KR20230031168A - Vinyl chloride resin composition - Google Patents

Abstract

The present invention provides a vinyl chloride resin composition that is environmentally friendly because the vinyl chloride resin composition can reduce carbon emissions and has low viscosity, excellent processability, migration resistance, and flame retardancy, making it useful for manufacturing an eco-friendly flame retardant wallpaper. Provided is the vinyl chloride resin composition, which contains, based on 100 parts by weight of the vinyl chloride resin, 70 to 90 parts by weight of a plasticizer, 50 to 90 parts by weight of an antimony-based flame retardant and 5 to 40 parts by weight of a phosphate-based flame retardant.

Description

Vinyl chloride resin composition {Vinyl chloride resin composition}

The present invention relates to a polyvinyl chloride resin composition that is environmentally friendly because it can reduce carbon emissions, and is useful for manufacturing eco-friendly flame retardant wallpaper because it exhibits low viscosity, excellent processability, migration resistance, and flame retardancy.

Recently, for environmental protection and resource recycling, research is being conducted to recover useful resources from waste synthetic resin or by-products generated during the synthetic resin manufacturing process. In addition, active research is being conducted to reduce carbon emissions generated during the production of synthetic resin products.

As a recycling technology for waste synthetic resin, a method for recycling waste polyester is known in particular. For example, a method of depolymerizing waste polyester in the presence of a catalyst to recycle terephthalic acid, dimethyl terephthalate, and ethylene glycol as raw materials is known. Regenerated terephthalic acid and dimethyl terephthalate can be recycled into dioctyl terephthalate, which is a useful material as a plasticizer, through esterification or transesterification. In addition, Chinese Laid-Open Patent Publication Nos. 104230714 and 104496819 disclose methods for recovering dioctyl terephthalate from wastewater in a polyester reduction process.

Dioctyl terephthalate is a widely used plasticizer, and dioctyl terephthalate recovered through the regeneration process can also be used as a plasticizer for polymer resins. However, regenerated dioctyl terephthalate has disadvantages in that it is yellow in color and has an unpleasant odor compared to pure dioctyl terephthalate due to impurities introduced in the recycling process. Accordingly, there is a problem in that regenerated dioctyl terephthalate can be used only when manufacturing relatively low-quality products.

Therefore, it is required to develop a plasticizer exhibiting excellent quality while being able to obtain effects of recycling resources and reducing carbon emissions in the manufacturing process.

On the other hand, vinyl chloride resin is a homopolymer of vinyl chloride and a copolymer containing 50% or more of vinyl chloride, and is one of five general-purpose thermoplastic resins produced by suspension polymerization and emulsion polymerization. Among them, vinyl chloride resin produced by emulsion polymerization is mixed with additives having special functions such as plasticizer, stabilizer, filler, blowing agent, and pigment to produce plastisol ( It is used in a wide range of fields such as flooring, wallpaper, tarpaulin, artificial leather, toys, and automobile lower coating materials through coating molding and mold coating molding processing in the form of Plastisol.

Wallpaper is the most exposed product in residential and office spaces, and more than 60% of it is manufactured using polyvinyl chloride resin. Recently, the main issue of wallpaper is related to eco-friendly wallpaper, and the criteria for eco-friendliness are the HB grades (best, excellent, good, etc.) Step 3), and whether it contains phthalate-based plasticizers, which are suspected of being endocrine disrupters that interfere with or disrupt human hormones.

In the case of wallpaper using vinyl chloride resin, plastisol is prepared by mixing vinyl chloride resin with solid raw materials such as fillers and pigments and liquid raw materials such as plasticizers, stabilizers, and viscosity reducing agents, and then the plastisol is mixed with paper. It is manufactured through processing processes such as coating, gelling, printing, foaming and embossing processes.

In the vinyl chloride resin composition for wallpaper, the plasticizer is a liquid component that occupies a large amount, and shows a migration phenomenon in which it is mixed with the vinyl chloride resin at the beginning of production and gradually leaks out of the vinyl chloride resin over time. When the leaked plasticizer enters the body, it inhibits the normal activity of the endocrine system, which is directly involved in life activities, or triggers an abnormal reaction, causing fatal harm. This is an important reason for limiting the use of plasticizers, especially phthalate-based plasticizers, in wallpaper, tarpaulin, artificial leather, toys, and automobile underside coating materials.

In addition, in the case of eco-friendly silk wallpaper, it is impossible to use phthalate-based plasticizers unlike conventional wallpapers, so DOTP (dioctyl terephthalate)-based non-phthalate-based plasticizers are mainly used. Since it is vulnerable to dye transfer due to its good properties, when silk wallpaper is installed on a gypsum board, there is a problem that the dye contained in the gypsum board base paper is transferred to the surface of the silk wallpaper, resulting in a large amount of spot discoloration.

Meanwhile, a vinyl chloride resin composition for wallpaper having flame retardancy has been used in order to minimize damage in the event of a fire and to prolong the spread of fire. However, the flame retardant for imparting flame retardancy is a solid raw material, and there is a problem of increasing the viscosity of the plastisol. The viscosity of plastisol in producing wallpaper is a major property that determines the coating properties and productivity of wallpaper in the coating process, and the lower the viscosity, the more advantageous it is. Accordingly, a vinyl chloride resin composition for wallpaper containing a solid flame retardant is formulated with an excessive amount of a viscosity-lowering agent in order to lower the viscosity. An excessive amount of the viscosity-lowering agent not only emits a large amount of volatile organic compounds but also deteriorates product quality. .

Therefore, it is necessary to develop a vinyl chloride resin composition for wallpaper that can reduce generation of volatile organic compounds and exhibits excellent flame retardancy, migration resistance and processability.

[Prior art literature]

[Patent Literature]

(Patent Document 1) Chinese Laid-Open Patent Publication No. 104230714

(Patent Document 2) Chinese Laid-Open Patent Publication No. 104496819

The present invention is to solve the problems of the prior art as described above, and is environmentally friendly because it can reduce carbon emissions, and exhibits low viscosity, excellent processability, migration resistance and flame retardancy, and is useful for the manufacture of eco-friendly flame retardant wallpaper. A vinyl chloride resin composition, And to provide a wallpaper manufactured using the same.

According to the present invention to achieve the above object,

With respect to 100 parts by weight of vinyl chloride resin,

70 to 90 parts by weight of a plasticizer,

50 to 90 parts by weight of an antimony-based flame retardant, and

5 to 40 parts by weight of a phosphate-based flame retardant,

The plasticizer is 20: A vinyl chloride resin composition comprising a weight ratio of 80 to 65:35 is provided.

According to another embodiment of the present invention, a wallpaper including the vinyl chloride resin composition is provided.

The vinyl chloride resin composition according to the present invention is environmentally friendly because it can reduce carbon emissions, and exhibits low viscosity, excellent processability, migration resistance, and flame retardancy.

Accordingly, the vinyl chloride resin composition can be used for flooring, wallpaper, tarpaulin, artificial leather, toys, or automobile lower coating materials. In particular, since it is eco-friendly and has excellent flame retardancy and discoloration properties, it is suitable for manufacturing wallpaper, especially eco-friendly flame retardant wallpaper. can be particularly useful.

Terms used in this specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as "comprise", "comprise" or "having" are intended to indicate that there is an embodied feature, step, component, or combination thereof, but one or more other features or steps; It should be understood that the presence or addition of components, or combinations thereof, is not previously excluded.

Since the present invention can have various changes and various forms, specific embodiments will be exemplified and described in detail below. However, it should be understood that this is not intended to limit the present invention to the specific disclosed form, and includes 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", which represents a mixture of a resin and a plasticizer so that it can be molded, molded, or processed into a continuous film by heating, and the plastic Stizol may be, for example, a paste obtained by mixing a vinyl chloride resin and a plasticizer.

Also, in the present specification, “DEHCH” refers to di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate. Also, “regenerated-DEHCH” or “R-DEHCH” refers to DEHCH prepared from a regenerated phthalate-based compound.

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

(Vinyl chloride resin composition)

The vinyl chloride resin composition according to the present invention includes 70 to 90 parts by weight of a plasticizer, 50 to 90 parts by weight of an antimony-based flame retardant, and 5 to 40 parts by weight of a phosphate-based flame retardant, based on 100 parts by weight of the vinyl chloride resin, and the plasticizer is A regenerated cyclohexane dicarboxylate-based compound having an acid value of more than 0.1 KOH mg/g and 0.3 KOH mg/g or less and a cyclohexane dicarboxylate-based compound having an acid value of 0.1 KOH mg/g or less are prepared in a ratio of 20:80 to 65 :35 by weight.

In the case of conventional eco-friendly silk wallpaper, a DOTP (dioctyl terephthalate) plasticizer was mainly included as a non-phthalate plasticizer. However, these DOTP-based plasticizers have a high basic viscosity, and when a solid flame retardant is additionally prescribed, the viscosity of the composition further increases. In addition, when an excessive amount of the viscosity reducing agent is added, a large amount of VOCs are released from the viscosity reducing agent, which causes environmental problems as well as deteriorating migration resistance and product quality.

In contrast, in the present invention, when preparing a vinyl chloride resin composition, a cyclohexane dicarboxylate-based compound plasticizer represented by DEHCH is used instead of a conventional DOTP-based plasticizer, but recycled-cyclohexane dicarboxylate obtained from recycled raw materials The above problem was solved and the present invention was completed by using a mixture of a rate compound and using a combination of an antimony flame retardant and a phosphate flame retardant exhibiting excellent compatibility with the plasticizer.

Specifically, the vinyl chloride resin composition can reduce carbon emissions in resource recycling and manufacturing processes, including recycled raw materials, has little yellow color and odor peculiar to recycled raw materials, excellent gelling properties, plasticization efficiency, And by including a plasticizer exhibiting migration resistance, it can exhibit environmentally friendly, low viscosity and excellent processability.

In addition, the vinyl chloride resin composition, while exhibiting excellent flame retardancy, includes a heterogeneous flame retardant having excellent compatibility with the components constituting the resin composition, such as a plasticizer, in an optimal combination, so that the gelling rate is increased, and as a result, productivity is also improved. can be improved In addition, excellent flame retardancy can be exhibited even with a reduced amount of flame retardant compared to the prior art, and an increase in viscosity due to the flame retardant can be reduced. Accordingly, the amount of additives such as a viscosity lowering agent and a liquid stabilizer, which are generally used to lower the viscosity of plastisol, can also be minimized, thereby reducing the amount of volatile organic compounds (TVOCs) generated by these additives.

In addition, the vinyl chloride resin composition can exhibit excellent migration resistance due to the use of a non-phthalate plasticizer and the use of a low content of a viscosity lowering agent, and as a result, dye migration is also prevented, resulting in significantly improved discoloration characteristics. .

Therefore, the vinyl chloride resin composition can be preferably used in the manufacture of silk wallpaper exhibiting excellent flame retardancy and eco-friendliness.

Hereinafter, the vinyl chloride resin composition of one embodiment will be described in detail for each component.

vinyl chloride resin

In the vinyl chloride resin composition according to the present invention, the vinyl chloride resin may be a homopolymer obtained by homopolymerization of a vinyl chloride monomer or a copolymer obtained by polymerization of a vinyl chloride monomer and a comonomer copolymerizable therewith. One or a mixture of two or more may be used for preparing the vinyl chloride resin composition.

Specifically, the comonomer copolymerizable with the vinyl chloride monomer may include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl stearate; vinyl ethers having an alkyl group such as methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether, and launyl vinyl ether; vinylidene halides such as vinylidene chloride; unsaturated carboxylic acids and acid anhydrides thereof, such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride; unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, monomethyl maleate, dimethyl maleate, and butylbenzyl maleate; Aromatic vinyl compounds, such as styrene, (alpha)-methyl styrene, and divinyl benzene; unsaturated nitriles such as acrylonitrile or methacrylonitrile; olefins such as ethylene or propylene; or a crosslinkable monomer such as diallyl phthalate, and any one or a mixture of two or more of these may be used. Among these, it is more preferable that the comonomer includes vinyl acetate or the like in that it has excellent compatibility with the vinyl chloride monomer and can improve the compatibility with the plasticizer constituting the resin composition after polymerization. .

As described above, the vinyl chloride resin may be prepared by polymerization of a vinyl chloride monomer alone or a vinyl chloride monomer and a comonomer copolymerizable therewith. In this case, the polymerization method is not particularly limited, and fine suspension polymerization, emulsion polymerization or It may be carried out according to a conventional polymerization method known in the art to which the present invention pertains, such as seed emulsion polymerization.

Among them, when produced by emulsion polymerization or fine suspension polymerization, the average particle size of the vinyl chloride resin produced is small and uniform compared to when 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 polymerization.

The average particle size (D ₅₀ ) of the vinyl chloride resin usable in the present invention may be 0.1 to 40 μm, more specifically 1 to 10 μm, and exhibits excellent dispersibility by having a particle size in the above range, and plasticization The fluidity of the modified vinyl chloride resin composition can be further improved.

When the average particle size (D ₅₀ ) exceeds 40 μm, the polyvinyl chloride resin particles themselves have low dispersibility, and when the average particle size (D 50 ) is less than 1 μm, the dispersibility may deteriorate due to aggregation between the vinyl chloride resin particles. On the other hand, in the present invention, the average particle size (D ₅₀ ) of the vinyl chloride resin can be measured using a laser diffraction method. Specifically, the particle size distribution is analyzed by measuring the diffraction pattern difference according to the particle size when the particles pass through the laser beam using a laser diffraction particle size measuring device, and from the result, 50% of the particle volume cumulative distribution according to the particle size is obtained. D50 can be obtained by calculating the particle diameter at the point.

In addition, the polymerization degree and weight average molecular weight of the vinyl chloride resin may affect the compatibility with the components constituting the vinyl chloride resin composition, particularly the plasticizer, and the processability of the plastisol. Through control of the polymerization conditions during polymerization, can be properly adjusted.

Specifically, the vinyl chloride resin may have a polymerization degree of 700 to 1,700 or a weight average molecular weight (Mw) of 45,000 to 200,000 g/mol. When the polymer has a degree of polymerization or a weight average molecular weight within the range described above, dispersibility is excellent, compatibility with plasticizers is good, and processability of plastisol can be improved.

If the degree of polymerization of the vinyl chloride resin is less than 700 or the Mw is less than 45,000 g/mol, the durability and workability of the wallpaper may deteriorate due to insufficient physical properties. There are concerns. More specifically, the degree of polymerization may be 900 or more and less than 1,050, or the weight average molecular weight (Mw) may be 60,000 to 150,000 g/mol.

The degree of polymerization of the vinyl chloride resin indicates the number of repeating units (units or monomers) constituting the polymer, and can be measured according to JIS K6720-2.

In addition, the weight average molecular weight (Mw) of the vinyl chloride resin can be measured by gel permeation chromatography, and is a standard polystyrene conversion value (measurement temperature: 160 ° C., solvent 1,2,4-trichlorobenzene).

plasticizer

In the vinyl chloride resin composition according to the present invention, the plasticizer includes a recycled cyclohexane dicarboxylate-based compound as a first plasticizer and a cyclohexane dicarboxylate-based compound as a second plasticizer.

The regenerated cyclohexane dicarboxylate-based compound is not synthesized from pure raw materials, but can be obtained from a regenerated phthalate-based compound recovered from waste through reprocessing.

For example, DEHCH can be obtained through a hydrogenation reaction on dioctylterephthalate (DOTP), a phthalate-based compound. In addition, the phthalate-based compound is generally prepared using terephthalic acid as a raw material. Accordingly, in the case of a pure cyclohexane dicarboxylate-based compound synthesized from pure raw materials, it is used in an additional process because it goes through not only the manufacturing process from the phthalate-based compound but also the manufacturing process of terephthalic acid, which is a raw material of the phthalate-based compound. There is a problem that carbon emissions increase compared to DOTP due to electricity, gas, steam, etc.

In contrast, in the present invention, by using a regenerated cyclohexane dicarboxylate-based compound prepared from a regenerated phthalate-based compound, there is an effect of reducing energy consumption and greenhouse gas emissions consumed in producing terephthalic acid, which is a raw material of a general phthalate-based compound. . Specifically, the recycled cyclohexane dicarboxylate-based compound used in the present invention is wastewater discharged during alkali reduction processing of polyester fibers, wastewater generated during the process of producing pure terephthalate-based compounds, or residues after filtration. from regenerated phthalate-based compounds obtained by extracting phthalic acid from waste materials such as waste materials and reacting it with alcohol, or depolymerizing waste polyester to obtain aromatic dicarboxylic acids or esters thereof and then reacting them with appropriate alcohols. can be manufactured Specifically, it can be produced through a hydrogenation reaction (or hydrogenation reaction) on the regenerated phthalate-based compound. At this time, the hydrogenation reaction may be carried out in a conventional manner.

On the other hand, carbon emission is a measure of the amount of carbon generated in the production process of various products. It's a shame. By obtaining phthalate-based compounds from renewable raw materials, it has the effect of reducing energy consumption and greenhouse gas emissions consumed in producing terephthalic acid, which is a raw material for general phthalate-based compounds, so the plasticizer of the present invention reduces carbon emissions equal to or less than DOTP level can be lowered.

In addition, the regenerated cyclohexane dicarboxylate-based compound, like the cyclohexane dicarboxylate-based compound prepared from pure raw materials, has low room temperature and low-temperature viscosity, can realize excellent work performance, has a fast gelling rate, and is plasticized. Excellent conversion efficiency and plasticizer migration resistance. However, since it contains impurities or by-products introduced in the process of regeneration from waste, it has a yellow color, smells like oil, and has a higher acid value than pure cyclohexane dicarboxylate-based compounds.

In order to obtain a plasticizer of higher quality, it is preferable to use a regenerated cyclohexane dicarboxylate-based compound having a low acid value, and the regenerated cyclohexane dicarboxylate-based compound in the present invention has a KOH mg/g of more than 0.1 and 0.3 KOH mg/g. has an acid value of mg/g KOH or less, more specifically greater than 0.1 mg/g KOH, or greater than or equal to 0.15 mg/g KOH, less than or equal to 0.3 mg/g KOH, or less than or equal to 0.25 mg/g KOH, or less than or equal to 0.2 mg/g KOH. It has an acid value of less than g.

The acid value of the recycled cyclohexane dicarboxylate-based compound is determined according to the acid value of the recycled phthalate-based compound as a raw material and the content of impurities or by-products introduced in the process of recycling waste. Generally, the higher the acid value of the regenerated phthalate-based compound, the higher the acid value of the regenerated cyclohexane dicarboxylate-based compound produced by hydrogenating the same. The acid value of the regenerated phthalate-based compound can be adjusted by controlling the neutralization process during the preparation of the phthalate-based compound. The neutralization process may be performed in a conventional manner, and for example, the acid value of the phthalate-based compound and the acid value of the regenerated phthalate-based compound produced therefrom may be lowered or increased by reducing or increasing the number of times of the neutralization process. .

In addition, the higher the content of impurities or by-products in the regenerated cyclohexane dicarboxylate-based compound, the higher the acid value of the regenerated cyclohexane dicarboxylate-based compound. Accordingly, when it is desired to increase the acid value of the regenerated cyclohexane dicarboxylate-based compound, the reaction temperature is increased during the regeneration reaction or by-products are increased through the recycling reaction. It can be controlled within an appropriate range through methods such as lowering the reaction temperature or reducing the number of recycling reactions.

In addition, in the present invention, in order to compensate for the high acid value of the regenerated cyclohexane dicarboxylate-based compound, a cyclohexane dicarboxylate-based compound prepared from pure raw materials and having a low acid value of 0.1 KOH mg/g or less is used together. do.

On the other hand, the acid value is the weight (mg) of potassium hydroxide (KOH) required to neutralize the acid contained in 1g of the sample, usually by titrating the sample solution with a 0.1N alcoholic KOH solution, specifically a 0.1N KOH ethanol solution. can be saved In the present invention, the acid value is measured according to JIS K 6751.

The regenerated cyclohexane dicarboxylate-based compound may be a compound prepared from reclaimed raw materials, satisfying the above acid value condition, and represented by Formula 1 below:

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently C _4-12 alkyl

Specifically, R ₁ and R ₂ are each independently a butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, an isononyl group, a 2-propylheptyl group, A C _4-12 straight-chain or branched alkyl such as a decyl group or an isodecyl group, and more specifically, R ₁ and R ₂ are each independently a butyl group, a 2-ethylhexyl group, or an isononyl group.

More specifically, Formula 1 may be represented by the following Formulas 1-1 to 1-3 depending on the substituent position:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Chemical Formulas 1-1 to 1-3, R ₁ and R ₂ are as defined in Chemical Formula 1.

Formula 1-1 is a cyclohexane-1,2-dicarboxylate-based compound, Formula 1-2 is a cyclohexane-1,3-dicarboxylate-based compound, and Formula 1-3 is a cyclohexane-based compound. It is a -1,4-dicarboxylate-based compound.

In one embodiment, the regenerated cyclohexane dicarboxylate-based compound is a regenerated di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate prepared from recycled raw materials and satisfying the above acid value conditions, Regenerated diisononylcyclohexane-1,2-dicarboxylate, di(2-ethylhexyl)cyclohexane-1,2-dicarboxylate, regenerated butyl(2-ethylhexyl)cyclohexane-1,4- It may be at least one selected from the group consisting of dicarboxylates and regenerated dibutylcyclohexane-1,4-dicarboxylates.

More specifically, the regenerated cyclohexane dicarboxylate-based compound is regenerated di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate represented by Formula 2 below (di(2-ethylhexyl) cyclohexane- 1,4-dicarboxylate, DEHCH):

[Formula 2]

The regenerated DEHCH can realize excellent work performance due to its low viscosity at room temperature and low temperature, has a fast gelling rate, and has better plasticization efficiency and plasticizer migration resistance than other regenerated cyclohexane dicarboxylate-based compounds.

In addition, the plasticizer includes a cyclohexane dicarboxylate-based compound as a second plasticizer in order to supplement the characteristics, high acid value, smell, and yellow color of the above-described regenerated cyclohexane dicarboxylate-based compound.

The cyclohexane dicarboxylate-based compound is manufactured from pure raw materials, and has the same structure as the regenerated cyclohexane dicarboxylate-based compound itself, except for differences in raw materials. Specifically, the cyclohexane dicarboxylate-based compound may be a compound represented by Chemical Formula 1, and more specifically represented by Chemical Formulas 1-1 to 1-3.

In one embodiment, the cyclohexane dicarboxylate-based compound is di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, diisononylcyclohexane-1,2-dicarboxylate, di (2-ethylhexyl)cyclohexane-1,2-dicarboxylate, butyl (2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and dibutylcyclohexane-1,4-dicarboxylate It may be one or more selected from the group consisting of rates.

Preferably, the cyclohexane dicarboxylate-based compound is di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (di(2-ethylhexyl) cyclohexane-1,4-dicarboxylate, DEHCH). can The DEHCH is transparent in color and odorless, has low room temperature and low temperature viscosity, can realize excellent coating properties, has a fast gelling rate, and has excellent foaming properties. In addition, plasticization efficiency and plasticizer migration resistance are excellent compared to other cyclohexane dicarboxylate-based compounds. The plasticizer in the wallpaper easily permeates to the surroundings by diffusion, and when it permeates into the paper layer in this way, there is a high possibility that the dye in the gypsum board base paper will be transferred to the surface of the wallpaper. However, since DEHCH has excellent migration resistance, the amount of diffusion to the outside of the wallpaper is small, and as a result, it is possible to prevent the phenomenon of dye migration due to less penetration into the paper. In addition, it is advantageous for discoloration because it does not mix well with ink compared to DOTP. Therefore, when such DEHCH is used, the physical properties of the plasticizer can be further improved while supplementing the problems of yellowness and odor caused by the regenerated cyclohexane dicarboxylate-based compound.

The plasticizer in the present invention may include the regenerated cyclohexane dicarboxylate-based compound and the cyclohexane dicarboxylate-based compound in a weight ratio of 20:80 to 65:35. When included in the above weight ratio, the plasticizer properties such as migration properties can be improved while the problems of yellowness, odor and high acid value caused by the use of the first plasticizer of the recycled cyclohexane dicarboxylate-based compound can be improved, and carbon emissions The reduction effect can be fully realized. When the “greater than” and “less than” weight ratios are based on the content of the regenerated cyclohexane dicarboxylate-based compound, the weight ratio of the regenerated cyclohexane dicarboxylate-based compound to the cyclohexane dicarboxylate-based compound is greater than Specifically, it may be 20:80 or more, or 30:70 or more, 35:65 or more, or 40:60 or more, or 50:50 or more, and 65:35 or less, or 60:40 or less, or 55:45 or less. For example, the weight ratio of the regenerated cyclohexane dicarboxylate-based compound and the cyclohexane dicarboxylate-based compound is 20:80 or more or 65:35 or less, that is, 20:80 to 63:35, or 30:70 to 65:35. 65:35, or 35:65 to 65:35, or 40:60 to 60:40, or 50:50 to 60:40. When the above weight ratio condition is satisfied, the above improvement effect can be further enhanced.

As described above, the plasticizer used in the present invention is environmentally friendly by reducing carbon emissions by including a recycled cyclohexane dicarboxylate-based compound obtained from recycled raw materials together with the cyclohexane dicarboxylate-based compound. It has low yellow color and odor peculiar to raw materials, and exhibits excellent gelling properties, plasticization efficiency, and migration resistance.

Specifically, the plasticizer has a carbon emission reduction rate of 3% or more, more specifically 3% or more, or 3.5% or more, or 4% or more, and 30% or less, or 20% or less, or 15% or less.

On the other hand, the carbon emission reduction rate of the plasticizer is a value calculated when compared with a plasticizer composition containing a cyclohexane dicarboxylate-based compound obtained from a pure phthalate-based compound instead of a cyclohexane dicarboxylate-based compound obtained from a recycled phthalate-based compound , which corresponds to the carbon emission reduction rate by using recycled phthalate-based raw materials. Specifically, the carbon emission reduction rate (%) of the plasticizer composition can be calculated as in Equation 1 below.

[Equation 1]

Carbon emission reduction rate (%) = 100 - [(A1/A2)×100]

In Equation 1 above,

A1 is the carbon emission of the plasticizer to be measured, for example, the plasticizer in the present invention (tCO ₂ eq / MT),

A2 is the carbon footprint of the control plasticizer (tCO ₂ eq/MT).

Specifically, A1 corresponds to the total amount of carbon emissions (tCO ₂ eq/MT) according to the composition ratio of each component included in the plasticizer, and A2 is pure cyclohexane dicarboxylate-based compound instead of recycled phthalate-based compound obtained from recycled phthalate-based compound. Sum of carbon emissions (tCO ₂ eq / MT) according to the composition ratio of each component in the control plasticizer having the same composition as the plasticizer in A1 above except for containing the cyclohexane dicarboxylate-based compound obtained from the phthalate-based compound corresponds to Here, the unit of carbon emissions is expressed as a weight equivalent (eq) of total CO ₂ emissions per metric ton.

The carbon emission of each component used in the plasticizer may be calculated by referring to the value provided by the manufacturer or calculated based on the manufacturing process and chemical reaction of each component. For a specific calculation method of the carbon emission reduction rate, reference may be made to an experimental example to be described later.

In addition, the plasticizer exhibits improved odor characteristics. In addition, the plasticizer has an excellent white index of 60 or more, more specifically, 61 or more, or 61.5 or more, as measured using a color difference meter.

The plasticizer as described above may be included in an amount of 70 to 90 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content of the plasticizer is less than 70 parts by weight, the viscosity of the vinyl chloride resin composition or plastisol increases, resulting in a decrease in coating properties or a decrease in the flexibility of the product, and if it exceeds 90 parts by weight, transferability and gelling rate characteristics deteriorate. As a result, a bleeding effect in which the plasticizer leaks out to the surface of the molded article is likely to occur, and as a result, surface stickiness may cause problems in processing and finished products, and flame retardant performance may be significantly deteriorated. Considering the more excellent effect on viscosity reduction, securing flame retardant performance, and suppression of bleeding phenomenon by controlling the content of the plasticizer for the vinyl chloride resin, the plasticizer is 70 parts by weight or more, or 75 parts by weight based on 100 parts by weight of the vinyl chloride resin Part or more, or 80 parts by weight or more, and may be included in 90 parts by weight or less, or 85 parts by weight or less.

antimony flame retardant

The vinyl chloride resin composition according to the present invention includes an antimony-based flame retardant as a first flame retardant together with the plasticizer described above.

The flame retardant is for imparting flame retardancy to the vinyl chloride resin composition, and is a halogen-based flame retardant such as a bromine-based flame retardant or a chlorine-based flame retardant, or aluminum hydroxide, magnesium hydroxide, zinc stannate, phosphorus-based flame retardant, or molybdate, which can be used in the vinyl chloride resin composition. Although inorganic flame retardants such as flame retardants and antimony-based flame retardants can be used, in the present invention, an antimony-based flame retardant that exhibits the best flame retardancy and has excellent compatibility with the plasticizer described above is used as the first flame retardant.

The antimony-based flame retardant is specifically at least one selected from the group consisting of antimony trioxide (Sb ₂ O ₃ ), antimony pentoxide (Sb ₂ O ₅ ), metallic antimony (Sb), and antimony trichloride (SbCl ₃ ). can be used. Of these, antimony trioxide, which can secure effective flame retardancy in a small amount, can be preferably used.

Meanwhile, in the present invention, a cyclohexane carboxylate-based compound having excellent flame retardancy is used as a plasticizer and a phosphate-based flame retardant described later is used in combination, resulting in excellent flame retardancy even with the reduced flame retardant compared to conventional flame retardant vinyl chloride resin compositions. characteristics can be obtained. Specifically, the antimony-based flame retardant may be included in 50 to 90 parts by weight based on 100 parts by weight of the vinyl chloride resin, more specifically, 50 parts by weight or more, or 60 parts by weight or more, or 65 parts by weight or more, and 90 parts by weight or less, or 80 parts by weight or less, or may be included in an amount of 70 parts by weight or less. If the content of the antimony-based flame retardant exceeds 90 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, the viscosity of the resin composition increases due to the solid flame retardant, and there is a problem that an additional viscosity lowering agent must be prescribed. If it is less than parts by weight, it is difficult to obtain a sufficient flame retardant effect.

Meanwhile, the vinyl chloride resin composition according to the present invention may also use inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide in a range that does not impair the effects of the present invention together with the above flame retardants.

Phosphate-based flame retardant

The vinyl chloride resin composition according to the present invention includes a phosphate-based flame retardant as a second flame retardant together with the above plasticizer and antimony-based flame retardant.

The phosphate-based flame retardant exhibits flame retardant properties, has low viscosity at room temperature and low temperature, and has good foaming properties. In addition, it is eco-friendly because there is little risk of volatile organic compounds or endocrine disruptors.

Specifically, as the phosphate-based flame retardant, isopropylphenyl phosphate (or Isopropylated Triphenyl Phosphate or cas no 68937-41-7), tricresyl phosphate, or cresyl diphenyl phosphate And the like, any one or a mixture of two or more of them may be used. Also commercially available, Reofos™ 65 (manufactured by LANXESS) or the like may be used.

The phosphate-based flame retardant may be included in an amount of 5 to 40 parts by weight based on 100 parts by weight of the plasticizer. If the content of the phosphate-based compound is less than 5 parts by weight, it is difficult to obtain a sufficient effect of improving flame retardancy, so an excessive amount of a flame retardant must be separately prescribed. In this case, a viscosity lowering agent needs to be additionally prescribed in order to prevent an increase in the viscosity of the resin composition due to an excessive amount of the flame retardant, and a large amount of volatile organic compounds may be generated or a bleeding problem may occur due to the additionally prescribed viscosity lowering agent. On the other hand, since the phosphate-based flame retardant is a liquid, when the content exceeds 40 parts by weight, the viscosity is lowered, the gelling rate is reduced, and the migration property may be increased. In addition, thermal stability and foaming properties may be deteriorated. More specifically, the phosphate-based flame retardant is 5 parts by weight or more, or 7 parts by weight or more, or 10 parts by weight or more, and 40 parts by weight or less, or 30 parts by weight or less, or 20 parts by weight or less, based on 100 parts by weight of the vinyl chloride resin. It may be included in an amount less than or equal to part.

On the other hand, the vinyl chloride resin composition according to the present invention can further enhance the above effect through optimization of the combination and content of the flame retardant for the plasticizer.

For example, the antimony-based flame retardant and the phosphate-based flame retardant may be included in a weight ratio of 1.5: 1 to 15: 1, and more specifically, based on the content of the antimony-based flame retardant, 15: 1 or less, or 14: 1 or less, or 10:1 or less, or 9:1 or less, and may be included in a weight ratio of 1.5:1 or more, or 1.75:1 or more, or 2:1 or more, or 5:1 or more, or 7:1 or more. When included in the above weight ratio, it is possible to greatly improve the flame retardancy of the resin composition while minimizing the amount of flame retardant used.

As another example, the flame retardant including the antimony-based flame retardant and the phosphate-based flame retardant may be included in an amount of 60 to 140 parts by weight based on 100 parts by weight of the plasticizer, and more specifically, 60 parts by weight or more, or 70 parts by weight or more, or 75 parts by weight or more More than 80 parts by weight, or more than 90 parts by weight, 140 parts by weight or less, or 130 parts by weight or less, or 125 parts by weight or less, or 110 parts by weight or less, or 100 parts by weight or less. When included in the above content range, it may exhibit more improved flame retardancy while maintaining excellent migration characteristics of the plasticizer.

As another example, in the plasticizer, the first plasticizer is recycled di (2-ethylhexyl) cyclohexane-1,4-dicarboxylate, and the second plasticizer is di (2-ethylhexyl) cyclohexane-1 ,4-dicarboxylate, the antimony-based flame retardant may be antimony trioxide, and the phosphate-based flame retardant may be isopropylphenyl phosphate (cas no 68937-41-7) or Reofos™ 65 (manufactured by LANXESS). The di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate of the first and second plasticizers has excellent plasticization efficiency and plasticizer migration resistance compared to other cyclohexane dicarboxylate compounds, As the phosphate-based flame retardant, isopropylphenyl phosphate has excellent flame retardancy compared to other phosphate-based compounds and excellent compatibility with additives included in the resin composition. Accordingly, plasticization efficiency, migration resistance, and flame retardancy of the plasticizer may be further improved by using a combination of the plasticizer and the flame retardant.

additive

In addition, the vinyl chloride resin composition according to the present invention, together with the above-described vinyl chloride resin, plasticizer and flame retardant, may further include a) a viscosity reducing agent, and also according to the physical properties of the resin composition to be improved b) nonionic At least one additive selected from the group consisting of a surfactant, c) a dispersing agent, d) a stabilizer, e) a foaming agent, f) a filler, and g) a fat sugar may be optionally further included.

a) viscosity-lowering agent

The vinyl chloride resin composition according to the present invention may optionally further include a viscosity lowering agent for the purpose of improving processability by lowering the viscosity of the composition.

At this time, as the viscosity lowering agent, a carboxylic acid ester-based compound that has excellent compatibility with the plasticizer and the vinyl chloride resin and can reduce the amount of volatile organic compounds generated when used in the vinyl chloride resin composition due to low volatility is used. can

The carboxylic acid ester-based compound is a monocarboxylic acid ester-based compound, and may be prepared by esterifying a C _8-22 carboxylic acid with an alcohol having a C _8-22 alkyl group. More specifically, it may be a compound represented by Formula 3 below:

[Formula 3]

In Formula 3, R _a and R _b are each independently a C _8-22 straight-chain or branched alkyl group such as n-octyl, t-butyl, n-nonyl, or n-decyl.

In addition, commercially available viscosity lowering agents include BYK LP-R 22274™, Viscobyk™ 5025, 5125 and 5050, Jayflex™ 615 or Exxsol™ D100, etc. It can be used more preferably than BYK LP-R 22274™, which has a low gelation rate and a high gelling rate.

In addition, the viscosity-lowering agent has a density of 0.85 to 0.9 g/cm ³ , more specifically 0.87 to 0.9 g/cm ³ at 20 °C, and a solidification point of -7 °C or less, more specifically -10 to -40 °C, and may have a flash point of 120 °C or higher, more specifically 130 °C to 200 °C. When the solidification point and the flash point are satisfied together with the above density conditions, the gelling rate is fast and the viscosity lowering ability is excellent, so that the processability of the resin composition can be further improved.

The viscosity lowering agent may be included in an amount of 5 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin, more specifically, 5 parts by weight or more, or 10 parts by weight or more, 20 parts by weight or less, or 15 parts by weight or less. can be included If the content of the viscosity-lowering agent is less than 5 parts by weight, the viscosity of the formulation is high, and defects such as sol drop may occur in the processing process. There is a possibility that the formability is lowered.

b) nonionic surfactants

The vinyl chloride resin composition according to the present invention may optionally further include a nonionic surfactant.

At this time, as the nonionic surfactant, polyethylene glycol (polyethylen glycol; PEG), polypropylene glycol (PPG), polyethylene-propylene copolymer (polyethylene-propylene copolymer), polyoxyethylene oxide (PEO) , polyethylene oxide, or polypropylene oxide, and the like, and any one or a mixture of two or more of them may be used.

In addition, the nonionic surfactant may have a density of 0.9 to 1.3 g/cm ³ , more specifically, 0.90 to 1.1 g/cm ³ at 20 °C. When the above density conditions are satisfied, dispersion stability may be improved and the effect of reducing the viscosity of the resin composition may be further improved.

In addition, the nonionic surfactant may have a flash point of 80 °C or higher, more specifically, 100 °C to 300 °C. By having a flash point within the above range, the thermal stability of the resin composition may be improved.

The nonionic surfactant 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 nonionic surfactant is less than 0.5 parts by weight, the dispersion stability of the formulation may decrease, and if it exceeds 5 parts by weight, the foamability of the wallpaper may decrease. Considering the remarkable effect of improving the nonionic surfactant content control for the vinyl chloride resin, the nonionic surfactant is more specifically 0.5 parts by weight or more, or 1 part by weight or more, based on 100 parts by weight of the vinyl chloride resin, It may be included in 5 parts by weight or less, or 3 parts by weight or less.

c) dispersant

The dispersant is adsorbed on the surface to reduce the attractive force between the particles and prevent re-aggregation, thereby facilitating the movement of the particles and stabilizing the viscosity and behavior of the resin composition.

As the dispersant, a fatty acid ester may be used, which not only exhibits excellent dispersibility in the vinyl chloride resin but also exhibits an additional viscosity lowering effect due to the property of lowering the viscosity of the formulation. Specifically, stearyl cetyl stearates (CETS), ethylene glycol distearate (EGDS), glyceryl monooleate (GMO), pentaerythritol distearate (PentaErythritol Distearate; PEDS), PentaErythritol Tetrastearate (PETS), Glyceryl Monostearate (GMS), or Stearyl Stearate, Distearyl Pthalate, and the like. Any one of them or two or more compounds may be used.

In addition, the dispersant has a density of 0.9 to 1.3 g/cm ³ , more specifically 0.90 to 1.1 g/cm ³ at 20° C., and an acid value of 80 to 120 mgKOH/g, more specifically 90 to 100 mgKOH/g. may be g. When the above density and acid value conditions are satisfied, excellent dispersibility may be exhibited and the viscosity lowering effect of the resin composition may be further improved.

In addition, the dispersant may have a flash point of 80 °C or higher, more specifically, 100 °C to 300 °C. By having a flash point within the above range, the thermal stability of the resin composition may 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 parts by weight, there is a concern about poor dispersibility of the formulation, and if it exceeds 5 parts by weight, there is a concern about deteriorating the foamability of the wallpaper. Considering the remarkable dispersibility and foaming effect of the dispersant content control for the vinyl chloride resin, the dispersant is more specifically 0.5 parts by weight or more, or 1 part by weight or more, and 5 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin. , or may be included in 3 parts by weight or less.

d) stabilizer

In addition, the stabilizer is added for the purpose of preventing various changes in physical properties caused by separation of HCl from the vinyl chloride resin to form a polyene structure, which is a chromophore, causing cutting and crosslinking of the main chain, and may be a liquid compound. Specific examples include Na-Zn-based compounds, Ca-Zn-based compounds, K-Zn-based compounds, Ba-Zn-based compounds, organic Tin-based compounds, metallic soap-based compounds, phenol-based compounds, or phosphorous acid ester-based compounds. Any one of them or a mixture of two or more may be used. More specific examples include Na-Zn-based compounds; Ca-Zn-based compounds; K-Zn-based compounds; Ba-Zn-based compounds; organic Tin-based compounds such as mercaptide-based compounds, maleic acid-based compounds, or carboxylic acid-based compounds; metallic soap-based compounds such as Mg-stearate, Ca-stearate, Pb-stearate, Cd-stearate, or Ba-stearate; phenolic compounds; or phosphite ester compounds, among which, in the present invention, Ca-Zn compounds, Na-Zn compounds, or K-Zn compounds can be more preferably used. Moreover, LFX910D-1™ (made by KD Chem) etc. can be used commercially.

The stabilizer is preferably 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 stabilizer is less than 0.5 parts by weight, there is a problem of poor thermal stability, and if it exceeds 7 parts by weight, more than necessary thermal stability may be expressed. More specifically, the stabilizer is 0.5 parts by weight or more, or 1 part by weight or more, or 3 parts by weight or more, and 7 parts by weight or less, or 5 parts by weight or less, or 4 parts by weight or less, based on 100 parts by weight of the vinyl chloride resin. can be included

e) blowing agent

In addition, the foaming agent may include a chemical foaming agent or a physical foaming agent, and any one or a mixture of the two may be used.

Specifically, the chemical blowing agent is not particularly limited as long as it is a compound that decomposes at a specific temperature or higher to generate gas, and azodicarbonamide, azodiisobutyro-nitrile, benzenesulfonylhydra Zide (benzenesulfonhydrazide), 4,4-oxybenzenesulfonyl-semicarbazide, p-toluene sulfonyl semi-carbazide, barium azodica Boxylate (barium azodicarboxylate), N,N'-dimethyl-N,N'-dinitrosoterephthalamide (N,N'-dimethyl-N,N'-dinitrosoterephthalamide), trihydrazino triazine etc. can be cited as an example. Further examples thereof include sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium carbonate, and ammonium carbonate.

In addition, physical foaming agents include 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, a halogenated aliphatic hydrocarbon compound containing 1 to 4 carbon atoms, etc. of organic foaming agents. In addition, methane, ethane, propane, normal butane, isobutane, normal pentane, isopentane, or neopentane may be mentioned as the aliphatic hydrocarbon compound, and methanol, ethanol, normal propanol, or isopropanol may be used as the aliphatic alcohol. and the like, and as the halogenated aliphatic hydrocarbon compound, methyl fluoride, perfluoromethane, ethyl fluoride, 1,1-difluoroethane (1,1- difluoroethane, HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (1,1,1, 2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoromethane (HFC-134), 1,1,1,3,3-pentafluoro Butane (1,1,1,3,3-pentafluorobutane, HFC-365mfc), 1,1,1,3,3-pentafluoropropane (1,1,1,3,3-pentafluoropropane, HFC.sub. 13 245fa), pentafluoroethane, difluoromethane, perfluoroethane, 2,2-difluoropropane, 1,1,1- Trifluoropropane, perfluoropropane, dichloropropane, difluoropropane, perfluorobutane, perfluorocyclobutane ( perfluorocyclobutane), methyl chloride, methylene chloride, ethyl chloride, 1,1,1-trichloroethane, 1,1-dichloro -1-fluoroethane (1,1-dichloro-1-fluoroethane, HCFC-141b), 1-chloro-1,1-difluoroethane (1-chloro-1,1-difluoroethane, HCFC-142b), Chlorodifluoromethane (HCFC-22), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), 1 -Chloro-1,2,2,2-tetrafluoroethane (1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124), trichloromonofluoromethane (CFC-11), dichloro Dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-113), 1,1,1-trifluoroethane (1,1,1-trifluoroethane), pentafluoroethane ( pentafluoroethane), dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane, or dichlorohexafluoropropane. Any one of the above compounds or a mixture of two or more may be used as a blowing agent. Also commercially, DWPX03™ (manufactured by Dongjin Semichem Co., Ltd.) or the like can be used.

The foaming agent as described above 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 foaming agent is less than 0.5 parts by weight, the amount of gas generated for foaming is too small, and the foaming effect is insignificant or cannot be expected at all, and if it exceeds 7 parts by weight, the amount of gas generated is too large, making it difficult to expect the required physical properties. . More specifically, it may be included in 0.5 parts by weight or more, or 1 part by weight or more, or 3 parts by weight or more, and 7 parts by weight or less, or 5 parts by weight or less.

f) filler

In addition, the filler is used for the purpose of improving productivity and dry touch of the vinyl chloride resin composition. Specific examples of the filler include calcium carbonate, calcite, talc, kaolin, silica, alumina, magnesium hydroxide or clay, and any one or a mixture of two or more of these may be used. Moreover, Omya-10™ (manufactured by Omya Korea Company) or the like can be used commercially.

The filler may be included in an amount of 30 to 150 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 in that dimensional stability and economical efficiency are lowered, and if it exceeds 150 parts by weight, the foamed surface is not good and there is a concern that workability is lowered. More specifically, the filler is 30 parts by weight or more, or 50 parts by weight or more, or 80 parts by weight or more, or 100 parts by weight or more, or 120 parts by weight or more, based on 100 parts by weight of the vinyl chloride resin, 150 parts by weight or less, Or it may be included in an amount of 140 parts by weight or less, or 130 parts by weight or less, or 125 parts by weight or less.

g) fat sugar

In addition, the lipid sugar (TiO ₂ ) serves to improve the whiteness and hiding properties of the vinyl chloride resin composition.

The fat sugar may be included in an amount of 1 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content of paper sugar is less than 1 part by weight, whiteness and hiding properties are lowered, so that the color does not come out properly after printing, and if it exceeds 20 parts by weight, the foamed surface properties may be deteriorated. More specifically, the fat sugar is 1 part by weight or more, or 3 parts by weight or more, or 5 parts by weight or more, or 10 parts by weight or more, 20 parts by weight or less, or 15 parts by weight or less, based on 100 parts by weight of the vinyl chloride resin. or 12 parts by weight or less.

The physical properties and characteristics of the vinyl chloride resin composition can be further improved by optimizing the content and composition of the above additives.

Specifically, the vinyl chloride resin composition according to the present invention, based on 100 parts by weight of the vinyl chloride resin, based on 100 parts by weight of the vinyl chloride resin, 70 to 90 parts by weight of the plasticizer, 50 to 90 parts by weight of an antimony-based flame retardant, and phosphate 5 to 40 parts by weight of a flame retardant, and 5 to 20 parts by weight of a viscosity reducing agent may be further included.

More specifically, the vinyl chloride resin composition is based on 100 parts by weight of the vinyl chloride resin, 70 to 90 parts by weight of the plasticizer, 50 to 90 parts by weight of the antimony-based flame retardant, and 5 to 5 parts by weight of the phosphate-based flame retardant 40 parts by weight, 5 to 20 parts by weight of a viscosity reducing agent, 0.5 to 5 parts by weight of a nonionic surfactant, 0.5 to 7 parts by weight of a stabilizer, 0.5 to 7 parts by weight of a foaming agent, 30 to 150 parts by weight of a filler and 1 to 20 parts by weight of paper sugar Wealth may be further included. In this case, better flame retardancy, migration resistance and processability can be exhibited.

On the other hand, the vinyl chloride resin composition according to the present invention can be prepared by a method generally known in the art using the above-described vinyl chloride resin and additives such as a plasticizer, an antimony-based flame retardant, a phosphate-based flame retardant, and optionally a viscosity lowering agent. It may be, and the manufacturing method is not particularly limited.

The vinyl chloride resin composition having the above composition can reduce carbon emissions by including a plasticizer obtained from the recycled raw material, and thus is environmentally friendly.

In addition, the vinyl chloride resin composition may exhibit low viscosity and improved processability. Accordingly, the content of additives such as a viscosity lowering agent and a liquid stabilizer, which are usually added to lower the viscosity of plastisol, can be minimized, and as a result, the amount of volatile organic compounds (TVOCs) generated from these additives can be reduced.

Specifically, the vinyl chloride resin composition has a viscosity of 10,000 cps or less, more specifically 9,900 cps or less, or 9,850 cps or less, or 9,500 cps or less, or 9,000 cps or less, or 8,500 cps or less, or 8,000 cps or less, or Below 7,500 cps. The viscosity of the vinyl chloride resin composition is preferably lower, but the viscosity of the resin composition may be 1,000 cps or more, or 5,000 cps or more, or 6,000 cps or more, 6,300 cps or more, or 6,500 cps or more in consideration of feasibility.

On the other hand, in the present invention, the viscosity of the vinyl chloride resin composition can be measured using a Brookfield viscometer (spindle #6, 20 RPM) after aging for 1 hour in a 25 ° C. constant temperature oven, and will be described in more detail in the following test examples. .

In addition, the vinyl chloride resin composition exhibits excellent migration resistance, and as a result, it can exhibit significantly improved discoloration characteristics.

Specifically, the vinyl chloride resin composition has a low migration rate of 7% or less, or 6% or less, or 5.5% or less, or 4.9% or less, or 4.6% or less, or 4% or less when migration is evaluated according to Equation 2 below. indicate Since lower transferability means better, the lower limit is not limited, but may be, for example, 0.001% or more, or 0.01% or more.

[Equation 2]

Transferability (%) = [(weight of wallpaper before test under harsh conditions - weight of wallpaper after leaving for 24 hours under harsh conditions) / weight of wallpaper before test under harsh conditions] × 100

In the evaluation of transferability, after preparing a wallpaper using the vinyl chloride resin composition, a sample was prepared by placing the wallpaper between oiled paper, and the prepared sample was subjected to harsh conditions (temperature: 60 ° C., pressure: 3 cm in diameter) A 5 kg weight is placed on the phosphorus sample) for 24 hours, and the weight change of the wallpaper before and after being left under harsh conditions is measured, and the above equation 2 is used.

Accordingly, the polyvinyl chloride resin composition can be used for flooring, wallpaper, tarpaulin, artificial leather, toys, or automobile lower coating materials, and is particularly useful for producing wallpaper, especially eco-friendly flame retardant wallpaper, because it is environmentally friendly and has excellent flame retardancy and discoloration properties. can do.

Hereinafter, the present invention will be described in more detail based on examples. However, the following examples are only to illustrate the present invention, and the detailed description of the present invention is not limited by the following examples.

In addition, "%" and "parts" representing contents in the following examples and comparative examples are based on weight unless otherwise specified.

In addition, the acid value of the plasticizer compound used in the following Examples and Comparative Examples is the weight (mg) of potassium hydroxide (KOH) required to neutralize the acid contained in 1g of the plasticizer compound sample, and was measured according to JIS K 6751.

Example One

Regenerated di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (R-DEHCH ^a , acid value = 0.175 KOH mg/g) was mixed with DEHCH ^a (acid value = 0.018 KOH mg/g) and R-DEHCH ^a :DEHCH ^a was mixed to a weight ratio of 50:50 to prepare a plasticizer.

Thereafter, 80 parts by weight of the plasticizer prepared above, 70 parts by weight of antimony trioxide as an antimony-based flame retardant, phosphate-based flame retardant (Reofos ™65, manufactured by LANXESS) 10 parts by weight, liquid stabilizer (LFX910D-1™, manufactured by KD Chem) 3 parts by weight, paper sugar (TiO ₂ ) 10 parts by weight, calcite filler (Omya-10™, manufactured by Omya Korea Company) 125 Parts by weight, foaming agent (DWPX03™, manufactured by Dongjin Semichem) 3 parts by weight, carboxylic acid ester-based viscosity lowering agent (BYK LP-R 22274™, manufactured by BYK, density at 20° C. = 0.879 g/cm ³ , solidification point: <- 13 ℃, flash point: >140 ℃) 10 parts by weight, and BYK-1163 (manufactured by BYK, density at 20 ℃ = 1.018 g / cm ³ , flash point: 140 ℃) as a nonionic surfactant 1 part by weight in a Mathis mixer minutes to prepare a vinyl chloride resin composition (plastisol).

Example 2 and 3

A vinyl chloride resin composition was prepared in the same manner as in Example 1, except for using a plasticizer prepared by mixing R-DEHCH ^a and DEHCH ^a in a weight ratio shown in Table 1 below.

Examples 4 and 5

A vinyl chloride resin composition was prepared in the same manner as in Example 2, except that the plasticizer was used in the amount shown in Table 1 below.

Examples 6 and 7

A vinyl chloride resin composition was prepared in the same manner as in Example 2, except that the antimony-based flame retardant was used in the amount shown in Table 1 below.

Examples 8 and 9

A vinyl chloride resin composition was prepared in the same manner as in Example 2, except that the phosphate-based flame retardant was used in the amount shown in Table 1 below.

Example 10

A vinyl chloride resin composition was prepared in the same manner as in Example 2, except that R-DEHCH ^b having an acid value of 0.263 KOH mg/g was used instead of R-DEHCH ^a in Example 2.

Example 11

A vinyl chloride resin composition was prepared in the same manner as in Example 2, except that R-DEHCH ^c having an acid value of 0.13 KOH mg/g was used instead of R-DEHCH ^a in Example 2.

Comparative Example 1

A vinyl chloride resin composition was prepared in the same manner as in Example 1, except that 80 parts by weight of DOTP (acid value: 0.015 KOH mg/g) alone was used as a plasticizer.

Comparative Example 2

As shown in Table 2 below, a vinyl chloride resin composition was prepared in the same manner as in Example 1, except that 80 parts by weight of DEHCH ^a (acid value: 0.018 KOH mg/g) alone was used as a plasticizer.

Comparative Example 3

As shown in Table 2 below, a vinyl chloride resin composition was prepared in the same manner as in Example 1, except that 80 parts by weight of R-DEHCH ^a (acid value: 0.175 KOH mg/g) was used alone as a plasticizer.

Comparative Examples 4 and 5

A vinyl chloride resin composition was prepared in the same manner as in Example 1, except for using a plasticizer prepared by mixing R-DEHCH ^a and DEHCH ^a in a weight ratio shown in Table 2 below.

Comparative Example 6

A vinyl chloride resin composition was prepared in the same manner as in Example 2, except that only the antimony-based flame retardant was used in the amount shown in Table 2 below without the phosphate-based flame retardant.

Comparative Example 7

A vinyl chloride resin composition was prepared in the same manner as in Example 2, except that only the phosphate-based flame retardant was used without the antimony-based flame retardant in the amount shown in Table 2 below.

Comparative Example 8

As shown in Table 2 below, a vinyl chloride resin composition was prepared in the same manner as in Example 2, except for using Aluminum Trihydrate (ATH) (OSA-10™, manufactured by Ohseong Enterprises) instead of the antimony-based flame retardant. did

Comparative Examples 9 and 10

A vinyl chloride resin composition was prepared in the same manner as in Example 2, except that the plasticizer was used in the amount shown in Table 2 below.

Comparative Example 11

A vinyl chloride resin composition was prepared in the same manner as in Example 2, except that the antimony-based flame retardant was used in the amount shown in Table 2 below.

Comparative Example 12

A vinyl chloride resin composition was prepared in the same manner as in Example 2, except that the phosphate-based flame retardant was used in the amount shown in Table 2 below.

Comparative Example 13

A vinyl chloride resin composition was prepared in the same manner as in Example 2, except that R-DEHCH ^d having an acid value of 0.45 KOH mg/g was used instead of R-DEHCH ^a in Example 2.

Comparative Example 14

A vinyl chloride resin composition was prepared in the same manner as in Example 2, except that DEHCH ^b having an acid value of 0.2 KOH mg/g was used instead of DEHCH ^a in Example 2.

Comparative Example 15

Except for using recycled DOTP (R- ^DOTP ) having an acid value of 0.23 KOH mg/g and DOTP having an acid value of 0.015 KOH mg/g instead of R-DEHCH a and DEHCH ^a in Example 2, the above A vinyl chloride resin composition was prepared in the same manner as in Example 2.

Example
(parts by weight) One 2 3 4 5 6 7 8 9 10 11 vinyl chloride resin 100 100 100 100 100 100 100 100 100 100 100 plasticizer type
(weight ratio) R-DEHCH ^a : DEHCH ^a 50:50 R-DEHCH ^a : DEHCH ^a 60:40 R-DEHCH ^a : DEHCH ^a 30:70 R-DEHCH ^a : DEHCH ^a 60:40 R-DEHCH ^a : DEHCH ^a 60:40 R-DEHCH ^a : DEHCH ^a 60:40 R-DEHCH ^a : DEHCH ^a 60:40 R-DEHCH ^a : DEHCH ^a 60:40 R-DEHCH ^a : DEHCH ^a 60:40 R-DEHCH ^b : DEHCH ^a 60:40 R-DEHCH ^c : DEHCH ^a 60:40 Plasticizer Usage 80 80 80 70 90 80 80 80 80 80 80 antimony flame retardant 70 70 70 70 70 50 90 70 70 70 70 Phosphate flame retardant 10 10 10 10 10 10 10 5 40 10 10 Other flame retardants - - - - - - - - - - - stabilizator 3 3 3 3 3 3 3 3 3 3 3 Jidang 10 10 10 10 10 10 10 10 10 10 10 filler 125 125 125 125 125 125 125 125 125 125 125 blowing agent 3 3 3 3 3 3 3 3 3 3 3 viscosity lowering agent 10 10 10 10 10 10 10 10 10 10 10 nonionic surfactant One One One One One One One One One One One

comparative example
(parts by weight) One 2 3 4 5 6 7 8 9 10 11 12 13 14 15 vinyl chloride resin 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 plasticizer type
(weight ratio) DOTP DEHCH ^a R-DEHCH ^a R-DEHCH ^a : DEHCH ^a 70:30 R-DEHCH ^a : DEHCH ^a 10:90 R-DEHCH ^a : DEHCH ^a 60:40 R-DEHCH ^a : DEHCH ^a 60:40 R-DEHCH ^a : DEHCH ^a 60:40 R-DEHCH ^a : DEHCH ^a 60:40 R-DEHCH ^a : DEHCH ^a 60:40 R-DEHCH ^a : DEHCH ^a 60:40 R-DEHCH ^a : DEHCH ^a 60:40 R-DEHCH ^d :DEHCH ^a 60:40 R-DEHCH ^a : DEHCH ^b 60:40 R-DOTP: DOTP
60:40 Plasticizer Usage 80 80 80 80 80 80 80 80 60 100 80 80 80 80 80 antimony flame retardant 70 70 70 70 70 80 - - 70 70 100 70 70 70 70 Phosphate-based flame retardant 10 10 10 10 10 - 80 10 10 10 10 50 10 10 10 Other flame retardants - - - - - - - 70 - - - - - - - stabilizator 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Jidang 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 filler 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 blowing agent 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 viscosity lowering agent 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 nonionic surfactant One One One One One One One One One One One One One One One

In Tables 1 and 2 above, the compounds used are as follows:

Vinyl chloride resin: EL-103™ (manufactured by Hanwha Solutions, degree of polymerization 950±50)

Antimony flame retardant: antimony trioxide

Phosphate-based flame retardant: Reofos™65 (manufactured by LANXESS)

Other flame retardants: Aluminum Trihydrate (ATH) (OSA-10™, manufactured by Ohsung Corporation)

Stabilizer: Liquid stabilizer (LFX910D-1™, manufactured by KD Chem)

Fat sugar: TiO ₂

Filler: Calcite filler (Omya-10™, manufactured by Omya Korea Company)

Foaming agent: DWPX03™ (manufactured by Dongjin Semichem)

Viscosity-lowering agent: carboxylic acid ester-based viscosity-lowering agent (BYK LP-R 22274™, manufactured by BYK, density at 20°C = 0.879 g/cm ³ , silidification point: <-13°C, flash point: >140 ℃)

Nonionic surfactant: BYK-1163™ (manufactured by BYK, density at 20°C = 1.018 g/cm ³ , flash point: 140°C)

Also, in Tables 1 and 2, the amount of each component used is a relative weight ratio (parts by weight) based on 100 parts by weight of the vinyl chloride resin.

Experimental example

The physical properties of the plasticizer and the finally prepared vinyl chloride resin composition used in Examples and Comparative Examples were evaluated by the following methods, and the results are shown in Tables 3 and 4.

(1) Carbon emission of plasticizer and carbon emission reduction rate

For the plasticizers used in the above examples and comparative examples, the carbon emission reduction rate (%) was calculated according to Equation 1 below.

[Equation 1]

Carbon emission reduction rate (%) = 100 - [(A1/A2)×100]

In Equation 1 above,

A1 is the carbon emission of the plasticizer in Examples or Comparative Examples (tCO ₂ eq / MT),

A2 is the carbon footprint of the control plasticizer (tCO ₂ eq/MT).

Specifically, in Equation 1, A1 corresponds to the sum of carbon emissions (tCO ₂ eq/MT) according to the composition ratio of each component included in the plasticizer, and A2 is recycled cyclohexane dicarboxylic acid obtained from a recycled phthalate-based compound. Carbon emissions (tCO ₂ eq /MT). Here, the unit of carbon emissions is expressed as a weight equivalent (eq) of total CO ₂ emissions per metric ton.

As an example, the carbon emission (A1) of a plasticizer containing R-DEHCH and DEHCH in a 50:50 ratio is the sum of the carbon emissions of each component according to this composition ratio, that is, the carbon emission of R-DEHCH × 0.5 + the carbon emission of DEHCH × Calculated by 0.5, this is 0.608 tCO ₂ eq/MT. In addition, the control plasticizer for the plasticizer contains only DEHCH, and its carbon emission (A2) is 0.651 tCO ₂ eq/MT calculated as the carbon emission of DEHCH × 1. Therefore, according to Equation 1, the carbon emission reduction rate of the plasticizer containing R-DEHCH and DEHCH at a ratio of 50:50 is 6.6%.

Here, the carbon emissions of each component used in the plasticizers of Examples and Comparative Examples are as follows.

- Polyvinyl chloride (PVC, Hanwha Solution P-1000): 0.182 tCO ₂ eq/MT

- Regenerated di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (R-DEHCH): 0.565 tCO ₂ eq/MT

- pure di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (DEHCH, or Pure-DEHCH): 0.651 tCO ₂ eq/MT

- Pure di(octyl)terephthalate (DOTP, or Pure-DOTP): 0.571 tCO ₂ eq/MT

- Regenerated di(octyl)terephthalate (R-DOTP): 0.485 tCO ₂ eq/MT

Among these, the carbon emissions of polyvinyl chloride (PVC) and DOTP were referred to the values provided by the manufacturer. Carbon emissions of R-DEHCH and DEHCH are calculated as the sum of carbon emissions from each process when manufactured from recycled di(octyl)terephthalate (R-DOTP, carbon emissions 0.485 tCO ₂ eq/MT) and Pure-DOTP, respectively is a value

In addition, the carbon emission of recycled dioctyl terephthalate (R-DOTP) is 70% of the carbon emission of recycled PTA (Purified terephthalic acid) used in R-DOTP, and PTA and 2-EH (2-ethylhexanol ) is a value calculated with the same carbon emissions. PTA and 2-EH are raw materials for producing DOTP.

(2) Smell

The odor of the plasticizer used in the above Examples and Comparative Examples was comparatively evaluated through a sensory test.

(Excellent, good without odor) ◎ > ○ > △ > X (very poor, oily smell)

(3) Whiteness

White index of the plasticizers used in Examples and Comparative Examples was measured using a color difference meter (Konica Minolta, CR-400) under conditions of a 2° field of view and a C light source. A higher number means better.

(4) Viscosity of the vinyl chloride resin composition

After aging the vinyl chloride resin composition prepared in each Example and Comparative Example in a constant temperature oven at 25 ° C. for 1 hour, the viscosity at 25 ° C. was measured using a Brookfield viscometer (spindle # 6, 20 RPM). When the viscosity is 1,000 to 10,000 cPs, the viscosity characteristics can be evaluated as excellent.

(5) Gelling rate of vinyl chloride resin composition

The gelling rate, which is the rate at which the plasticizer is absorbed into PVC, was measured using SVNC equipment. Specifically, in the SVNC equipment, the same content of the vinyl chloride resin compositions of Examples and Comparative Examples was put into a pot in which the temperature was fixed at 120 ° C., and a vibrating needle was inserted to monitor the vibration of the needle while Plastisol hardened. Gelling speed was measured. The results were scored from a minimum of 1 point to a maximum of 5 points to compare and evaluate the gelling speed. At this time, the higher the score, the faster the gelling rate.

(6) Transferability of the vinyl chloride resin composition

Wallpaper was manufactured using the vinyl chloride resin compositions of Examples and Comparative Examples. Each sample was prepared by placing the prepared wallpaper between oiled paper, and the prepared sample was left for 24 hours under harsh conditions (temperature: 60 ° C, pressure: a 5 kg weight was placed on a sample with a diameter of 3 cm), The weight change of the wallpaper was observed. Transferability was evaluated according to Equation 2 below using the weight value of the wallpaper measured before and after the test under the harsh conditions.

[Equation 2]

Transferability (%) = [(weight of wallpaper before test under harsh conditions - weight of wallpaper after leaving for 24 hours under harsh conditions) / weight of wallpaper before test under harsh conditions] × 100

(7) Flame retardancy of vinyl chloride resin composition

Wallpaper was prepared using the polyvinyl chloride resin compositions of the above Examples and Comparative Examples, and in accordance with 「Fire Retardant Performance Standards」 (Fire Agency Notification No. 2019-2) Article 6 'Measurement Criteria and Method for Flame Retardant Performance of Thin Fabrics', Carbon area (cm ² ) was measured using a tester (UL94). The smaller the carbonization area, the better the flame retardancy.

Example One 2 3 4 5 6 7 8 9 10 11 Plasticizer Carbon Emissions
(tCO ₂ eq/MT) 0.608 0.599 0.625 0.599 0.599 0.599 0.599 0.599 0.599 0.599 0.599 Plasticizer Carbon Emission Reduction Rate
(%) 6.6 7.9 4.0 7.9 7.9 7.9 7.9 7.9 7.9 7.9 7.9 smell ◎ ○ ◎ ○ ○ ○ ○ ○ ○ ○ ○ whiteness 63.95 62.8 64.6 63.2 62.2 63.1 62.6 62.8 62.7 61.6 62.53 viscosity
(cPs) 8,350 8,345 8,360 9,820 7,145 6,930 9,995 9,140 6,350 8,405 8,370 transitivity
(%) 4.6 4.5 4.4 3.9 4.9 4,5 4.3 4.3 5.5 4.5 4.4 carbon area
(cm ² ) 28.8 28.6 28.9 27.9 29.4 29.8 26.2 29.3 27.8 29.0 28.7 gelling speed 4 4 4 4 4 4 4 4 3.5 4 4

comparative example One 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Plasticizer Carbon Emissions
(tCO ₂ eq/MT) 0.571 0.651 0.565 0.591 0.642 0.599 0.599 0.599 0.599 0.599 0.599 0.599 0.599 0.599 0.519 Plasticizer Carbon Emission Reduction Rate
(%) 12.3 0.0 13.2 9.2 1.3 7.9 7.9 7.9 7.9 7.9 7.9 7.9 7.9 7.9 20.2 smell ◎ ◎ X △ ○ ○ ○ ○ ◎ △ ○ ○ △ ○ ○ whiteness 65.65 65.95 58.5 59.75 64.5 62.65 62.1 63.2 63.8 60.9 62 62.2 58.57 62.8 61.9 viscosity
(cPs) 13,250 8,275 8,630 8,495 8,550 10,435 5,670 8,485 16,535 6,210 11,545 5,980 8,345 8,345 13,950 transitivity
(%) 9.2 4.5 4.5 4.6 4.6 4.2 6.8 4.5 3.5 5.2 4.1 7.2 4.5 4.5 8.9 carbon area
(cm ² ) 28.3 29.1 28.3 29 28.6 27.9 29.8 32.1 27.5 30.1 25.3 27.7 28.6 28.6 28.5 gelling speed 2 4 4 4 4 4 3 4 4.5 3 4 3 4 4 2

As a result of the experiment, the resin compositions according to Examples 1 to 11 exhibited low viscosity, excellent processability, transition resistance and flame retardancy, along with a reduction in carbon emissions.

In particular, the resin compositions according to Examples 1 to 11 exhibited significantly lower viscosity and transitivity than Comparative Example 1 using DOTP as a plasticizer and Comparative Example 15 using a mixture of R-DOPT and DOPT, and the gelling rate was also fast.

In addition, the resin compositions according to Examples 1 to 11 had the same level of viscosity, transferability and gelling rate as compared to Comparative Example 2 using only DEHCH obtained from pure raw materials as a plasticizer, but R-DEHCH obtained from recycled raw materials The inclusion of the plasticizer carbon emission greatly reduced, and accordingly, a high carbon emission reduction rate of 4% or more was exhibited. In addition, under the condition of the same type and content of other components except for the plasticizer, Examples 1 to 3 showed more improved flame retardancy than Comparative Example 2 as the compatibility increased with the optimal combination of the plasticizer and the flame retardant.

In addition, the resin compositions according to Examples 1 to 11 exhibited increased plasticizer carbon emission and reduced carbon emission reduction rate compared to Comparative Example 3 using only R-DEHCH obtained from recycled raw materials as a plasticizer, but the odor was improved Whiteness increased. In addition, under the condition of the same type and content of other components except for the plasticizer, the viscosity of the resin composition of Examples 1 to 3 was lower than that of Comparative Example 3 due to the mixed use of DEHCH having a low acid value.

In addition, the resin compositions according to Examples 1 to 11 have a low plasticizer carbon emission reduction effect compared to Comparative Example 4 containing an excess of R-DEHCH out of the range of the weight ratio of R-DEHCH and DEHCH in the plasticizer, but the plasticizer Odor characteristics and whiteness were improved. In addition, the viscosity characteristics and flame retardancy of the resin compositions of Examples 1 to 3 were more improved than those of Comparative Example 4 under the condition that the types and contents of other components were the same except for the plasticizer.

Claims (14)

With respect to 100 parts by weight of vinyl chloride resin,
70 to 90 parts by weight of a plasticizer,
50 to 90 parts by weight of an antimony-based flame retardant, and
5 to 40 parts by weight of a phosphate-based flame retardant,
The plasticizer is 20: In a weight ratio of 80 to 65:35,
A vinyl chloride resin composition.
According to claim 1,
The cyclohexane dicarboxylate-based compound and the regenerated cyclohexane dicarboxylate-based compound are each independently a compound represented by Formula 1 below, a vinyl chloride resin composition:
[Formula 1]

In Formula 1,
R ₁ and R ₂ are each independently C _4-12 alkyl.
According to claim 1,
The cyclohexane dicarboxylate compound and the regenerated cyclohexane dicarboxylate compound are each independently di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, diisononylcyclohexane-1 ,2-dicarboxylate, di(2-ethylhexyl)cyclohexane-1,2-dicarboxylate, butyl(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and dibutylcyclo At least one member selected from the group consisting of hexane-1,4-dicarboxylate, a vinyl chloride resin composition.
According to claim 1,
The antimony-based flame retardant and the phosphate-based flame retardant are included in a weight ratio of 1.5: 1 to 15: 1, a vinyl chloride resin composition.
According to claim 1,
The total content of the antimony-based flame retardant and the phosphate-based flame retardant is 60 to 140 parts by weight based on 100 parts by weight of the plasticizer, the vinyl chloride resin composition.
According to claim 1,
The antimony-based flame retardant is antimony trioxide, antimony pentoxide, metal antimony, antimony trichloride or a mixture thereof, a vinyl chloride resin composition.
According to claim 1,
The phosphate-based flame retardant is isopropylphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, or a vinyl chloride resin composition comprising a mixture thereof.
According to claim 1,
The vinyl chloride resin has a polymerization degree of 700 to 1,700, or a weight average molecular weight of 45,000 to 200,000 g / mol, a vinyl chloride resin composition.
According to claim 1,
A vinyl chloride resin composition further comprising 5 to 20 parts by weight of a viscosity lowering agent based on 100 parts by weight of the vinyl chloride resin.
According to claim 9,
The viscosity reducing agent is a carboxylic acid ester-based compound having a density of 0.85 to 0.9 g/cm ³ at 20 °C, a solidification point of -7 °C or less, and a flash point of 120 °C or more, a vinyl chloride resin composition.
According to claim 1,
The vinyl chloride resin composition further comprises at least one additive selected from the group consisting of a nonionic surfactant, a dispersing agent, a stabilizer, a foaming agent, a filler, and a fat sugar, the vinyl chloride resin composition.
According to claim 1,
The vinyl chloride resin composition, based on 100 parts by weight of the vinyl chloride resin, 5 to 20 parts by weight of a viscosity lowering agent, 0.5 to 5 parts by weight of a nonionic surfactant, 0.5 to 7 parts by weight of a stabilizer, 0.5 to 7 parts by weight of a foaming agent, and a filler A vinyl chloride resin composition further comprising 30 to 150 parts by weight and 1 to 20 parts by weight per paper.
According to claim 1,
After aging at 25 ° C. for 1 hour, the vinyl chloride resin composition has a viscosity of 1,000 to 10,000 cps at 25 ° C. measured at spindle number 6 and rotational speed of 20 RPM using a rotational viscometer. A vinyl chloride resin composition.
Wallpaper comprising the vinyl chloride resin composition according to claim 1.