WO2019203498A1 - Composition de résine de chlorure de vinyle pour papier peint ayant une résistance améliorée à la décoloration - Google Patents

Composition de résine de chlorure de vinyle pour papier peint ayant une résistance améliorée à la décoloration Download PDF

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Publication number
WO2019203498A1
WO2019203498A1 PCT/KR2019/004371 KR2019004371W WO2019203498A1 WO 2019203498 A1 WO2019203498 A1 WO 2019203498A1 KR 2019004371 W KR2019004371 W KR 2019004371W WO 2019203498 A1 WO2019203498 A1 WO 2019203498A1
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Prior art keywords
vinyl chloride
chloride resin
weight
wallpaper
resin composition
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PCT/KR2019/004371
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English (en)
Korean (ko)
Inventor
장태영
김재송
류성민
Original Assignee
한화케미칼 주식회사
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Priority claimed from KR1020190041998A external-priority patent/KR102297787B1/ko
Application filed by 한화케미칼 주식회사 filed Critical 한화케미칼 주식회사
Priority to CN201980026431.6A priority Critical patent/CN111989367B/zh
Priority to EP19787719.4A priority patent/EP3783062A4/fr
Publication of WO2019203498A1 publication Critical patent/WO2019203498A1/fr

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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
    • 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
    • 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
    • C08K5/101—Esters; Ether-esters of monocarboxylic 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/18—Paper- or board-based structures for surface covering
    • D21H27/20—Flexible structures being applied by the user, e.g. wallpaper

Definitions

  • the present invention relates to a vinyl chloride resin composition for wallpaper having environmentally friendly and significantly improved discoloration characteristics.
  • Vinyl chloride resin is a hybrid polymer containing at least 50% of a vinyl chloride homopolymer and vinyl chloride, and is one of five general-purpose thermoplastic resins produced by suspension polymerization and emulsion polymerization.
  • the vinyl chloride resin prepared by emulsion polymerization is mixed with a subsidiary material having special functions such as a plasticizer, a stabilizer, a filler, a blowing agent, a pigment, and a plastisol. It is used in a wide range of applications such as flooring, wallpaper, tarpaulin, artificial leather, toys and undercarriage coatings through coating molding and mold coating molding processing in the form of (Plastisol).
  • Wallpaper is the most exposed product in residential and office space, and more than 60% is manufactured using vinyl chloride resin. Recently, the main issue of wallpaper is related to eco-friendly wallpaper, and the criterion for eco-friendliness is HB grade (best, excellent, good) according to the amount of volatile organic compounds (VOCs) conducted by the Korea Air Cleaning Association. Up to 3 steps) and phthalate plasticizer suspected to be an environmental hormone, an endocrine disruptor that disrupts or disrupts human hormonal action.
  • VOCs volatile organic compounds
  • Plastisols are prepared by mixing solid raw materials such as pigments and liquid raw materials such as plasticizers, stabilizers and viscosity reducing agents, and then coating the plastisols on paper and processing the gelling, printing, foaming and embossing processes. Manufactured through the process.
  • the plasticizer in the vinyl chloride resin composition for wallpaper is a liquid component that occupies a large amount and exhibits a migrat ion phenomenon that is mixed with the vinyl chloride resin at the initial stage of manufacture and gradually flows out of the vinyl chloride resin over time.
  • Spilled plasticizers can cause fatal harm by inhibiting the normal activity of the endocrine system or by triggering abnormal reactions when they enter the body, which can cause a direct impact on the human body. This is an important reason for limiting the use of plasticizers in wallpaper, tarpaulin, artificial leather, toys, automotive undercoats, and especially phthalate plasticizers.
  • the viscosity of the plastisol in the wallpaper manufacturing is the main physical properties that determine the coating properties and productivity of the wallpaper in the coating process, the lower the viscosity is advantageous.
  • the volatile organic compounds generated in the vinyl chloride resin wallpaper are mostly generated from the viscosity lowering agent added to lower the viscosity of the plastisol, the liquid stabilizer, and the solvent of the oil ink used in the printing process.
  • the viscosity reducing agent is added in excess, there is a problem that not only volatile organic compounds are generated but also the quality of the product is reduced. Therefore, in order to reduce the generation of volatile organic compounds, it is necessary to minimize the addition amount of a viscosity reducing agent and a liquid stabilizer, which causes the generation of volatile organic compounds.
  • the present invention is to solve the problems of the prior art as described above, and to provide a vinyl chloride resin composition for wallpaper having environmentally friendly and significantly improved discoloration characteristics.
  • Said 13) plasticizer is di (2-ethylnuclear) cyclonucleic acid-1,4-dicarboxylate), or the di (2-ethylnuclear) cyclonucleic acid-1,4-dicarboxylate and the following formula (1)
  • a vinyl chloride resin composition for wallpaper comprising a mixture of compounds represented by:
  • 3 ⁇ 4 is hydrogen or acetyl
  • 3 ⁇ 4 to 3 ⁇ 4 are each independently 0 2-8 alkyl.
  • it provides a wallpaper comprising the vinyl chloride resin composition.
  • the vinyl chloride resin composition for wallpaper according to the present invention is di (2-ethylnuclear) cyclonucleic acid-1,4-dicarboxylate.
  • plasticizer comprising a mixture of the compound represented by the formula (1), by using a combination of carboxylic acid ester viscosity-lowering agent and acidic ester-based dispersant excellent in compatibility therewith, exhibits excellent migration resistance, 2019/203498 1 »(1 ⁇ 1 ⁇ 2019/004371
  • the dyeing phenomenon by the dye can be prevented to exhibit a markedly improved discoloration characteristics.
  • the vinyl chloride resin composition is greatly reduced in the content of the liquid additives such as plasticizers that are diffused to the outside when applied to the wallpaper, etc., can prevent the occurrence of environmental problems.
  • the vinyl chloride resin composition exhibits a low viscosity by including a carboxylic acid ester-based viscosity reducing agent together with the plasticizer, and as a result, a viscosity reducing agent added to lower the viscosity of the plastisol, and may be optionally included.
  • a viscosity reducing agent added to lower the viscosity of the plastisol, and may be optionally included.
  • the vinyl chloride resin composition may be used for flooring, wallpaper, tarpaulin, artificial leather, toys, automotive undercoat, and the like, but may be particularly useful for the manufacture of wallpaper, especially eco-friendly silk wallpaper, because it has environmentally friendly and excellent discoloration properties.
  • 1 is a schematic diagram showing a discoloration mechanism occurring on the wallpaper due to the dye in the gypsum board.
  • Example 2 is a graph showing the results of the performance evaluation for the plastisol of Example 1 and Comparative Example 1.
  • Figure 3 is a photograph of the discoloration of the oil paper during the evaluation of the transferability of the plastisol of Comparative Example 1
  • Figure 3 ⁇ 4 is a photograph of the discoloration of the oil paper during the evaluation of the transferability of the plastisol of Example 1 to be.
  • Figure 4 is a graph showing the results of measuring the viscosity of the plastisol of Example 1 and Comparative Example 1.
  • ⁇ comprise, '' ⁇ include, '' or ⁇ have '' refer to a feature, step, component, or combination thereof that is embodied.
  • ⁇ refers to a feature, step, component, or combination thereof that is embodied.
  • ⁇ vinyl chloride resin composition '' includes "plastisol (1313 0 1)", which refers to a mixture of resin and plasticizer so as to be formed into a mold, mold or continuous film by heating.
  • the plastisol may be, for example, a paste mixture of a vinyl chloride resin and a plasticizer.
  • Vinyl chloride resin composition for wallpaper according to an embodiment of the present invention Per 100 parts by weight of vinyl chloride resin,
  • the plasticizer is di (2-ethylnucleyl) cyclonucleic acid-1,4-dicarboxylate ⁇ ), or the di (2-ethylnuclear) cyclonucleic acid-1,4-dicarboxylate and the following formula (1) Contains mixtures of the compounds represented:
  • 3 ⁇ 4 is hydrogen or acetyl
  • 3 ⁇ 4 are each independently 0 2-8 alkyl.
  • each component will be described in detail.
  • the vinyl chloride resin may be a homopolymer in which a vinyl chloride monomer is homopolymerized, or a copolymer in which a vinyl chloride monomer and a comonomer copolymerizable therewith are polymerized. Either or a mixture of the two may be used for the preparation of the vinyl chloride resin composition.
  • the comonomer copolymerizable with the vinyl chloride monomer is specifically vinyl esters such as vinyl acetate, vinyl propionate and vinyl stearate; Vinyl ethers having lower alkyl groups such as methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether, and lauryl vinyl ether (1 to 11); Halogenated vinylidene such as vinylidene chloride; Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, maleic anhydride and itaconic anhydride and acid anhydrides thereof; Unsaturated carboxylic acid esters (6) such as methyl acrylate, ethyl acrylate, monomethyl maleate, dimethyl maleate, and butylbenzyl maleate; Styrene, Aromatic vinyl compounds such as methyl styrene and divinyl benzene; Unsaturated nitriles such as acrylonitrile or
  • the comonomer may more preferably contain vinyl acetate in view of excellent compatibility with the vinyl chloride monomer and improved compatibility with the plasticizer constituting the resin composition after polymerization.
  • the resin is a vinyl chloride monomer alone, 2019/203498 1 »(: 1 ⁇ 1 ⁇ 2019/004371
  • the polymerization method is not particularly limited, and conventional polymerization known in the art, such as fine suspension polymerization, emulsion polymerization or seed emulsion polymerization It can be carried out according to the method. Among them, when prepared by emulsion polymerization or fine suspension polymerization, the average particle size of the vinyl chloride resin produced is small and uniform as compared with the case produced by other polymerization methods.
  • the average particle size and uniformity of the vinyl chloride resin can be further controlled by controlling the polymerization conditions during the polymerization, and the average particle size (3 ⁇ 4 0 ) of the vinyl chloride resin usable in the present invention is 0.1 to 40; Specifically, it may be from 1 to 10 ⁇ ⁇ , having a particle size in the above range, exhibits excellent dispersibility, and can further improve the fluidity of the plasticized vinyl chloride resin composition. If the average particle size 1 ⁇ 2) exceeds 40, the dispersibility is low in the vinyl chloride resin particles themselves, and if the average particle size 1 ⁇ 2) is less than 0.1 m, the dispersibility may decrease due to aggregation between the vinyl chloride resin particles. On the other hand, in the present invention, the average particle size of 01 ⁇ 2) of the vinyl chloride resin may be measured according to a conventional particle size distribution measurement method such as optical microscope observation method, light scattering measurement method.
  • the degree of polymerization and weight average molecular weight of the vinyl chloride resin may affect the compatibility of the components constituting the vinyl chloride resin composition, in particular, plasticizers and workability of the plastisol, through the control of the polymerization conditions during polymerization Can be adjusted appropriately.
  • the vinyl chloride resin has a degree of polymerization of 700 to 1,700 or a weight average molecular weight of 45,000 to 200,000. Can be.
  • the degree of polymerization and weight average molecular weight in the above range is excellent in dispersibility, good compatibility with the plasticizer, it is possible to improve the processability of the plastisol.
  • the degree of polymerization of vinyl chloride resin is less than 700 or 3 ⁇ 41 ⁇ 2 is less than 45,000 2 0 1, there is a possibility that the durability and workability of the wallpaper may be deteriorated due to insufficient physical properties, and the degree of polymerization is more than 1,700. If it exceeds 200,000 yo01, there is a fear of deterioration of foamability. More specifically, the degree of polymerization may be 900 or more but less than 1,050 or the weight average molecular weight (3 ⁇ 41 ⁇ 2) is 60,000 to 150,000. On the other hand, in the present invention, the weight average molecular weight of the vinyl chloride resin 0) 2019/203498 1 »(: 1 ⁇ 1 ⁇ 2019/004371
  • the plasticizer may be di (2-ethylnucleosil) cyclonucleic acid-1,4-dicarboxylate ⁇ ) alone, or the zero bond and Formula 1 above.
  • the plasticizer exhibits excellent compatibility with additives included in the vinyl chloride resin composition, and may increase productivity by increasing the gelling speed of the resin composition.
  • di (2-ethylnuclear) cyclonucleic acid-1,4-dicarboxylate di (2-ethylnucleosil) cyclonucleic acid-1,4-dicarboxylate ⁇ ) alone, or the zero bond and Formula 1 above.
  • I) ⁇ ⁇ ) is a compound represented by the following formula (I), which is sometimes referred to as zero example in English abbreviation.
  • Zero ties can realize excellent coating properties due to low temperature and low temperature viscosity, fast gelling speed, and excellent foaming properties.
  • the generation of volatile organic compounds can be minimized, the stability to the environment is high.
  • the plasticizer in the wallpaper is likely to be cut out to the surroundings by diffusion, and if it is bleeded into the paper layer in this way, the dye on the plasterboard base is likely to be transferred to the wallpaper surface.
  • the 0s have excellent migration resistance, the amount of folliculus spreading out of the wallpaper is less, and as a result, a phenomenon that the dye is less easily cut off on the paper can be prevented.
  • 001? Because it does not mix well with contrast ink, it is advantageous for discoloration. 1 is used with 00 ⁇ as a conventional plasticizer, It is a schematic diagram showing the discoloration mechanism that occurs in the wallpaper due to the dye in the gypsum board when using DEHCH in the invention. Referring to FIG.
  • the plasticizer contains a mixture of the compound represented by the formula (1) together with DEHCH, while maintaining the excellent properties of DEHCH as a plasticizer, it is possible to further suppress the transition of DEHCH.
  • the compound represented by Chemical Formula 1 is an ester compound of citric acid and C 2-8 alcohol, but is not limited in theory, and the plasticizer is moved to the outside of the vinyl chloride resin due to the interaction of hydrogen bond between the ester group and the DEHCH ester group. Do not spill.
  • 3 ⁇ 4 to 3 ⁇ 4 is preferably each independently butyl or octyl.
  • tributyl citrate TBC
  • tri (butyl octyl) citrate tr i (butyl octyl) citrate
  • the compound represented by Chemical Formula 1 may be purchased commercially and used, and may also be prepared by the same method as in Scheme i below.
  • the plasticizer is When the mixture of the compound represented by Formula 1 is included, the weight ratio of the two compounds may be preferably 9.5: 1 to 1: 9.5. When included in the above weight ratio, it is possible to improve the thermal stability and foamability of the resin composition while effectively improving the transition characteristics of the plasticizer.
  • the weight ratio of the zodiac to the compound represented by the formula (1) is less than 1: 9.5, there is a risk that the thermal stability and foamability of the resin composition may be lowered because the content of the zero bond and the content are excessively small. More preferably, the weight ratio of Example 11 to the compound represented by Formula 1 may be 9: 1 to 5: 5, even more preferably 9: 1 to 6: 4.
  • Such a plasticizer may be included in an amount of 50 to 90 parts by weight based on 100 parts by weight of the vinyl chloride resin.
  • the content of the plasticizer is less than 50 parts by weight, the viscosity of the vinyl chloride resin composition or the plastisol may increase, resulting in a decrease in coating properties or a decrease in the flexibility of the product.
  • the content of the plasticizer is greater than 90 parts by weight, the plasticizer may form a surface of the molded article.
  • the bleeding phenomenon 13166 ratio, 13 ⁇ 4 6 £ group 6
  • the plasticizer may be more specifically included in an amount of 60 to 80 parts by weight based on 100 parts by weight of the vinyl chloride resin in view of better effect on viscosity reduction and suppression of bleeding due to plasticizer content control of the vinyl chloride resin.
  • the viscosity reducing agent serves to lower the viscosity of the vinyl chloride resin composition to improve processability, and specifically, a carboxylic ester compound may be used.
  • the carboxylic acid ester-based viscosity lowering agent is a plasticizer and
  • the compatibility with vinyl chloride resin is excellent, and low volatility can reduce the amount of volatile organic compounds generated when used in a vinyl chloride resin composition.
  • the viscosity reducing agent is to prepare a carboxylic acid of 22 to 3 ⁇ 4- alcohol and ester reaction with an alkyl 3 ⁇ 4- 22, it may be a carboxylic acid ester represented by the following general formula 2:
  • R a and R b are each independently a C 8-22 linear or branched alkyl group such as n-octyl, t-butyl, n-nonyl, or n-decyl.
  • Viscosity reducing agents include BYK LP-R 22274ä,
  • Vi scobyhim 5025, 5125 and 5050, Jayf lexä 615 or Exxsolä D100, etc. can be used.
  • the viscosity lowering agent has a density of 0.85 to 0.9 g / cm 3 at 2CTC, more specifically 0.87 to 0.9 g ⁇ : m 3 , and a solidification point (Sol idi fi cat ion point) of -7 ° C. or less, and Specifically, it is -10 to -40 V, the flash point (fl ash point) may be 120 ° C subphase, more specifically 130 to 200 ° C.
  • the gelling speed is high and the viscosity lowering force is excellent, thereby further improving the processability of the resin composition.
  • the viscosity reducing agent may be included in 5 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content of the viscosity reducing agent is less than 5 parts by weight, the viscosity of the compound is high, there is a risk of defects such as Sol drop in the processing process, if exceeding 20 parts by weight, the foaming properties of the wallpaper is poor and excessive viscosity decreases There exists a possibility that moldability may fall. Considering the remarkable effects of defect generation and molding lowering effect due to the control of the viscosity lowering agent content of the vinyl chloride resin, the viscosity lowering agent is more specifically vinyl chloride resin 100 It may be included in 10 to 20 parts by weight based on parts by weight. d) dispersants
  • the dispersant is adsorbed on the surface to reduce the attraction between the particles, prevent reaggregation, thereby facilitating the movement of the particles, and serves to stabilize the viscosity and behavior of the resin composition.
  • At least one acidic ester (Acidi c ester) compound having excellent dispersibility may be used as the dispersant.
  • the acid ester compound may exhibit an excellent dispersibility for the vinyl chloride resin as well as exhibit an additional viscosity lowering effect due to the property of lowering the viscosity of the blend.
  • the acid ester compound may include a phosphate ester compound such as phosphate ester; Or Stearyl Cetyl Stearates (CETS), Ethylene Glycol Di stearate (EGDS), GlycerylMonoOleate (GM0), Pentaerythritol distearate (Penta & ythr i tol) Di stearate; PEDS), Pentaerythritol tetrastearate (PETS), Glyceryl Monostearate (GMS), or Stearyl Stearate, Distearyl Phthalate (Di fatty acid esters such as stearyl Pthal ate), and any one or two or more of these compounds may be used.
  • a phosphate ester compound may be preferable.
  • BYK-LP W 21809ä may be used commercially.
  • the dispersing agent has a density at 20 ° C. of 0.9 to 1.3 g / cra 3 , more specifically 0.90 to 1.1 gA: m 3 , an acid value of 80 to 120 mgK0H / g, more specifically 90 to 100 mgK0H / g.
  • excellent dispersibility can be exhibited and the effect of lowering the viscosity on the resin composition can be further improved.
  • the dispersant has a flash point of 80 ° C or more, 2019/203498 1 »(: 1 ⁇ 1 ⁇ 2019/004371
  • it may be 100 to 300.
  • the thermal stability of a resin composition can be improved.
  • the dispersant may be included in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content of the dispersant is less than 0.5 part by weight, there is a fear of poor dispersibility of the formulation, while if the content of the dispersant is more than 5 parts by weight, the foamability of the wallpaper may be lowered. Considering the remarkable dispersibility and foaming effect according to the dispersant content control for the vinyl chloride resin, the dispersant may be included in more specifically 1 to 3 parts by weight based on 100 parts by weight of the vinyl chloride resin. 6 Other additives
  • the vinyl chloride resin composition according to one embodiment of the invention optionally further comprises one or more additives selected from the group consisting of stabilizers, foaming agents, fillers and fat sugars (0 2 ) according to the properties to be improved in the composition can do.
  • the stabilizer is a vinyl chloride resin It is added to prevent the various physical property changes caused by the separation and crosslinking of the main chain to form a polyene structure is separated chromophore, it may be a liquid compound.
  • Specific examples are Compound, 0k-3 ⁇ 41 compound, The compound, an 8-3 ⁇ 4 type compound, an organic 11 type compound, a metallic soap type compound, a phenol type compound, or a phosphite ester type compound etc. are mentioned, Any one or a mixture of two or more of these can be used.
  • compound; compound; Organic 11-based compounds such as mercaptiated (3 ⁇ 43 ⁇ 40 1) 1 ⁇ (16) -based compounds, maleic acid-based compounds, or carboxylic acid-based compounds; 03-stearate,? 1) _stearate, 0 (1-stearate, or Metallic soap compounds such as acrylate; Phenolic compounds; Or phosphorous acid ester compounds, and among these, in the present invention, £ 1-3 ⁇ 4-based compounds or The compound can be used more preferably.
  • the additive stabilizer is preferably 0.5 based on 100 parts by weight of the vinyl chloride resin. 2019/203498 1 »(: 1/10 ⁇ 019/004371
  • the content of the stabilizer is less than 0.5 parts by weight, there is a problem that the thermal stability is inferior, and if more than 7 parts by weight, more than the required thermal stability can be expressed.
  • the blowing agent may include a chemical blowing agent or a physical blowing agent, and any one or a mixture thereof may be used.
  • the chemical blowing agent is not particularly limited as long as it is a compound that decomposes above a certain temperature to generate a gas, azodicarbonamide,
  • inorganic foaming agents such as carbon dioxide, nitrogen, argon, water, air and helium; Or an aliphatic hydrocarbon compound containing 1 to 9 carbon atoms, an aliphatic alcohol containing 1 to 3 carbon atoms, and a halogenated aliphatic hydrocarbon compound containing 1 to 4 carbon atoms organic foaming agents such as ic hydrocarbon).
  • the aliphatic hydrocarbon compound may include methane, ethane, propane, normal butane, isobutane, normal pentane, isopentane or neopentane, and the aliphatic alcohol may be methanol, ethanol, normal propanol, or isopropanol.
  • halogenated aliphatic hydrocarbon compounds such as methyl fluoride, perf luoromethane ethyl fluoride, and 1,1-difluoroethane (1,1_ (1). 11H01,061: 11 to 6 , HFC-152a), 1,1,1- 2019/203498 1 »(: 1/10 ⁇ 019/004371
  • Trifluoroethane (1,1, 1-trif luoroethane, HFC - 143a), 1, 1, 1,2-tetrafluoroethane (1,1,1, 2-tetraf luoroethane, HFC-134a), 1, 1,2,2-tetrafluoroethane (1, 1,2,2-tetraf luoromethane, HFC-134), 1, 1, 1,3,3-pentafluorobutane (1, 1, 1,3, 3-pentaf luorobutane, HFC-365mfc ), 1, 1, 1,.
  • 1,3,3-pentafluoropropane (1, 1, 1, 3, 3-pent af 1 uor opr opane, HFC.sub.13 245f a), pentafluoroethane, difluoromethane (di f luoromethane), per f luoroethane, 2, 2-difluoropropane (2, 2- dif luoropropane), 1, 1, 1-trifluoropropane (1, 1, l_tr if luoropropane, perf luoropropane, dichloropropane, dichloropropane, dif luoropropane, perfluoro butane, perf luorobutane, perfluoro cyclobutane, methyl chloride chloride), methylene chloride, ethyl chloride, 1, 1,1-trichloroethane (1, 1,1-tr i chloroethane
  • Dichlorotetraf luoroethane (CFC-114), chloroheptaf luoropropane, dichlorohexaf luoropropane and the like. Any one or a mixture of two or more of the above compounds may be used as blowing agent. 2019/203498 1 »(: 1 ⁇ 1 ⁇ 2019/004371
  • Such a blowing agent may be included in an amount of 0.5 to 7 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content of the blowing agent is less than 0.5 parts by weight, the amount of gas generated for foaming is too small, so the foaming effect is insignificant or not expected at all, and if it exceeds 7 parts by weight, it is difficult to expect the required physical properties. .
  • the said filler is used for the purpose of improving the productivity of a vinyl chloride resin composition, and the feeling of dryness 0) 7 1: 011 (: 11).
  • specific examples of the fillers include calcium carbonate, calsite (Xi, talc, kaolin, silica, alumina, magnesium hydroxide or clay, etc.), any one or a mixture of two or more thereof may be used.
  • the filler may be included in an amount of 30 to 150 parts by weight, more preferably 50 to 130 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the content of the filler is less than 30 parts by weight, there is a problem that the dimensional stability and economics are lowered. If the content of the filler is more than 150 parts by weight, the foam surface is not good, and workability may be lowered.
  • the fat saccharide (0 2 ) serves to improve the whiteness and concealability of the vinyl chloride resin composition.
  • the fat sugar may be included in an amount of 1 to 20 parts by weight, and more preferably 3 to 15 parts by weight, based on 100 parts by weight of the vinyl chloride resin.
  • the content of the fat sugar is less than 1 part by weight, the whiteness and concealability is lowered, so that the color does not come out properly after printing, and when it exceeds 20 parts by weight, the foamed surface characteristics may be lowered.
  • the vinyl chloride resin composition according to the embodiment of the present invention may be, as other additives, based on 100 parts by weight of the vinyl chloride resin, 0.5 to 7 parts by weight of stabilizer, 0.5 to 7 parts by weight of blowing agent, 30 to 150 parts by weight of filler, and When it contains 1 to 20 parts by weight of fat (0 2 ), it is possible to further improve the discoloration prevention effect.
  • the vinyl chloride resin composition according to an embodiment of the invention may be prepared by a method generally known in the art using an additive, and is not particularly limited in the method.
  • the vinyl chloride resin composition includes di (2-ethylnucleosil) cyclonucleic acid-1,4-dicarboxylate or a mixture of the DEHCH and the compound represented by the formula (1).
  • the plasticizer by combining the carboxylic acid ester-based viscosity lowering agent and the acidic ester-based dispersant, it exhibits excellent migration resistance, as a result can prevent the dyeing phenomenon due to the dye can exhibit a markedly improved discoloration characteristics.
  • the vinyl chloride resin composition is greatly reduced in the amount of plasticizer diffused to the outside when applied to wallpaper, etc., it is possible to prevent the occurrence of environmental problems.
  • the vinyl chloride resin composition has a low viscosity by including an acidic ester-based dispersant together with the plasticizer, the content of a viscosity lowering agent and a liquid stabilizer added to lower the viscosity of the plastisol can be minimized. Accordingly, it is possible to reduce the generation of volatile organic compounds generated from the viscosity reducing agent and the liquid stabilizer, and to prevent the tacky phenomenon generated during the wallpaper production process.
  • the vinyl chloride resin composition according to one embodiment of the invention the viscosity is 4, 000 to 12, 000 cps, more specifically 6, 000 to 10, 000 cps, stable processability within the above range Can be represented.
  • the viscosity of the vinyl chloride resin composition in the present invention can be measured by using a Brookf ield viscometer (spindle # 6, 20RPM) after aging for 1 hour in a 25 ° C constant temperature oven.
  • the vinyl chloride resin composition may be used as a flooring material, wallpaper, tarpaulin, artificial leather, toys, automotive undercoat, etc., and may be particularly useful because it can prevent discoloration when applied to the production of environmentally friendly silk wallpaper.
  • the present invention will be described in more detail with reference to Examples. However, the following examples are merely to illustrate the present invention, the contents of the present invention It is not limited by the embodiment.
  • “%” and “part” which show content in the following example and a comparative example are a basis of weight unless there is particular notice.
  • Example 4 2019/203498 1 »(: 1 ⁇ 1 ⁇ 2019/004371
  • Plastisol was prepared in the same manner as in Example 1, except that the plasticizer mixed in the weight ratio of 9.5: 0.5 was used instead of the plasticizer in Example 1.
  • Example 5 the plasticizer mixed in the weight ratio of 9.5: 0.5 was used instead of the plasticizer in Example 1.
  • Example 6 A plastisol was prepared in the same manner as in Example 1, except that a plasticizer mixed in a weight ratio was used.
  • Example 7 Plastisol # was prepared in the same manner as in Example 1, except that a plasticizer mixed in a weight ratio was used.
  • Example 1 In the same manner as in Example 1, except that a plasticizer in which Example 1 and acetyltributyl citrate (IX) were mixed in a weight ratio of 8: 2 was used instead of the plasticizer in Example 1. To make a plastisol. Comparative Example 1
  • a plastisol was prepared in the same manner as in Example 1, except that 1) 0 was used instead of the 0 ⁇ 01 plasticizer in Example 1. Comparative Example 2
  • Plastisol was prepared in the same manner as in Example 1, except that each component was used in the amount shown in Table 1 below.
  • Wallpaper was prepared using the plastisols of Example 1 and Comparative Example 1 each using # 101 and 0 as plasticizers. Each sample was prepared by placing the prepared wallpaper between oil papers, and the prepared sample was placed on a sample under severe conditions (temperature: 60 V, pressure: 3011 diameter). The weight change of the wallpaper was observed after leaving for 24 hours. The transferability was evaluated according to the following Equation 1 using the weight value of the wallpaper measured before and after the test of the harsh conditions. The results are shown in FIG.
  • Example 2 the plastisols prepared in Example 1 and Comparative Example 1 were aged for 1 hour in a 25 ° C. constant temperature oven, and the viscosity was measured using a Brookf ield viscometer (spindle ⁇ , 20 RPM). The results are shown in FIG. In spite of the same amount of plasticizer formulation, the plastisol of Example 1 showed a markedly reduced viscosity compared to Comparative Example 1.
  • Example 1 The viscosity change of the plastisol with time was observed from Example 1 and Comparative Example 2.
  • the viscosity was measured according to the conditions described in Table 2 in the same manner as in Experimental Example 1, the results are shown together in Table 2 below.
  • Example 2 using an acidic ester-based dispersant showed a significantly lower viscosity compared to the plastisols of Comparative Examples 3 and 4 due to the excellent dispersing effect of the dispersant.
  • Experimental Example 4
  • the plastisols prepared in Examples 1 to 7 and Comparative Examples 1 to 10 were each aged for 1 hour in a 25 C constant temperature oven, and the viscosity was measured using a Brookf ield viscometer (spindle # 6, 20 RPM). .
  • the plastisols prepared in Examples 1 to 7 and Comparative Examples 1 to 10 were thinly coated on a paper (paper) used as wallpaper, foamed at 230 t for 40 seconds, and then cut in cross section to form a cel l state.
  • Paper used as wallpaper
  • the prastisol of Examples 1 to 7 is 25 V, 20 Viscosity measured under conditions is 6,000 to 10,000 The transition performance was as low as 2.3% or less, and the wetting phenomenon and the foamability were excellent at 4 or more, respectively.
  • Comparative Example 1 using a conventional plasticizer showed the same level of foamability as compared with Examples 1, 3 to 7 having the same composition except for the plasticizer, but the viscosity was increased and the transferability was greatly increased to more than 4%. As a result, the wetting phenomenon worsened.
  • the comparative example 3 using the conventional fatty acid dispersing agent a viscosity exceeded 12,00-3, and foamability fell.
  • the comparative example 4 using the conventional polyurethane dispersant showed a relatively low viscosity and transferability compared with the comparative example 3, and thus improved wetting phenomenon, but exhibited reduced properties in terms of foamability.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine de chlorure de vinyle respectueuse de l'environnement pour papier peint ayant notamment une résistance à la décoloration améliorée.
PCT/KR2019/004371 2018-04-17 2019-04-11 Composition de résine de chlorure de vinyle pour papier peint ayant une résistance améliorée à la décoloration WO2019203498A1 (fr)

Priority Applications (2)

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CN201980026431.6A CN111989367B (zh) 2018-04-17 2019-04-11 具有改善的耐变色性的用于墙纸的氯乙烯树脂组合物
EP19787719.4A EP3783062A4 (fr) 2018-04-17 2019-04-11 Composition de résine de chlorure de vinyle pour papier peint ayant une résistance améliorée à la décoloration

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KR10-2018-0044632 2018-04-17
KR20180044632 2018-04-17
KR1020190041998A KR102297787B1 (ko) 2018-04-17 2019-04-10 변색을 개선한 벽지용 염화비닐 수지 조성물
KR10-2019-0041998 2019-04-10

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CN113150467A (zh) * 2021-04-23 2021-07-23 贵州理工学院 一种微发泡pvc溶胶及其制备方法
CN114867775A (zh) * 2019-12-26 2022-08-05 韩华思路信(株) 氯乙烯树脂组合物

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KR20160047221A (ko) * 2014-10-22 2016-05-02 한화케미칼 주식회사 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트 및 시트레이트계 화합물을 포함하는 가소제 조성물, 및 이를 포함하는 염화비닐 수지 조성물
KR20170015424A (ko) * 2013-05-08 2017-02-08 주식회사 엘지화학 벽지용 염화비닐계 수지 조성물
KR101711761B1 (ko) * 2015-11-20 2017-03-02 주식회사 엘지화학 친환경 염화비닐 플라스티졸 및 그 제조방법

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US8283411B2 (en) * 2001-09-25 2012-10-09 Exxonmobil Chemical Patents Inc. Plasticised polyvinyl chloride
KR20090067946A (ko) * 2007-12-21 2009-06-25 주식회사 코렉스 2차 가소제 조성물, 그 제조방법 및 이를 포함하는페이스트 ｐｖｃ 플라스티졸
KR20170015424A (ko) * 2013-05-08 2017-02-08 주식회사 엘지화학 벽지용 염화비닐계 수지 조성물
KR20160047221A (ko) * 2014-10-22 2016-05-02 한화케미칼 주식회사 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트 및 시트레이트계 화합물을 포함하는 가소제 조성물, 및 이를 포함하는 염화비닐 수지 조성물
KR101711761B1 (ko) * 2015-11-20 2017-03-02 주식회사 엘지화학 친환경 염화비닐 플라스티졸 및 그 제조방법

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114867775A (zh) * 2019-12-26 2022-08-05 韩华思路信(株) 氯乙烯树脂组合物
CN113150467A (zh) * 2021-04-23 2021-07-23 贵州理工学院 一种微发泡pvc溶胶及其制备方法
CN113150467B (zh) * 2021-04-23 2022-05-24 贵州理工学院 一种微发泡pvc溶胶及其制备方法

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