 환경 호르몬 및 휘발성 유기 화합물의 발생 우려가 적어 친환경적이다.The expandable vinyl chloride resin composition according to the present invention is a vinyl chloride resin, di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and p,p'-oxybis(benzenesulfonylhydrazide) By including together, it shows excellent foaming properties. In addition, since the foamable vinyl chloride-based resin composition does not contain a phthalate-based plasticizer and ADCA, it is environmentally friendly because there is little concern about the occurrence of environmental hormones and volatile organic compounds.
이에, 본 발명의 발포성 염화비닐계 수지 조성물은 벽지, 발포 매트, 바닥재, 인조 피혁, 또는 자동차 내장재 등에 적합하게 사용될 수 있다.Accordingly, the foamable vinyl chloride resin composition of the present invention may be suitably used for wallpaper, foam mat, flooring, artificial leather, or automobile interior materials.
도 1은 실시예 및 비교예의 각 발포 시트의 단면을 촬영한 사진이다.1 is a photograph of a cross section of each foam sheet of Examples and Comparative Examples.
도 2는 실시예 및 비교예의 겔링 속도 측정 그래프이다. 2 is a graph of measuring gelling speeds of Examples and Comparative Examples.
본 명세서에서 사용되는 용어는 단지 예시적인 실시예들을 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도는 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. The terms used in the present specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise.
본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는 바, 특정 실시예들을 예시하고 하기에서 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.The present invention will be described in detail below and exemplify specific embodiments, as various changes may be made and may have various forms. However, this is not intended to limit the present invention to a specific form of disclosure, it is to be understood as including all changes, equivalents, and substitutes included in the spirit and scope of the present invention.
이하, 발명의 구체적인 구현예에 따라 발포성 염화비닐계 수지 조성물 및 성형품에 대해 보다 상세히 설명하기로 한다.Hereinafter, a foamable vinyl chloride resin composition and a molded article will be described in more detail according to a specific embodiment of the present invention.
본 발명에 따른 발포성 염화비닐계 수지 조성물은 p,p'-옥시비스(벤젠술포닐히드라지드)(OBSH)의 부족한 발포 성능을, 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트(DEHCH)를 함께 사용함으로써 보완할 수 있음에 착안한 것이다. 뿐만 아니라, 상기 발포성 염화비닐계 수지 조성물은 친환경적 발포제인 OBSH를 사용하고, 프탈레이트계 가소제를 포함하지 않으므로, 휘발성 유기 화합물 발생이나 환경 호르몬 방출의 위험이 크게 감소된 친환경 소재로서 사용될 수 있다.The foamable vinyl chloride-based resin composition according to the present invention has the insufficient foaming performance of p,p'-oxybis(benzenesulfonylhydrazide) (OBSH), di(2-ethylhexyl)cyclohexane-1,4-dicar It was conceived that it can be supplemented by using a deoxylate (DEHCH) together. In addition, since the foamable vinyl chloride-based resin composition uses OBSH, an eco-friendly foaming agent, and does not contain a phthalate plasticizer, it can be used as an eco-friendly material that greatly reduces the risk of generation of volatile organic compounds or release of environmental hormones.
본 발명의 일 구현예에 따른 발포성 염화비닐계 수지 조성물은 염화비닐계 수지, 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트, 및 p,p'-옥시비스(벤젠술포닐히드라지드)를 포함한다.The expandable vinyl chloride resin composition according to an embodiment of the present invention includes a vinyl chloride resin, di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and p,p'-oxybis(benzenesulfuryl). Phonylhydrazide).
본 명세서 전체에서 염화비닐계 수지란 염화비닐계 단량체 단독, 또는 염화비닐계 단량체 및 이와 공중합 가능한 공단량체가 공중합된 (공)중합체를 지칭한다. 이 외에 현탁제, 완충제, 및 중합 개시제 등을 혼합하여 현탁 중합, 미세 현탁 중합, 유화 중합, 또는 미니에멀전 중합 등의 중합 방법에 의해 제조될 수 있다.Throughout the present specification, the vinyl chloride-based resin refers to a vinyl chloride-based monomer alone or a (co)polymer in which a vinyl chloride-based monomer and a comonomer copolymerizable therewith are copolymerized. In addition, it may be prepared by a polymerization method such as suspension polymerization, micro-suspension polymerization, emulsion polymerization, or mini-emulsion polymerization by mixing a suspension agent, a buffer, and a polymerization initiator.
상기 염화비닐계 수지는 폴리비닐클로라이드(polyvinyl chloride, PVC)로서, OBSH 발포제와의 상용성을 고려하여 중합도(Degree of polymerization)가 800 이상 내지 1,700 미만인 것을 사용할 수 있다. 또는, 상기 염화비닐계 수지의 중합도는 900 내지 1500일 수 있다. 만일 염화비닐계 수지의 중합도가 1,700이상으로 너무 높은 경우, OBSH 발포제가 발포되는 온도에서 발포 시트가 형성되지 않고 기화된 발포제가 모두 빠져나가 발포가 원활히 일어나지 못할 수 있고, 반대로 중합도가 800 미만인 경우, 발포제가 기화되기 전 성형이 완료되어 발포가 일어나지 못하는 문제가 있을 수 있다. The vinyl chloride-based resin is polyvinyl chloride (PVC), and a degree of polymerization of 800 or more to less than 1,700 may be used in consideration of compatibility with an OBSH foaming agent. Alternatively, the degree of polymerization of the vinyl chloride-based resin may be 900 to 1500. If the degree of polymerization of the vinyl chloride-based resin is too high, above 1,700, foam sheets are not formed at the temperature at which the OBSH foaming agent is foamed, and all of the vaporized foaming agent escapes and foaming may not occur smoothly. Conversely, if the degree of polymerization is less than 800, There may be a problem that foaming does not occur because the molding is completed before the foaming agent is evaporated.
상기 염화비닐 수지의 중합도는 JIS K 6720-2에 의하여 측정될 수 있다. The degree of polymerization of the vinyl chloride resin can be measured according to JIS K 6720-2.
상기 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트(Di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate; DEHCH)는 하기 화학식 1로 표시되는 화합물로서, 본 발명에서 염화비닐계 수지의 가소제로 사용된다. DEHCH는 상온 및 저온 점도가 낮아 우수한 코팅 특성을 구현할 수 있으며, 겔링 속도가 빠르고, 발포 물성이 우수하다. 또, 기존 프탈레이트계 가소제에 비하여 휘발성 유기 화합물의 발생을 최소화할 수 있으며, DOTP와 달리 분자 구조 내 벤젠 고리를 포함하지 않으므로 잠재적 위험성을 줄일 수 있다.The di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (Di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate; DEHCH) is a compound represented by the following Chemical Formula 1, and is chlorinated in the present invention. It is used as a plasticizer for vinyl resins. DEHCH has low viscosity at room temperature and low temperature, so it can realize excellent coating properties, has a fast gelling speed, and has excellent foaming properties. In addition, it is possible to minimize the generation of volatile organic compounds compared to existing phthalate plasticizers, and unlike DOTP, since it does not contain a benzene ring in the molecular structure, it is possible to reduce the potential risk.
[화학식 1][Formula 1]
Figure PCTKR2020009962-appb-img-000001
Figure PCTKR2020009962-appb-img-000001
상기 DEHCH는 염화비닐계 수지 100 중량부에 대하여 50 내지 120 중량부, 또는 70 내지 100 중량부로 포함될 수 있다. 만일 DEHCH의 함량이 염화비닐계 수지 100 중량부에 대하여 50 중량부 미만이면 점도가 너무 높아 가공이 어려우며, OBSH의 발포 성능 보완 효과를 얻을 수 없다. 또, DEHCH 함량이 염화비닐계 수지 100 중량부에 대하여 120 중량부를 초과할 경우, 점도가 너무 낮아 가공이 어려우며, 겔링이 너무 느려져서 발포제가 기화할 때 발생하는 가스가 셀을 형성하지 못하고 다 빠져나가 발포성이 열세해지는 문제가 있어 바람직하지 않다.The DEHCH may be included in an amount of 50 to 120 parts by weight, or 70 to 100 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content of DEHCH is less than 50 parts by weight based on 100 parts by weight of the vinyl chloride-based resin, the viscosity is too high and processing is difficult, and the effect of supplementing the foaming performance of OBSH cannot be obtained. In addition, if the DEHCH content exceeds 120 parts by weight based on 100 parts by weight of the vinyl chloride resin, the viscosity is too low to process, and the gelling is too slow, so that the gas generated when the foaming agent evaporates does not form a cell and escapes. There is a problem that the foamability is inferior, which is not preferable.
바람직하기로, 본 발명의 발포성 염화비닐계 수지 조성물은 가소제로 DEHCH 만을 단독으로 포함하고, DEHCH 이외의 가소제를 더 포함하지 않을 수 있다.Preferably, the expandable vinyl chloride resin composition of the present invention contains only DEHCH as a plasticizer, and may not further contain a plasticizer other than DEHCH.
상기 p,p'-옥시비스(벤젠술포닐히드라지드)(p,p'-Oxybis(benzenesulfonyl hydrazide); OBSH)는 하기 화학식 2로 표시되는 화합물로서, 본 발명에서 발포제로 사용된다. The p,p'-oxybis (benzenesulfonyl hydrazide) (p,p'-Oxybis (benzenesulfonyl hydrazide); OBSH) is a compound represented by the following formula (2), and is used as a blowing agent in the present invention.
[화학식 2][Formula 2]
Figure PCTKR2020009962-appb-img-000002
Figure PCTKR2020009962-appb-img-000002
상기 OBSH는 염화비닐계 수지 100 중량부에 대하여 0.5 내지 12 중량부, 또는 5 내지 10 중량부로 포함하는 것이 바람직하다. 만일 OBSH의 함량이 염화비닐계 수지 100 중량부에 대해 0.5 중량부 미만이면 충분한 발포가 일어나지 않는 문제가 있고, 12 중량부를 초과하면 발포 셀의 안정성이 열세해지는 문제가 있을 수 있다. The OBSH is preferably included in an amount of 0.5 to 12 parts by weight, or 5 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content of OBSH is less than 0.5 parts by weight based on 100 parts by weight of the vinyl chloride-based resin, there is a problem that sufficient foaming does not occur, and if it exceeds 12 parts by weight, there may be a problem that the stability of the foaming cell is poor.
OBSH는 ADCA와 달리 포름아마이드, 암모니아 등의 유해 성분 발생이 적어 친환경적이다. 그러나 OBSH의 가스 방출량은 약 125 ml/g 정도로 ADCA(약 220 ml/g)에 미치지 못하고, 분해 온도가 157 내지 160 ℃로 낮아, 동일 가공 조건에서 발포 성능이 ADCA에 비해 떨어지는 문제가 있다. 이에, 본 발명에서는 상술한 DEHCH를 가소제로 사용함으로써 OBSH의 부족한 발포 성능을 보완하였다. Unlike ADCA, OBSH is eco-friendly because it does not generate harmful components such as formamide and ammonia. However, the amount of gas released from OBSH is about 125 ml/g, which does not reach ADCA (about 220 ml/g), and the decomposition temperature is low at 157 to 160° C., and foaming performance is lower than that of ADCA under the same processing conditions. Accordingly, in the present invention, the insufficient foaming performance of OBSH is supplemented by using the above-described DEHCH as a plasticizer.
상기 효과를 확보하기 위하여, 상기 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트, 및 p,p'-옥시비스(벤젠술포닐히드라지드)의 중량비는 20:1 내지 7:1, 또는 10:1 내지 7:1 범위인 것이 바람직하다. 상기 중량비를 만족하는 범위 내에서, 충분한 가소화 효과와 동시에 우수한 발포 성능을 기대할 수 있다. In order to secure the effect, the weight ratio of the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and p,p'-oxybis(benzenesulfonylhydrazide) is 20:1 to 7 It is preferably in the range of :1, or 10:1 to 7:1. Within a range that satisfies the above weight ratio, a sufficient plasticizing effect and excellent foaming performance can be expected.
한편, 본 발명의 발포성 염화비닐계 수지 조성물은 발포제로서 상기 OBSH 만을 단독으로 사용하고, OBSH 이외의 발포제를 더 포함하지 않을 수 있다. 이와 같이 발포성 염화비닐계 수지 조성물에 DEHCH 가소제와 함께 발포제로 OBSH만을 사용할 경우, 보다 우수한 발포 성능을 나타낼 수 있다.On the other hand, the foamable vinyl chloride resin composition of the present invention may use only the above OBSH as a foaming agent, and may not further contain a foaming agent other than OBSH. As described above, when only OBSH is used as a foaming agent together with a DEHCH plasticizer in the foamable vinyl chloride resin composition, more excellent foaming performance may be exhibited.
한편, 본 발명의 일 구현예에 따른 발포성 염화비닐계 수지 조성물은, 상기 염화비닐계 수지 100 중량부에 대하여, 상기 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트 50 내지 120 중량부, 및 상기 p,p'-옥시비스(벤젠술포닐히드라지드) 0.5 내지 12 중량부를 포함할 수 있다. On the other hand, the expandable vinyl chloride resin composition according to an embodiment of the present invention, based on 100 parts by weight of the vinyl chloride resin, the di (2-ethylhexyl) cyclohexane-1,4-dicarboxylate 50 to 120 parts by weight, and 0.5 to 12 parts by weight of the p,p'-oxybis (benzenesulfonyl hydrazide) may be included.
또, 본 발명의 다른 일 구현예에 따른 발포성 염화비닐계 수지 조성물은, 상기 염화비닐계 수지 100 중량부에 대하여, 상기 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트 70 내지 100 중량부, 및 상기 p,p'-옥시비스(벤젠술포닐히드라지드) 5 내지 10 중량부를 포함할 수 있다.In addition, the expandable vinyl chloride resin composition according to another embodiment of the present invention, based on 100 parts by weight of the vinyl chloride resin, the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate 70 To 100 parts by weight, and 5 to 10 parts by weight of the p,p'-oxybis (benzenesulfonyl hydrazide).
상기 염화비닐계 수지 조성물은 첨가제, 예를 들어 안정제, 충전제 등을 추가로 포함할 수 있다. 상기 첨가제는 염화비닐계 수지 조성물에서 향상시키고자 하는 물성에 따라 적합하게 선택될 수 있다. The vinyl chloride-based resin composition may further include additives such as stabilizers and fillers. The additive may be appropriately selected according to physical properties to be improved in the vinyl chloride resin composition.
상기 안정제는 염화비닐계 수지에서 HCl이 분리되어 발색단인 폴리엔 구조를 형성하여 주쇄의 절단, 가교 현상을 일으켜 발생하는 여러 가지 물성 변화를 예방하는 목적으로 첨가되는 것으로, Ca-Zn계 화합물, K-Zn계 화합물, Ba-Zn계 화합물, 유기 Tin계 화합물, 메탈릭 비누계 화합물, 페놀계 화합물, 인산 에스테르계 화합물 및 아인산 에스테르계 화합물로 이루어진 군으로부터 선택되는 어느 하나 이상인 것을 포함한다. The stabilizer is added for the purpose of preventing various changes in physical properties caused by cutting and crosslinking of the main chain by separating HCl from the vinyl chloride-based resin to form a polyene structure, which is a chromophore, and Ca-Zn-based compound, K -Zn-based compounds, Ba-Zn-based compounds, organic Tin-based compounds, metallic soap-based compounds, phenolic compounds, phosphoric acid ester compounds and phosphorous acid ester compounds include any one or more selected from the group consisting of.
본 발명에서 사용될 수 있는 안정제로 보다 구체적인 예는 Ca-Zn계 화합물; K-Zn계 화합물; Ba-Zn계 화합물; 머캡티드(Mercaptide)계 화합물, 말레인산계 화합물 또는 카르복실산계 화합물과 같은 유기 Tin계 화합물; Mg-스테아레이트, Ca-스테아레이트, Pb-스테아레이트, Cd-스테아레이트, 또는 Ba-스테아레이트 등과 같은 메탈릭 비누계 화합물; 페놀계 화합물; 인산 에스테르계 화합물; 또는 아인산 에스테르계 화합물 등이며, 사용 목적에 따라 선택적으로 포함된다. 본 발명에서는 특히 K-Zn계 화합물, 바람직하게는 K-Zn계 복합 유기화합물을 사용하는 것이 바람직하다. More specific examples as a stabilizer that can be used in the present invention are Ca-Zn-based compounds; K-Zn-based compounds; Ba-Zn-based compounds; Organic Tin-based compounds such as mercaptide-based compounds, maleic acid-based compounds, or carboxylic acid-based compounds; Metallic soap-based compounds such as Mg-stearate, Ca-stearate, Pb-stearate, Cd-stearate, or Ba-stearate; Phenolic compounds; Phosphoric acid ester compounds; Or a phosphorous acid ester compound, and the like, and is optionally included depending on the purpose of use. In the present invention, it is particularly preferable to use a K-Zn-based compound, preferably a K-Zn-based complex organic compound.
상기 안정제는 염화비닐계 수지 100 중량부에 대하여 바람직하게는 0.5 내지 5 중량부, 더욱 바람직하게는 1 내지 3 중량부가 포함된다. 안정제의 함량이 0.5 중량부 미만이면, 열안정성이 떨어지는 문제점이 있고, 5 중량부를 초과하면 가공성이 떨어지는 문제가 있다.The stabilizer is preferably 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content of the stabilizer is less than 0.5 parts by weight, there is a problem that the thermal stability is poor, and if it exceeds 5 parts by weight, there is a problem that the workability is poor.
본 발명의 충전제는 염화비닐계 수지 조성물의 생산성, 건조 상태의 감촉(Dry touch)감을 향상시키는 목적으로 사용되며, 탄산칼슘, 탈크, 이산화티탄, 카올린, 실리카, 알루미나, 수산화마그네슘 및 점토로 이루어진 군에서 선택되는 어느 하나 이상인 것을 포함한다.The filler of the present invention is used for the purpose of improving the productivity and dry touch of a vinyl chloride resin composition, and is a group consisting of calcium carbonate, talc, titanium dioxide, kaolin, silica, alumina, magnesium hydroxide, and clay. It includes any one or more selected from.
상기 본 발명에 따른 염화비닐계 수지 조성물에서 상기 충전제는 바람직하게는 10 내지 100 중량부, 더욱 바람직하게는 20 내지 50 중량부 포함될 수 있다. 충전제가 10 중량부 미만으로 포함된 경우, 치수안정성과 경제성이 낮아지는 문제점이 있고, 100 중량부 초과하여 포함된 경우, 발포 표면이 좋지 않으며, 가공성이 저하되는 문제점이 있다.In the vinyl chloride resin composition according to the present invention, the filler may preferably be 10 to 100 parts by weight, more preferably 20 to 50 parts by weight. When the filler is included in an amount of less than 10 parts by weight, there is a problem that dimensional stability and economy are lowered, and when it is included in an amount exceeding 100 parts by weight, the foaming surface is not good, and there is a problem that the workability is deteriorated.
본 발명에 따른 발포성 염화비닐계 수지 조성물은 염화비닐계 수지, 가소제로 DEHCH, 발포제로 OBSH, 및 선택적으로 첨가제를 사용하여 당업계에 일반적으로 알려진 방법에 의하여 제조될 수 있으며, 그 방법에 있어서 특별히 한정되지는 않는다.The expandable vinyl chloride-based resin composition according to the present invention may be prepared by a method generally known in the art using a vinyl chloride-based resin, DEHCH as a plasticizer, OBSH as a foaming agent, and optionally additives. It is not limited.
본 발명의 발포성 염화비닐계 수지 조성물은 DEHCH 및 OBSH를 함께 포함하여 기존의 ADCA 발포제와 유사한 수준의 우수한 발포 특성을 나타낸다. 이에, 상기 발포성 염화비닐계 수지 조성물은 벽지, 발포 매트, 바닥재, 인조 피혁, 자동차 내장재 등으로 사용될 수 있다. 특히, 본 발명의 발포성 염화비닐계 수지 조성물은 프탈레이트계 가소제를 포함하지 않고, 포름아마이드 등 휘발성 유기 화합물을 발생시키는 발포제를 배제하여 인체 유해성이 크게 저감된 바, 놀이방용 매트 등 유해 물질의 배제가 요구되는 분야에 적합하게 사용될 수 있다.The foamable vinyl chloride-based resin composition of the present invention includes DEHCH and OBSH together and exhibits excellent foaming properties similar to those of the existing ADCA foaming agent. Thus, the foamable vinyl chloride-based resin composition may be used as wallpaper, foam mat, flooring, artificial leather, automobile interior materials, and the like. In particular, the expandable vinyl chloride-based resin composition of the present invention does not contain a phthalate plasticizer, and a foaming agent that generates volatile organic compounds such as formamide is greatly reduced, thereby reducing harmful substances such as playroom mats. It can be suitably used in a required field.
한편, 본 발명의 다른 일 측면에 따르면, 상기 염화비닐계 수지 조성물을 포함하는 성형품이 제공된다. 상기 성형품은 그 용도에 따라 상기 염화비닐계 수지 조성물에 안정제, 충진제, 및/또는 발포제 등의 첨가제를 추가로 첨가하여 제조될 수 있다. 상기 성형품은 벽지, 발포 매트, 바닥재, 인조 피혁, 자동차 내장재 등으로 사용될 수 있다.Meanwhile, according to another aspect of the present invention, a molded article including the vinyl chloride-based resin composition is provided. The molded article may be manufactured by additionally adding additives such as a stabilizer, a filler, and/or a foaming agent to the vinyl chloride-based resin composition according to its use. The molded article may be used as wallpaper, foam mat, flooring, artificial leather, automobile interior material, and the like.
이하, 하기 실시예에 의하여 본 발명을 더욱 상세하게 설명하고자 한다. 단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐 본 발명의 범위가 이들만으로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail by the following examples. However, the following examples are for illustrative purposes only, and the scope of the present invention is not limited thereto.
[실시예][Example]
<발포성 염화비닐계 수지 조성물 및 발포 시트의 제조><Production of foamable vinyl chloride resin composition and foam sheet>
실시예 1Example 1
폴리비닐클로라이드(중합도 1000) 100 중량부에 대하여, 가소제로 DEHCH 90 중량부, 발포제로 OBSH 10 중량부를 계량하고 Mixer로 15분 동안 혼합하여 발포성 염화비닐계 수지 조성물(플라스티졸)을 제조하였다.With respect to 100 parts by weight of polyvinyl chloride (polymerization degree 1000), 90 parts by weight of DEHCH as a plasticizer and 10 parts by weight of OBSH as a foaming agent were weighed and mixed for 15 minutes with a mixer to prepare a foamable vinyl chloride-based resin composition (plastisol).
실시예 2Example 2
가소제로 DEHCH 80 중량부를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 발포성 염화비닐계 수지 조성물을 제조하였다.A foamable vinyl chloride resin composition was prepared in the same manner as in Example 1, except that 80 parts by weight of DEHCH was used as a plasticizer.
실시예 3Example 3
가소제로 DEHCH 70 중량부를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 발포성 염화비닐계 수지 조성물을 제조하였다.A foamable vinyl chloride resin composition was prepared in the same manner as in Example 1, except that 70 parts by weight of DEHCH was used as a plasticizer.
비교예 1Comparative Example 1
고중합도 폴리비닐클로라이드(중합도 1700) 100 중량부에 대하여, 가소제로 디옥틸테레프탈레이트(DOTP) 90 중량부, 발포제로 아조디카본아마이드(ADCA) 5 중량부를 계량하고 Mixer로 15분 동안 혼합하여 발포성 염화비닐계 수지 조성물(플라스티졸)을 제조하였다.With respect to 100 parts by weight of high polymerization polyvinyl chloride (polymerization degree 1700), 90 parts by weight of dioctyl terephthalate (DOTP) as a plasticizer, 5 parts by weight of azodicarbonamide (ADCA) as a foaming agent are weighed and mixed for 15 minutes with a mixer for foamability. A vinyl chloride resin composition (plastisol) was prepared.
비교예 2Comparative Example 2
고중합도 폴리비닐클로라이드(중합도 1700) 100 중량부에 대하여, 가소제로 DOTP 90 중량부, 발포제로 OBSH 10 중량부를 계량하고 Mixer로 15분 동안 혼합하여 발포성 염화비닐계 수지 조성물(플라스티졸)을 제조하였다.With respect to 100 parts by weight of high polymerization polyvinyl chloride (polymerization degree 1700), 90 parts by weight of DOTP as a plasticizer and 10 parts by weight of OBSH as a blowing agent are weighed and mixed for 15 minutes with a mixer to prepare a foamable vinyl chloride resin composition (plastisol). I did.
비교예 3Comparative Example 3
가소제로 DOTP를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 발포성 염화비닐계 수지 조성물을 제조하였다.A foamable vinyl chloride resin composition was prepared in the same manner as in Example 1, except that DOTP was used as a plasticizer.
<실험예><Experimental Example>
(1) 발포 시트 제조 및 발포성 측정(1) Foam sheet manufacturing and foaming property measurement
실시예(Ex.) 및 비교예(C.Ex.)의 각 플라스티졸을 어플리케이터를 이용하여 종이 위에 1.0 mm 두께로 코팅한 후 190 ℃ 내지 230 ℃ 오븐에서 80 내지 160초 동안 열을 가하여 발포시켜 발포 시트를 제작하였다. Each plastisol of Examples (Ex.) and Comparative Examples (C.Ex.) was coated to a thickness of 1.0 mm on paper using an applicator, and then heated in an oven at 190°C to 230°C for 80 to 160 seconds to foam To prepare a foam sheet.
상기 발포 시트의 두께를 측정하고, 발포 셀의 균일도를 육안으로 확인하였다. 도 1은 각 발포 시트의 단면을 촬영한 사진이다. The thickness of the foam sheet was measured, and the uniformity of the foam cell was visually confirmed. 1 is a photograph of a cross section of each foam sheet.
(2) 겔링 속도(2) gelling speed
실시예(Ex.) 및 비교예(C.Ex.)의 각 플라스티졸을 SVNC 장비를 이용하여 120 ℃에서 겔링 속도를 측정하였다. SVNC 장비에서 겔링이 진행될수록 진폭(amplitude)이 감소하는데, 이 값이 감소하는 속도를 이용하여 겔링 속도를 비교 측정하였다. 도 2는 겔링 속도 측정 그래프이다.Each plastisol of Example (Ex.) and Comparative Example (C.Ex.) was measured for gelling rate at 120° C. using SVNC equipment. In the SVNC equipment, as the gelling proceeds, the amplitude decreases, and the gelling speed was compared and measured using the rate at which this value decreases. 2 is a graph of measuring gelling speed.
(3) 포름아마이드 방출 여부(3) Whether formamide is released
실시예 및 비교예의 플라스티졸을 이용하여 제작한 발포시트를, 반지름 3cm의 원형태로 샘플링하여 40 ℃에서 1시간 동안 전처리를 진행하였다. 이후 발생하는 기체시료를 채취 및 가스크로마토그래피(Gas Chromatography)를 이용하여 포름아마이드 방출량을 측정하였다. Foam sheets prepared using the plastisols of Examples and Comparative Examples were sampled in a circle shape with a radius of 3 cm, and pretreated at 40° C. for 1 hour. The gas sample generated after that was collected and the amount of formamide released was measured using Gas Chromatography.
상기 실험 결과를 하기 표 1에 정리하였다.The experimental results are summarized in Table 1 below.
실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3
발포 시트 두께(mm)Foam sheet thickness (mm) 7.07.0 6.56.5 6.56.5 6.06.0 1.0 (발포되지 않음)1.0 (no foam) 5.05.0
발포 셀 균일도Foam cell uniformity ◎◎ ◎◎ ◎◎ ○○ -- ◎◎
겔링 속도Gelling speed ◎◎ ◎◎ ◎◎ △△ △△ ○○
포름아마이드 방출량(μg / m 3)Formamide emission (μg / m 3 ) -- -- -- 4031.854031.85 -- --
(매우 높음) ◎ > ○ > △ > X (매우 낮음)(Very High) ◎> ○> △> X (Very Low)
발포 제품에서 가장 중요한 것은 발포성이다. 발포성은 제품의 표면 상태, 발포 배율, 발포 셀의 크기 및 발포 셀의 균일성을 말한다. The most important thing in foam products is foamability. Foaming refers to the surface condition of the product, the foaming ratio, the size of the foaming cell and the uniformity of the foaming cell.
실험 결과, 실시예 1 내지 3의 발포성 염화비닐계 수지 조성물은 친환경적이면서도, 기존의 ADCA 발포제 및 DOTP 가소제를 포함하는 염화비닐계 수지 조성물과 비교하여 겔링 속도가 우수하면서, 동등 이상의 발포 특성을 나타내는 것을 확인할 수 있었다. 그러나 비교예 2 및 3과 같이 DEHCH 가소제 및 OBSH 발포제의 조합을 만족하지 못하는 경우는 발포가 일어나지 않거나, 발포성이 떨어지고, 겔링 속도가 저하되는 것을 확인할 수 있다.As a result of the experiment, the foamable vinyl chloride resin composition of Examples 1 to 3 was environmentally friendly, and exhibited equal or higher foaming characteristics while having excellent gelling speed compared to the conventional vinyl chloride resin composition containing the ADCA foaming agent and the DOTP plasticizer. I could confirm. However, when the combination of the DEHCH plasticizer and the OBSH foaming agent is not satisfied as in Comparative Examples 2 and 3, it can be seen that foaming does not occur, foaming property is poor, and the gelling speed is lowered.

Claims (11)

  1. 염화비닐계 수지, 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트, 및 p,p'-옥시비스(벤젠술포닐히드라지드)를 포함하는 발포성 염화비닐계 수지 조성물.A foamable vinyl chloride resin composition comprising a vinyl chloride resin, di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and p,p'-oxybis(benzenesulfonylhydrazide).
  2. 제1항에 있어서,The method of claim 1,
    상기 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트를 염화비닐계 수지 100 중량부에 대하여 50 내지 120 중량부로 포함하는 발포성 염화비닐계 수지 조성물.An expandable vinyl chloride resin composition comprising 50 to 120 parts by weight of the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate based on 100 parts by weight of the vinyl chloride resin.
  3. 제1항에 있어서,The method of claim 1,
    상기 p,p'-옥시비스(벤젠술포닐히드라지드)를 염화비닐계 수지 100 중량부에 대하여 0.5 내지 12 중량부로 포함하는 발포성 염화비닐계 수지 조성물.An expandable vinyl chloride-based resin composition comprising 0.5 to 12 parts by weight of the p,p'-oxybis (benzenesulfonyl hydrazide) based on 100 parts by weight of the vinyl chloride resin.
  4. 제1항에 있어서,The method of claim 1,
    상기 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트, 및 p,p'-옥시비스(벤젠술포닐히드라지드)를 20:1 내지 7:1의 중량비로 포함하는 발포성 염화비닐계 수지 조성물.Effervescent chloride containing the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and p,p'-oxybis(benzenesulfonylhydrazide) in a weight ratio of 20:1 to 7:1 Vinyl resin composition.
  5. 제1항에 있어서,The method of claim 1,
    상기 염화비닐계 수지는 중합도가 800 이상 내지 1,700 미만인 발포성 염화비닐계 수지 조성물.The vinyl chloride-based resin has a degree of polymerization of 800 or more to less than 1,700 expandable vinyl chloride-based resin composition.
  6. 제1항에 있어서,The method of claim 1,
    상기 염화비닐계 수지 100 중량부에 대하여,Based on 100 parts by weight of the vinyl chloride resin,
    상기 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트 70 내지 100 중량부, 및 70 to 100 parts by weight of the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and
    상기 p,p'-옥시비스(벤젠술포닐히드라지드) 5 내지 10 중량부를 포함하는 발포성 염화비닐계 수지 조성물.Foamable vinyl chloride resin composition comprising 5 to 10 parts by weight of the p,p'-oxybis (benzenesulfonyl hydrazide).
  7. 제1항에 있어서,The method of claim 1,
    안정제 및/또는 충전제를 더 포함하는 발포성 염화비닐계 수지 조성물.A foamable vinyl chloride resin composition further comprising a stabilizer and/or a filler.
  8. 제7항에 있어서,The method of claim 7,
    상기 안정제는 Ca-Zn계 화합물, K-Zn계 화합물, Ba-Zn계 화합물, 유기 Tin계 화합물, 메탈릭 비누계 화합물, 페놀계 화합물, 인산 에스테르계 화합물 및 아인산 에스테르계 화합물로 이루어진 군에서 선택되는 어느 하나 이상인 발포성 염화비닐계 수지 조성물.The stabilizer is selected from the group consisting of Ca-Zn-based compounds, K-Zn-based compounds, Ba-Zn-based compounds, organic Tin-based compounds, metallic soap-based compounds, phenolic compounds, phosphoric acid ester compounds, and phosphorous ester compounds Any one or more foamable vinyl chloride resin composition.
  9. 제7항에 있어서,The method of claim 7,
    상기 충전제는 탄산칼슘, 탈크, 이산화티탄, 카올린, 실리카, 알루미나, 수산화마그네슘 및 점토로 이루어진 군에서 선택되는 어느 하나 이상인 발포성 염화비닐계 수지 조성물.The filler is any one or more selected from the group consisting of calcium carbonate, talc, titanium dioxide, kaolin, silica, alumina, magnesium hydroxide, and clay.
  10. 제1항 내지 제9항 중 어느 한 항의 염화비닐계 수지 조성물을 포함하는 성형품.A molded article comprising the vinyl chloride resin composition of any one of claims 1 to 9.
  11. 제10항에 있어서,The method of claim 10,
    벽지, 발포 매트, 바닥재, 인조 피혁, 또는 자동차 내장재인, 성형품.Molded articles that are wallpaper, foam mats, flooring, artificial leather, or automotive interiors.
PCT/KR2020/009962 2019-07-31 2020-07-29 Expandable vinyl chloride resin composition WO2021020869A1 (en)

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