WO2019203498A1

WO2019203498A1 - Vinyl chloride resin composition for wall paper having improved discoloration resistance

Info

Publication number: WO2019203498A1
Application number: PCT/KR2019/004371
Authority: WO
Inventors: 장태영; 김재송; 류성민
Original assignee: 한화케미칼 주식회사
Priority date: 2018-04-17
Filing date: 2019-04-11
Publication date: 2019-10-24

Abstract

The present invention provides an environmentally-friendly vinyl chloride resin composition for wallpaper having notably improved discoloration resistance.

Description

【Specification】

[Name of invention]

Vinyl chloride resin composition for wallpaper with improved discoloration

Technical Field

Cross Citation with Related Application (s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0044632 of April 17, 2018 and Korean Patent Application No. 10-2019-0041998 of April 10, 2019. All content disclosed in the literature is included as part of this specification.

The present invention relates to a vinyl chloride resin composition for wallpaper having environmentally friendly and significantly improved discoloration characteristics.

Background Art

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. Among them, 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.

In case of wallpaper using vinyl chloride resin, filler with vinyl chloride resin, 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.

In addition, in the case of eco-friendly silk wallpaper, it is impossible to use phthalate-based plasticizers unlike conventional wallpaper, so DOTP (dioctyl phthalate) -based non-phthalate-based plasticizers are mainly used. Because of good compatibility and susceptible to dye transfer by dyes, when a silk wallpaper is applied on a gypsum board, there is a problem that a large amount of spot discoloration is likely to occur due to the dye contained in the base of the gypsum board being transferred to the surface of the silk wallpaper.

On the other hand, 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. However, 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. In particular, when 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.

Detailed Description of the Invention 2019/203498 1 »（： 1 ^ 1 {2019/004371

[Technical problem]

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.

Technical Solution

According to one embodiment of the present invention to achieve the above object,

Per 100 parts by weight of vinyl chloride resin,

50 to 90 parts by weight of a plasticizer;

0) 5 to 20 parts by weight of a carboxylic acid ester viscosity reducing agent; And

(1) 0.5 to 5 parts by weight of an acidic ester (near) -based dispersant;

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) Provided is a vinyl chloride resin composition for wallpaper, comprising a mixture of compounds represented by:

[Formula 1]

In Chemical Formula 1,

¾ is hydrogen or acetyl, and

¾ to ¾ are each independently 0 _2-8 alkyl.

Further, according to another embodiment of the invention, it provides a wallpaper comprising the vinyl chloride resin composition.

【Effects of the Invention】

The vinyl chloride resin composition for wallpaper according to the present invention is di (2-ethylnuclear) cyclonucleic acid-1,4-dicarboxylate.

Along with the 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

As a result, the dyeing phenomenon by the dye can be prevented to exhibit a markedly improved discoloration characteristics.

In addition, 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.

In addition, 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. As other additives, it is possible to minimize the content of the liquid stabilizer and the like, and also to prevent the generation of volatile organic compounds generated from the viscosity lowering agent and the liquid stabilizer and thereby the deterioration of the product quality.

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.

[Brief Description of Drawings]

1 is a schematic diagram showing a discoloration mechanism occurring on the wallpaper due to the dye in the gypsum board.

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 ¾ 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.

[Best form for implementation of the invention]

The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the invention. Singular expression 2019/203498 1 »（： 1 ^ 1 {2019/004371

Including plural expressions unless the context clearly indicates otherwise. As used herein, the terms `` comprise, '' `` include, '' or `` have '' refer to a feature, step, component, or combination thereof that is embodied. One or more other It is to be understood that the present invention does not exclude the possibility of the presence or the addition of features, steps, components, or a combination thereof.

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to a specific disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

In the present invention, the term `` 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.

Hereinafter, the vinyl chloride resin composition for wallpaper according to a specific embodiment of the present invention will be described in detail.

Vinyl chloride resin composition for wallpaper according to an embodiment of the present invention,

Per 100 parts by weight of vinyl chloride resin,

Non-plasticizer 50 to 90 parts by weight;

(1) acid

6 61) 0.5 to 5 parts by weight of a dispersant;

The plasticizer is di (2-ethylnucleyl) cyclonucleic acid-1,4-dicarboxylate 犯), or the di (2-ethylnuclear) cyclonucleic acid-1,4-dicarboxylate and the following formula (1) Contains mixtures of the compounds represented:

[Formula 1] 2019/203498 1 ＞（1 '/ 1? 2019/004371

In Chemical Formula 1,

¾ is hydrogen or acetyl, and

To ¾ ¾ are each independently 0 _2-8 alkyl. Hereinafter, each component will be described in detail.

3) vinyl chloride resin

In the vinyl chloride resin composition according to an embodiment of the present invention, 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 methacrylonitrile; Olefins such as ethylene or propylene; Or crosslinkable monomers, such as dimalyl phthalate, etc. are mentioned, Any one or a mixture of two or more of these can be used. Among these, 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.

As described above, the resin is a vinyl chloride monomer alone,

2019/203498 1 »（： 1 ^ 1 {2019/004371

Or it may be prepared by polymerizing a vinyl chloride monomer and a comonomer copolymerizable therewith, 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. In addition, 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 (¾ 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 ½) exceeds 40, the dispersibility is low in the vinyl chloride resin particles themselves, and if the average particle size ½) 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 0½) 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.

In addition, 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. Specifically, 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. When 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. If the degree of polymerization of vinyl chloride resin is less than 700 or ¾½ 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 (¾½) 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

Standard polystyrene conversion value by gel permeation chromatography. Plasticizer

In addition, in the vinyl chloride resin composition according to an embodiment of the present invention, the plasticizer may be di (2-ethylnucleosil) cyclonucleic acid-1,4-dicarboxylate 犯) alone, or the zero bond and Formula 1 above. By including the mixture of compounds represented by the above, not only the viscosity of the vinyl chloride resin composition at room temperature can be lowered, but also the viscosity can be prevented from rising at low temperatures in winter. Accordingly, it is possible to minimize the amount of highly volatile viscosity reducing agent added. In addition, 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. In the above plasticizer, di (2-ethylnuclear) cyclonucleic acid-1,4-dicarboxylate (

I) 抑抑) 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. In addition, since the generation of volatile organic compounds can be minimized, the stability to the environment is high.

In addition, 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. However, since 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. Again, 001? Because it does not mix well with contrast ink, it is advantageous for discoloration. 1 is used with 00 시 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. 1, in the wallpaper using D0TP, the dye on the baseboard of the gypsum board spreads to the outside of the wallpaper according to the spread of the plasticizer, whereas in the case of using the tie, the spread of the plasticizer outside the wallpaper is small. Disinfection can be prevented.

In addition, when 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.

More specifically, in Formula 1, ¾ to ¾ is preferably each independently butyl or octyl.

Representative examples of the compound represented by the formula (1), tributyl citrate (TBC), tri (butyl octyl) citrate (tr i (butyl octyl) citrate),

Trioctyl citrate or acetyl tributyl citrate (ATBC), and the like, wherein tri (butyl octyl) citrate is represented by R ₂ to ¾ of Formula 1 It is meant generically to compounds that are some butyl and some octyl. 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.

Scheme 1

2019/203498 1 »（： 1 ^ 112019/004371

In the esterification reaction, depending on the structure of ¾ to ¾ may be prepared by performing the reaction sequentially in one reaction or by varying the reactants. Conditions for the reaction may be used conventional esterification conditions in the art. In the vinyl chloride resin composition according to an embodiment of the invention 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. I) When 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. When 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. When 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, 1¾ 6 £ group 6), which is easily leaked, is likely to occur, resulting in surface stickiness, which may cause problems in processed and finished products. 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. 0) Viscosity Reducing Agent

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.

Specifically, the viscosity reducing agent is to prepare a carboxylic acid of ₂₂ to ¾- alcohol and ester reaction with an alkyl ¾- _22, it may be a carboxylic acid ester represented by the following general formula 2:

[Formula 2]

In 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.

Commercially available viscosity reducing agents include BYK LP-R 22274ä,

Vi scobykä 5025, 5125 and 5050, Jayf lexä 615 or Exxsolä D100, etc. can be used. Among these, BYK LP-R 22274ä with less migrat ion and faster gelling speed due to its excellent compatibility with the plasticizer. It can be used preferably.

In addition, 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 八: 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. When the solidification point and the flash point are satisfied together with the above-mentioned density conditions, 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.

In the vinyl chloride resin composition according to an embodiment of the present invention, as the dispersant, at least one acidic ester (Acidi c ester) compound having excellent dispersibility may be used. 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.

Specifically, 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. Of these, a phosphate ester compound may be preferable. In addition, BYK-LP W 21809ä may be used commercially.

In addition, 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. When the above density and acid value conditions are satisfied, excellent dispersibility can be exhibited and the effect of lowering the viscosity on the resin composition can be further improved. ·

In addition, the dispersant has a flash point of 80 ^° C or more, 2019/203498 1 »（： 1 ^ 1 {2019/004371

Specifically, it may be 100 to 300. By having the flash point of the said range, 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

In addition, 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-¾1 compound,

The compound, an 8-¾ 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. More specific examples

compound;

compound; Organic 11-based compounds such as mercaptiated (¾¾0 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, £ 1-¾-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 公 019/004371

To 7 parts by weight, more preferably 1 to 4 parts by weight. If 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.

In addition, the blowing agent may include a chemical blowing agent or a physical blowing agent, and any one or a mixture thereof may be used.

Specifically, 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,

Azodiisobutyronitrile (azodi isobutyrc 广 nitr i le) ，

Benzenesulfonylhydrazide, 4,4-oxybenzene sul fonyl-semicarbazide p-toluene sulfonyl semi-carbazide, Barium azodi carboxylate, -dimethyl '-dinitrosoterephthalamide (N, N' -dimethyl _N, N '-dinit rosoterephthal amide), trihydrazino triazine Examples thereof include sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium carbonate, ammonium carbonate and the like.

As the physical blowing agent, 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. And 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 公 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,. 1,3,3-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), 1, 1-dichloro- 1-fluoroethane ( 1, 1-dichloro-l-f luoroethane, HCFC_141b), 1-chloro-1,1-difluoroethane (l-chloro-l, l-dif luoroethane, HC FC-142b), chlorodif luoromethane (HCFC-22), 1,1-dicoolo-2,2,2-trifluoroethane (1,1- ₍ ± 1010-2,2, 2- tr if luoroethane, HCFC-123), 1-chloro-1,2,2,2-tetrafluoroethane (1-chloro-1, 2, 2, 2-tetraf luoroethane, HCFC-124), trichloro Monochloromethane (CFC-11), di chi orodif luoromethane (CFC-12), trifluorochlorofluoroethane (CFC-113), 1,1 , 1-trifluoroethane (1，1，1- tr if luoroethane) ， pentaf luoroethane ，

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. .

Moreover, 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.

In addition, 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. When 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.

More specifically, 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.

On the other hand, the vinyl chloride resin composition according to an embodiment of the invention, the vinyl chloride resin, plasticizer, viscosity reducing agent, dispersant and optionally It may be prepared by a method generally known in the art using an additive, and is not particularly limited in the method.

In the vinyl chloride resin composition having the composition described above, 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). In addition to 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.

In addition, 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. In addition, since 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. Specifically, 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.

On the other hand, 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. Hereinafter, 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. In addition, "%" and "part" which show content in the following example and a comparative example are a basis of weight unless there is particular notice.

70 parts by weight of DEHCH, liquid stabilizer (manufactured by L 照 910D-1 ™, KD Chem) based on 100 parts by weight of vinyl chloride resin (EL-103, manufactured by Hanwha Chemical Co., Ltd., polymerization degree 950 + 50).

3 parts by weight, 10 parts by weight (Ti¾), 125 parts by weight of Calsite filler (Omya-lOä, manufactured by Omya Korea Company), 3 parts by weight of blowing agent (DWPX03ä, manufactured by Dongjin Semicam Co., Ltd.), carboxylic acid ester viscosity reducing agent ( BYK LP-R 22274ä, manufactured by BYK, 20 ° C density = 0.879 g / cm ³ , freezing point: <-13 ° C, flash point:> 140 ^° C) 10 parts by weight and dispersant (BYK-LP W 21809ä, manufactured by BYK, 20 ^° C. density = 1.092 g / cm ³ , acid value: about 100 mgK0H / g, flash point:> 100 ° C) 1 part by weight was mixed in a Mathi s mixer for 10 minutes to prepare a plastisol. ^"Example 2

Vinyl resin (EL-103, Hanwha Chemical Co., degree of polymerization 950 + 50) chloride, based on 100 parts by weight, DEHCH 62 parts by weight of the liquid phase stabilizer (LFX910D-1 ™, KD Chem Co., Ltd.) 3 parts by weight, per (Ti0 ₂₎ 14 Parts by weight, Calsite filler (Omya-10ä, manufactured by Omya Korea Company) 8 ◦ parts by weight, blowing agent (DWPX03ä, manufactured by Dongjin Semicam Co.) 3 parts by weight, carboxylic acid ester viscosity reducing agent (BYK LP-R 22274ä, manufactured by BYK) 10 parts by weight and 2 parts by weight of a dispersant (BYK-LP W 21809ä, manufactured by BYK) were mixed in a Mathi s mixer for 10 minutes to prepare a plastisol. Example 3

Zero bond and tributylcitray in place of the plasticizer in Example 1 above

A plastisol was prepared in the same manner as in Example 1, except that a plasticizer mixed in a weight ratio was used. 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

Instead of the plasticizer in Example 1 above

A plastisol was prepared in the same manner as in Example 1, except that a plasticizer mixed in a weight ratio was used. Example 6

Instead of the plasticizer in Example 1 above

Plastisol # was prepared in the same manner as in Example 1, except that a plasticizer mixed in a weight ratio was used. Example 7

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

In place of the carboxylic acid ester-based viscosity lowering agent in Example 1, a hydrocarbon-based viscosity lowering agent (3 (：( 犯 ¾ 5130ä,

Density = 0.86 _^8/3, freezing point: <-15 Flash Point X:> and are the but using 150 ^° 0 Plastisol was prepared in the same manner as in Example 1. Comparative Example 3

Fatty acid dispersant 犯 ¾ 1162ä in place of the dispersant in Example 2,

Plastisol was prepared in the same manner as in Example 2 except for the use. Comparative Example 4

Example 2 except for using a polyurethane-based dispersant (BYK 9077ä, manufactured by BYK, acid value = 70 mgKOH / g, density: 0.96 g / cm ³ , flash point: 185 ^° C) instead of the dispersant in Example 2 Plastisol was prepared in the same manner as in. Comparative Examples 5 to 10

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.

Table 1

2019/203498 1 »(： 1/10 公 019/004371

2019/203498 1 »（： 1 ^ 1 {2019/004371

* In Table 1, the content unit 'parts by weight' of each component is vinyl chloride resin 100 _. It is a relative unit of content based on parts by weight. Experimental Example 1

<Evaluation of performance by plasticizer ñ

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.

[Equation 1]

Transition (%) = [(Weight of wallpaper before testing under harsh conditions-weight of wallpaper after standing for 24 hours under severe conditions) / Weight of wallpaper before testing under harsh conditions] X

100

As a result of the experiment, in the case of Comparative Example 1 using 汉 ^^ as a plasticizer, the transferability was 4.01%, while in Example 1 using the zero band, it was 2.23%, which was significantly reduced compared to Comparative Example 1. In addition, as a result of the above experiment, discoloration of the oil paper by the liquid additives cut out from the wallpaper by the oil paper was observed, and the results are shown in Figs. 3 and 3, respectively (Fig. 33: Comparative Examples 1 and 31). : Example 1).

The higher the amount of liquid additives (plasticizers and viscosity-reducing agents) drawn from the wallpaper, the darker the oil paper. Experimental results 1) of Comparative Example 1 using this? In the case of a large amount of liquid additives (plasticizers and viscosity-lowering agents) in the wallpaper sample, the wet paper and the oil paper were significantly wet, whereas in Example 1, the wetting phenomenon was significantly reduced compared to Comparative Example 1. This result is because the viscosity of the liquid mixture was diminished by using DEHCH as a plasticizer in Example 1, and the amount of the liquid additives such as the plasticizer and the viscosity reducing agent was reduced by about 10% or more compared with Comparative Example 1. From this, it can be expected that the plastisol of the example is more advantageous in reducing discoloration than the comparative example.

In order to evaluate the effect of the plasticizer on the viscosity of the plastisol, the viscosity of the plastisols of Example 1 and Comparative Example 1 using DEHCH and D0TP, respectively, was measured.

Specifically, 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 抑, 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. Experimental Example 2

The viscosity change of the plastisol with time was observed from Example 1 and Comparative Example 2. In the plastisols of Example 1 and Comparative Example 2

After 1 hour and 1 day in a constant temperature oven, 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.

[Table 2]

2019/203498 1 »（： 1 ^ 1 {2019/004371

As a result, after 1 hour, the viscosity of the plastisol of Comparative Example 2 was lower, but after 1 day, the viscosity of Example 1 was lower, and the viscosity was better than the change with time.

For each of the plastisols prepared in Example 1 and Comparative Example 2, the transferability according to the viscosity lowering agent difference was evaluated in the same manner as in the evaluation of the transferability according to the plasticizer in Experimental Example 1. The results are shown in Table 3 below.

Table 3

As a result, the plastisol of Example 1 using the carboxylic acid ester viscosity reducing agent showed a reduced performance compared to Comparative Example 2 using the hydrocarbon type viscosity reducing agent. Experimental Example 3

<Evaluation of Viscosity Change According to Dispersant ñ

In the plastisols prepared in Example 2 and Comparative Examples 3, 4

After 1 hour and 1 day in a constant temperature oven, the viscosity was measured according to the conditions described in Table 4 in the same manner as in Experimental Example 1, the results are shown in Table 4 below.

[Table 4]

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

For the plastisols prepared in Additive Examples 1 to 7, and Comparative Examples 1 to 10, the viscosity, transferability, wetting phenomenon and foamability were respectively measured and evaluated, and the results are shown in Table 5 below.

(1) viscosity

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). .

(2) Performance (%)

Wallpapers were prepared using the plastisols prepared in Examples 1 to 7, and Comparative Examples 1 to 10, respectively. Each sample is prepared by placing the prepared wallpaper between oil papers, and the prepared sample is allowed to stand for 24 hours under severe conditions (temperature: 60 ^° C., pressure: 5 kg weight on a sample having a diameter of 3 cm). The weight change of was observed. 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.

[Equation 1]

Transferability (% M (weight of wallpaper before testing under harsh conditions-weight of wallpaper after standing for 24 hours under severe conditions) / weight of wallpaper before testing under harsh conditions] X 100

(3) wetting phenomenon

(2) After the transferability evaluation, visually determine whether the oil paper is discolored. Observations were made by scoring the wetting phenomenon of the oily paper by the liquid additives (plasticizer and viscosity lowering agent) according to the following criteria. Specifically, the wetness caused by the liquid additives (plasticizer and viscosity lowering agent) was scored closer to 1 point (bad) as the discoloration was severe, and to 5 points (excellent) as the discoloration was less. (4) Foamability

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. Was evaluated by optical microscope and scored to a uniform degree of size, shape and arrangement of cells (cel l). Specifically, the more irregular and non-uniform cell size, shape, and arrangement, the closer it was to 1 point (defect), and the higher and uniform foaming rate was, the closer to 5 points (excellent) was evaluated.

Table 5

2019/203498 1 »（： 1 ^ 1 {2019/004371

Experimental results, 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.

On the other hand, 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.

In Comparative Example 2 using a hydrocarbon-based viscosity reducing agent, the transferability was greatly increased by more than 4 compared with Example 1, and the wetting phenomenon was also significantly worsened. From these results, it can be seen that the use of a combination of a plasticizer containing 카르 ¾ and a carboxylic acid ester-based viscosity reducing agent lowers the transferability and, as a result, greatly improves the wetting phenomenon.

Moreover, in the comparative example 3 using the conventional fatty acid dispersing agent, a viscosity exceeded 12,00-3, and foamability fell. In addition, 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.

In addition, in the case of Comparative Example 5 in which the amount of the plasticizer was not sufficient, the viscosity of the plastisol was markedly increased and poor foamability was observed. In the case of Comparative Example 6 in which the amount of the plasticizer was too high, the transferability exceeded 3%. Wetting phenomenon also significantly worsened.

In addition, even in the case of using the carboxylic acid-based viscosity reducing agent, the viscosity was excessively increased in the case of Comparative Example 7 in which the content was too low, and in the case of Comparative Example 8 in which the excessive amount was used, the viscosity was greatly decreased, and the transferability was greatly increased, and the wettability was increased. 2019/203498 1 »（： 1 ^ 1 {2019/004371

Development and foaming deteriorated.

In addition, in the case of Comparative Example 9, which does not satisfy the content condition of the acidic ester-based dispersant, the viscosity was greatly increased, and in Comparative Example 10 in which the dispersant was used in excess, the transferability was increased and the wettability and the foamability were deteriorated.

From these results, when satisfying the compositional requirements of the vinyl chloride resin composition together with the requirements of the content range, it has an appropriate viscosity to exhibit excellent foamability, and also reduces the performance and thereby improves the wetting phenomenon and prevents discoloration. You can see that you can.

Claims

2019/203498 1 »（： 1 ^ 1 {2019/004371 【claims】【claim 1】 3） to 100 parts by weight of vinyl chloride resin, I）） 50 to 90 parts by weight of plasticizer; 0) 5 to 20 parts by weight of a carboxylic acid ester viscosity reducing agent; And (1) 0.5 to 5 parts by weight of an acidic ester-based dispersant; wherein the preformative plasticizer is di (2-ethylnuclear) cyclonucleic acid-1,4-dicarboxylate, or di (2-ethylnuclear) Vinyl chloride resin composition for wallpaper, comprising a mixture of cyclonucleic acid-1,4-dicarboxylate and a compound represented by the following formula (1):

[Formula 1]

In Chemical Formula 1,

Is hydrogen or acetyl, and

¾ to ¾ are each independently C 2 _-S alkyl.

[Claim 2]

The method of claim 1,

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 solvents, vinyl chloride resin composition.

[Claim 3]

The method of claim 1,

The compound represented by the formula (1) is tributyl citrate, tri (butyl octyl) citrate, trioctyl citrate or acetyl tributyl citrate, vinyl chloride resin composition for wallpaper. 2019/203498 1 »（： 1 ^ 1 {2019/004371

[Claim 4]

The method of claim 1,

The mixture weight ratio of the said di (2-ethyl nucleus) cyclonucleic acid- 1, 4- dicarboxylate, and the compound represented by the addition formula (1) is 9.5: 1-1: 9.5, The vinyl chloride resin composition for wallpaper.

[Claim 5]

The method of claim 1,

The viscosity reducing agent is a carboxylic acid ester represented by the following formula (2), vinyl chloride resin composition for wallpaper:

[Formula 2]

In Formula 2, ¾ and ¾ are each independently a straight or branched alkyl group of ¾- ₂₂ .

[Claim 6]

The method of claim 1,

The viscosity reducing agent is 20 ^° (: a density of 0.85 to 0.9 for a / (L ^3, the freezing point is below -7 ° 0 in, a flash point of 120

The above is a vinyl chloride resin composition for wallpaper.

[Claim 7]

The method of claim 1,

The dispersant is a phosphate ester compound, a fatty acid ester compound, or a mixture thereof, vinyl chloride resin composition for wallpaper.

[Claim 8]

The method of claim 1, 2019/203498 1 »（： 1 ^ 1 {2019/004371

The dispersing agent has a density of from 0.9 to 1.3 for 201; , The acid value is 80 to 120

Vinyl chloride resin composition for wallpaper.

[Claim 9]

The method of claim 1,

The vinyl chloride resin composition for wallpaper further comprising at least one additive selected from the group consisting of a stabilizer, a blowing agent, a filler, and a fat sugar.

[Claim 10]

The method of claim 9,

The stabilizer is a Na-Zn-based compound,

compound,

The vinyl chloride resin composition for wallpaper which is at least 1 sort (s) chosen from the group which consists of a compound, a compound, an organic 11 type compound, a metallic soap type compound, a phenol type compound, and a phosphite ester type compound.

[Claim 11]

The method of claim 9,

The blowing agent comprises a chemical blowing agent, a physical blowing agent or a mixture thereof, vinyl chloride resin composition for wallpaper.

[Claim 12]

The method of claim 9,

The filler is at least one member selected from the group consisting of calcium carbonate, calsite, talc, kaolin, silica, alumina, magnesium hydroxide and clay, vinyl chloride resin composition for wallpaper.

[Claim 13]

According to claim 1

Per 100 parts by weight of the vinyl chloride resin, b) di (2-ethylnuclear) cyclonucleic acid-1,4-dicarboxylate, or a compound represented by the above-mentioned di (2-ethylnucleosil) cyclonucleic acid-1,4-dicarboxylate and the formula 60 to 80 parts by weight of a plasticizer comprising a mixture;

c) 10 to 20 parts by weight of a carboxylic acid ester ester lowering agent; And d) 1 to 3 parts by weight of an acidic ester-based dispersant;

The vinyl chloride resin composition for wallpaper further comprising 0.5 to 7 parts by weight of stabilizer, 0.5 to 7 parts by weight of foaming agent, 30 to 150 parts by weight of filler and 1 to 20 parts by weight per branch. [Claim 14]

The method of claim 1,

A vinyl chloride resin composition for wallpaper having a viscosity (measured at a condition of 20 RPM with a Brookfield viscometer after 25 hours of aging for 1 hour) of 4,000 to 12,000 cps. [Claim 15]

Wallpaper comprising the vinyl chloride resin composition for wallpaper according to claim 1.