KR20210017660A - Plasticizer composition and vinylchloride resin composition comprising the same - Google Patents

Abstract

The present invention relates to a plasticizer composition capable of improving migration properties and elongation of a plasticizer, and to a vinyl chloride resin composition comprising the same. The plasticizer composition comprises: a cyclohexane dicarboxylate-based compound; a compound; and epoxidized oil.

Description

Plasticizer composition, and vinyl chloride resin composition comprising the same {Plasticizer composition and vinylchloride resin composition comprising the same}

The present invention relates to a plasticizer composition capable of improving transfer characteristics and elongation of a plasticizer, and a vinyl chloride resin composition comprising the same.

Vinyl chloride resin is a homopolymer of vinyl chloride and a hybrid polymer containing 50% or more of vinyl chloride, and is one of the five general-purpose thermoplastic resins produced by suspension polymerization and emulsion polymerization. Among them, polyvinyl chloride resin produced by emulsion polymerization is a plasticizer, a stabilizer, a filler, a blowing agent, a pigment, a viscosity modifier, and a lipid sugar (TiO ₂ ). And it is used in a wide range of fields such as flooring, wallpaper, tarpaulin, artificial leather, toys, and automobile lower coatings through coating molding and mold coating molding processing in the form of plastisol by mixing auxiliary materials having special functions.

In particular, wallpaper is a product that is most exposed in residential and office spaces, and more than 60% of it is manufactured using vinyl chloride resin. Recently, the main issue of wallpaper is about eco-friendly wallpaper, and the criteria for determining eco-friendliness are HB grades (best, excellent, good), which are rated according to the amount of volatile organic compounds (VOCs) that the Air Purification Association enforces. Step 3) and whether it contains phthalate plasticizers (especially DEHP, BBP, DBP), which are considered suspicious substances for environmental hormones in Korea.

Among vinyl chloride resin compositions for wallpaper, plasticizer is a liquid component that occupies the largest amount. Examples of such plasticizers include phthalate products such as DEHP (Di-2-EthylHexyl Phthalate), DINP (Di-IsoNonyl Phthalate), DIDP (Di-Iso-Decyl Phthalate), BBP (Butyl Benzyl Phthalate), DBP (Di-n-butyl phthalate), and in particular DINP has been widely used.

However, phthalate-based plasticizers are suspicious of environmental hormones as an endocrine disrupter that interferes or disrupts human hormonal action socially, and there is a movement to regulate them. Therefore, recently, an example of using a non-phthalate plasticizer instead of a phthalate plasticizer has been reported.

Among the non-phthalate plasticizers, di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (DEHCH) is available, and its low viscosity at room temperature and low temperature enables excellent coating properties, fast gelling speed, and foaming properties. It is excellent in this, and has almost no environmental problems like phthalate plasticizers in particular, and is in the spotlight as a plasticizer for vinyl chloride resin.

However, in spite of the various advantages of DEHCH as described above, DEHCH has many limitations in its use for wallpaper, since its migration to paper is worse than that of existing eco-friendly plasticizers. The transition of plasticizer refers to a phenomenon in which the plasticizer is present in the vinyl chloride resin and then gradually leaks out of the vinyl chloride resin over time. This is especially a flooring material, wallpaper, tarpaulin, artificial leather, and toys that can directly affect the human body. , It is an important factor limiting its use in automobile underside coating materials.

The transition of plasticizers is somewhat difficult to predict because it is greatly affected by the physical/chemical properties between the plasticizer and the vinyl chloride resin. Therefore, it is necessary to test and evaluate the transition characteristics by applying various plasticizers.

In Korean Patent No. 1889540, a plasticizer composition containing di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate and tributyl citrate in a weight ratio of 9:1 to 1:1 was applied to reduce DEHCH. Disclosing content to improve the implementation characteristics. However, when the plasticizer composition of the registered patent is applied to wallpaper, the transition characteristics are improved, but there is a disadvantage in that it does not satisfy a predetermined elongation required for wallpaper for decoration.

Korean Registered Patent No. 1889540

Accordingly, an object of the present invention is to provide an eco-friendly plasticizer composition capable of improving the transfer characteristics of the plasticizer and achieving high elongation when applied to wallpaper.

In addition, the present invention is to provide a vinyl chloride resin composition comprising the plasticizer composition.

In addition, the present invention is to provide a molded article comprising the vinyl chloride resin composition.

In order to solve the above problems, according to an aspect of the present invention, a cyclohexane dicarboxylate-based compound represented by the following formula (1); A compound represented by the following formula (2); And a plasticizer composition comprising an epoxidized oil:

[Formula 1]

In Formula 1,

R ₁₁ and R ₁₂ are the same as each other and are C _4-20 alkyl,

[Formula 2]

In Chemical Formula 2,

R ₁ is hydrogen or acetyl,

R ₂ to R ₄ are each independently C _2-8 alkyl.

According to another aspect of the present invention, there is provided a vinyl chloride resin composition comprising the plasticizer composition.

According to another aspect of the present invention, there is provided a molded article comprising the vinyl chloride resin composition.

The plasticizer composition according to the present invention includes a cyclohexane dicarboxylate-based compound, a compound represented by Chemical Formula 2, and an epoxidized oil, thereby improving transfer characteristics of the plasticizer to prevent environmental problems.

In addition, since the plasticizer composition according to the present invention has a high gelling speed and can lower the processing temperature, it can be used by reducing the heat stabilizer added for thermal stability.

Therefore, the vinyl chloride resin composition comprising the plasticizer composition according to the present invention or a molded article comprising the same can be used for wallpaper, mat, flooring, tarpaulin, artificial leather, toys, automobile interior materials, or automobile lower coating materials, but it is eco-friendly and has excellent performance. Due to its properties and elongation, it can be particularly useful in the manufacture of wallpaper, especially eco-friendly decorative wallpaper.

The terms used in the present specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as "comprises", "includes" or "have" are intended to designate the existence of a feature, step, component, or combination of the implemented features, one or more other features or steps, It is to be understood that the possibility of the presence or addition of components, or combinations thereof, is not excluded in advance.

The present invention will be described in detail below and exemplify specific embodiments, as various changes may be made and may have various forms. However, this is not intended to limit the present invention to a specific form disclosed, it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

Plasticizer composition according to the present invention is a cyclohexane dicarboxylate-based compound represented by the following formula (1); A compound represented by the following formula (2); And epoxidized oils.

[Formula 1]

In Formula 1,

R ₁₁ and R ₁₂ are the same as each other and are C _4-20 alkyl,

[Formula 2]

In Chemical Formula 2,

R ₁ is hydrogen or acetyl,

R ₂ to R ₄ are each independently C _2-8 alkyl.

The plasticizer composition according to the present invention is used as a plasticizer for a vinyl chloride resin, and can significantly improve the transition characteristics and elongation of the plasticizer due to the interaction of three or more plasticizers.

The cyclohexane dicarboxylate-based compound may be represented by Formula 1 below.

[Formula 1]

In Formula 1,

R ₁₁ and R ₁₂ are the same as each other and are C _4-20 alkyl.

In Formula 1, R ₁₁ and R ₁₂ are the same as each other, and are a straight or branched alkyl group having 4 to 20 carbon atoms, more preferably 5 to 20 carbon atoms, and even more preferably 5 to 10 carbon atoms.

According to an embodiment of the present invention, the cyclohexane dicarboxylate-based compound represented by Formula 1 may be represented by the following Formulas 1-1 to 1-3.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3,

R ₁₁ and R ₁₂ are as defined in Chemical Formula 1.

Preferably, the cyclohexane dicarboxylate-based compound may be a compound represented by the following Formula 1-4.

[Formula 1-4]

The compound represented by Formula 1-4 is di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate)), and DEHCH as an abbreviation in English It is also called as.

DEHCH has low viscosity at room temperature and low temperature, so it can realize excellent coating properties, has a fast gelling speed, and has excellent foaming properties. In particular, since the generation of volatile organic compounds can be minimized compared to the existing phthalate plasticizers, the existing plasticizers can be replaced. Even when DEHCH is used alone as a plasticizer of a vinyl chloride resin, the desired physical properties of the vinyl chloride resin can be realized, but DEHCH has a problem of transfer characteristics.

Plasticizer migration refers to a phenomenon in which some of the plasticizer mixed with the polymer resin leaks out of the polymer resin.When the leaked plasticizer enters the body, it inhibits the normal activity of the endocrine system, which is directly involved in life activities. Since it causes fatal harm by triggering an abnormal reaction, the transfer of plasticizers should be suppressed as much as possible.

According to an embodiment of the present invention, based on 100 parts by weight of the total plasticizer composition, the cyclohexane dicarboxylate-based compound represented by Formula 1 is 50 parts by weight or more, or 60 parts by weight or more, and 90 parts by weight or less, or 85 parts by weight or less, or 80 parts by weight or less is preferable. If the content of the cyclohexane dicarboxylate-based compound is too small, the plasticization efficiency may be insufficient, and if the content of the cyclohexane dicarboxylate-based compound is too large, the plasticizer may be transferred more.

Accordingly, in the present invention, in order to maintain excellent properties as a plasticizer of a cyclohexane dicarboxylate-based compound as it is, and to suppress migration of the plasticizer, a compound represented by the following formula (2) is used together.

[Formula 2]

In Chemical Formula 2,

R ₁ is hydrogen or acetyl,

R ₂ to R ₄ are each independently C _2-8 alkyl.

The compound represented by Formula 2 is an ester compound of citric acid and C _2-8 alcohol, and is not limited in theory, but due to interactions such as hydrogen bonds between the ester group and the ester group of the cyclohexane dicarboxylate-based compound. Therefore, the plasticizer is prevented from spilling out of the vinyl chloride resin.

In Formula 2, it is preferable that R ₂ to R ₄ are each independently butyl or octyl.

Representative examples of the compound represented by Formula 2 are tributylcitrate, tri(butyloctyl) citrate, trioctylcitrate, or acetyltributylcitrate. )to be. Here, tri(butyloctyl)citrate means a generic term for compounds in which some of R ₂ to R ₄ of Formula 2 are butyl and some are octyl.

The compound represented by Formula 2 may be purchased and used commercially, and may also be prepared in the same manner as in Scheme 1 below.

[Scheme 1]

The reaction is an esterification reaction of citric acid or acetylcitric acid and C _2-8 alcohol, and can be prepared by performing the above reaction sequentially in one reaction according to the structure of R ₂ to R ₄ or by varying the reactants. Conditions for the reaction may use conventional esterification reaction conditions in the art.

Preferably, the weight ratio of the cyclohexane dicarboxylate-based compound represented by Formula 1 and the compound represented by Formula 2 is 9.5:1 to 1:9.5. If it exceeds 9.5:1, the content of the compound represented by Chemical Formula 2 is small, so the transfer characteristics of the plasticizer cannot be effectively improved, and if it is less than 1:9.5, the content of the cyclohexane dicarboxylate-based compound decreases, resulting in thermal stability. And foamability and volatility resistance are significantly inferior. Preferably, the weight ratio of the cyclohexane dicarboxylate-based compound and the compound represented by Formula 2 is 9:1 to 1:1.

According to an embodiment of the present invention, it was confirmed that when the weight ratio of the cyclohexane dicarboxylate-based compound and the compound represented by Formula 2 was adjusted to 9:1 to 1:1, the transfer characteristics of the plasticizer were more improved. .

According to an embodiment of the present invention, based on 100 parts by weight of the total plasticizer composition, the compound represented by Formula 2 may be included in an amount of 10 parts by weight or more, or 20 parts by weight or more, and 50 parts by weight or less, or 40 parts by weight or less. I can. If the content of the compound represented by Chemical Formula 2 is too small, plasticizer transfer may increase, and if the content of the compound represented by Formula 2 is too large, thermal stability, foaming property, and volatility resistance may decrease.

However, when only the cyclohexane dicarboxylate-based compound and the compound represented by Formula 2 are applied as a plasticizer for vinyl chloride resin, the transfer characteristics are improved, but the disadvantage of not satisfying the predetermined elongation required for decoration wallpaper, etc. have.

Accordingly, the present invention, when including the epoxidized oil in addition to the cyclohexane dicarboxylate-based compound and the compound represented by Formula 2, maintains excellent properties and improved transfer properties as a plasticizer, and at the same time When used, the present invention was brought to the attention of the fact that the elongation can be remarkably improved.

The epoxidized oil is epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearate. ), epoxidized oleate, epoxidized tall oil, and epoxidized linoleate may include at least one selected from the group consisting of.

There is a technology to improve the physical properties of the plasticizer by applying an epoxidized oil together with a terephthalate plasticizer compound in an amount of 10% by weight or more based on the total amount of the plasticizer composition. However, terephthalate-based plasticizer compounds are endocrine disruptors and have environmental problems.

In addition, there is known a technique for excluding a petroleum plasticizer compound and proposing a non-phthalate vegetable plasticizer composition comprising 60 to 95% by weight of epoxidized oil and 1 to 30% by weight of a citrate compound. However, the plasticizer composition contains an epoxidized oil as a main component in an amount of 60% by weight or more, so that heat stability and volatilization loss characteristics may be improved, but the content of DEHCH and TBC is relatively reduced, resulting in a decrease in plasticizer efficiency. In addition, due to the characteristic color of the epoxidized oil, the color becomes yellowish, and the viscosity is high, making it difficult to process.

Therefore. The plasticizer composition according to an embodiment of the present invention is a three-component plasticizer composition comprising a cyclohexane dicarboxylate compound represented by Formula 1, a compound represented by Formula 2, and an epoxidized oil. The problem as described above was solved. That is, the non-phthalate plasticizer compound prevents the occurrence of environmental problems while maintaining the plasticizing efficiency and improves the transfer characteristics of the plasticizer. In addition, the elongation can be improved while maintaining the viscosity of the plasticizer at an appropriate level by the interaction between the epoxidized oil and the compound represented by Chemical Formula 2.

According to one embodiment of the present invention, based on 100 parts by weight of the total plasticizer composition, the epoxidized oil may be included in an amount of 5 parts by weight or more, or 6 parts by weight or more, and 10 parts by weight or less, or 9 parts by weight or less. If the content of the epoxidized oil is too small, the elongation as well as heat resistance and heating loss characteristics may be poor, making it unsuitable for quality standards, and if the content of the epoxidized oil is too large, the color may turn yellow, and processing may be difficult due to high viscosity. have.

Vinyl chloride resin composition

The present invention provides a vinyl chloride resin composition comprising 100 parts by weight of a vinyl chloride resin, and 10 to 120 parts by weight of the plasticizer composition.

When the vinyl chloride resin composition includes the plasticizer composition according to the present invention, the transfer characteristics of the plasticizer and the elongation of the vinyl chloride resin composition can be improved.

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, Any one of these or a mixture of both may be used in the preparation of the vinyl chloride resin composition.

The comonomer copolymerizable with the vinyl chloride monomer specifically includes 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 lauryl vinyl ether; Vinylidene halides 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 such as methyl acrylate, ethyl acrylate, monomethyl maleate, dimethyl maleate, and butylbenzyl maleate; Aromatic vinyl compounds such as styrene, α-methyl styrene, and divinyl benzene; Unsaturated nitriles such as acrylonitrile or methacrylonitrile; Olefins such as ethylene or propylene; Alternatively, crosslinkable monomers such as diallyl phthalate may be used, and any one or a mixture of two or more of them may be used. Among these, the comonomer may more preferably contain vinyl acetate, etc., in that it has excellent compatibility with a vinyl chloride monomer and can improve compatibility with a plasticizer constituting the resin composition after polymerization. .

As described above, the vinyl chloride resin may be prepared by polymerization reaction of a vinyl chloride monomer alone or a vinyl chloride monomer and a comonomer copolymerizable therewith, and the polymerization method is not particularly limited, and fine suspension polymerization, emulsion polymerization or Seed emulsion polymerization and the like can be carried out according to conventional polymerization methods known in the art. Among these, when prepared by emulsion polymerization or micro-suspension polymerization, the average particle size of the vinyl chloride resin produced is small and uniform compared to the case of production 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 is 0.1 to 40 μm, more specifically It may be 1 to 10 μm, and by having a particle size in the above range, excellent dispersibility may be exhibited, and the fluidity of the plasticized vinyl chloride resin composition may be further improved. If the average particle size (D ₅₀ ) exceeds 40 μm, the dispersibility is low as the vinyl chloride resin particles themselves, and if it is less than 1 μm, the dispersibility may decrease due to aggregation between the vinyl chloride resin particles.

Meanwhile, in the present invention, the average particle size (D ₅₀ ) of the vinyl chloride resin may be measured according to a conventional particle size distribution measurement method such as an optical microscope observation method and a light scattering method.

In addition, the degree of polymerization and the weight average molecular weight of the vinyl chloride resin may affect the compatibility with the components constituting the vinyl chloride resin composition, in particular, the plasticizer and the processability of the plastisol. Can be adjusted appropriately.

Specifically, the vinyl chloride resin may have a degree of polymerization of 700 to 1,500, preferably 800 to 1,300, or a weight average molecular weight (Mw) of 45,000 to 200,000 g/mol. When it has a polymerization degree and a weight average molecular weight in the above range, it is excellent in dispersibility, 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 Mw is less than 45,000 g/mol, there is a possibility that the durability and workability of the wallpaper may be deteriorated due to lack of physical properties, and if the degree of polymerization is more than 1,500 or Mw is more than 200,000 g/mol, the foamability decreases. There is concern. More specifically, the degree of polymerization may be 900 or more and less than 1,050, or a weight average molecular weight (Mw) of 60,000 to 150,000 g/mol.

Meanwhile, in the present invention, the weight average molecular weight (Mw) of the vinyl chloride resin is a value in terms of standard polystyrene by gel permeation chromatography.

The plasticizer composition included in the vinyl chloride resin composition according to an embodiment of the present invention comprises a cyclohexane dicarboxylate compound represented by Formula 1, a compound represented by Formula 2, and an epoxidized oil, A detailed description of this is as described above.

The plasticizer composition as described above may be included in an amount of 10 parts by weight or more, or 50 parts by weight or more, 120 parts by weight or less, or 100 parts by weight or less, or 90 parts by weight or less based on 100 parts by weight of the vinyl chloride resin. If the content of the plasticizer composition is too small, the viscosity of the vinyl chloride resin composition or plastisol may increase, resulting in a decrease in coating properties or a possibility of reducing product flexibility. On the contrary, if the content of the plasticizer composition is too high, the plasticizer is likely to leak to the surface of the molded article, a bleeding effect, which causes surface stickiness, which may cause problems in processing and finished products. Therefore, from this point of view, the amount of the plasticizer composition may be within the above-described range.

In addition to the vinyl chloride resin and plasticizer composition, the vinyl chloride resin composition may further include any one or more selected from the group consisting of additives, for example, a stabilizer, a foaming agent, a filler, and a lipid sugar (TiO ₂ ). The additive may be appropriately selected according to the physical properties to be improved in the vinyl chloride resin composition.

The stabilizer is added for the purpose of preventing various changes in physical properties caused by cutting and crosslinking of the main chain by separating HCl from the vinyl chloride resin to form a polyene structure, which is a chromophore, and Ca-Zn-based compounds, K- Zn-based compounds, Ba-Zn-based compounds, and organic Tin-based compounds; It includes any one or more selected from the group consisting of a metallic soap compound, a phenol compound, a phosphoric acid ester compound, or a phosphorous acid ester compound. More specific examples as a stabilizer that can be used in the present invention are Ca-Zn-based compounds; K-Zn-based compounds; Ba-Zn-based compounds; Organic Tin-based compounds such as a mercaptide-based compound, a maleic acid-based compound, or a carboxylic acid-based compound; Metallic soap-based compounds such as Mg-stearate, Ca-stearate, Pb-stearate, Cd-stearate, or Ba-stearate; Phenolic compounds; Phosphoric acid ester compounds; Or a phosphorous acid ester compound, and the like, and is optionally included depending on the purpose of use. In the present invention, it is particularly preferable to use a K-Zn-based compound, preferably a K-Zn-based complex organic compound.

The stabilizer contains preferably 0.5 to 7 parts by weight, more preferably 1 to 4 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 in that thermal stability is poor, and if it exceeds 7 parts by weight, more than necessary thermal stability may be expressed.

The blowing agent used in the present invention includes any one or more selected from a chemical blowing agent, a physical blowing agent, or a mixture thereof.

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 a gas, and azodicarbonamide, azodiisobutyro-nitrile, benzenesulfonhydrazide ), 4,4-oxybenzene sulfonyl-semicarbazide, p-toluene sulfonyl semi-carbazide, barium azodicarboxylate ( barium azodicarboxylate), N,N'-dimethyl-N,N'-dinitrosoterephthalamide (N,N'-dimethyl-N,N'-dinitrosoterephthalamide), trihydrazino triazine, etc. Can be lifted. In addition, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium carbonate, ammonium carbonate, and the like are exemplified. In addition, as the physical blowing agent, inorganic blowing agents such as carbon dioxide, nitrogen, argon, water, air, and helium, aliphatic hydrocarbons containing 1 to 9 carbon atoms, aliphatic alcohols containing 1 to 3 carbon atoms. alcohol), a halogenated aliphatic hydrocarbon compound containing 1 to 4 carbon atoms, and other organic blowing agents.

Specific examples of such compounds include methane, ethane propane, normal butane, isobutane, normal pentane, isopentane, neopentane, etc. as aliphatic hydrocarbon compounds, and methanol, ethanol, normal propanol, isopropanol, etc. as aliphatic alcohols. And, as halogenated aliphatic hydrocarbon compounds, methyl fluoride, perfluoromethane, ethyl fluoride, and 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-tetrafluoroethane (1,1,2,2-tetrafluoromethane, HFC-134), 1,1,1,3,3-pentafluorobutane (1,1 ,1,3,3-pentafluorobutane, HFC-365mfc), 1,1,1,3,3-pentafluoropropane (1,1,1,3,3-pentafluoropropane, HFC.sub.13 245fa), pentafluoropropane Fluoroethane, difluoromethane, perfluoroethane, 2,2-difluoropropane, 1,1,1-trifluoropropane ( 1,1,1-trifluoropropane), perfluoropropane, dichloropropane, difluoropropane, perfluorobutane, perfluorocyclobutane, methyl chloride (methyl chloride), methylene chloride, ethyl chloride, 1,1,1-trichloroethane, 1,1-dichloro-1-ple Luoroethane (1,1-dichloro-1-fluoroethane, HCFC-141b), 1-chloro-1,1-difluoroethane (1-chloro-1,1-difluoroethane, HCFC-142b), chlorodifluoro Chlorodifluoromethane (HCFC-22), 1,1-dichloro-2,2,2-trifluoroethane (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), dichlorodifluoromethane 30-9 (dichlorodifluoromethane, CFC-12), trichlorotrifluoroethane (CFC-113), 1,1,1-trifluoroethane (1,1,1-trifluoroethane), pentafluoroethane ( pentafluoroethane), dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane, dichlorohexafluoropropane, and the like. The content of the above-described foaming agent is preferably 0.5 to 5 parts by weight based on 100 parts by weight of the vinyl chloride resin.If the content of the foaming agent is too small, the amount of gas generated for foaming is too small and the foaming effect is insignificant or can not be expected at all. If there is no, it is difficult to expect the required physical properties because the amount of gas generated is too large.

The filler of the present invention is used for the purpose of improving the productivity and dry touch of a vinyl chloride resin composition, and in the group consisting of calcium carbonate, talc, titanium dioxide, kaolin, silica, alumina, magnesium hydroxide, or clay. Includes any one or more selected.

In the vinyl chloride resin composition according to the present invention, the filler may preferably be 30 to 150 parts by weight, more preferably 50 to 130 parts by weight. When the filler is included in an amount of less than 50 parts by weight, there is a problem that dimensional stability and economical efficiency are lowered, and when it is included in an amount exceeding 130 parts by weight, the foaming surface is poor, and there is a problem that the workability is deteriorated.

The vinyl chloride resin composition of the present invention may improve whiteness and hiding properties by adding a lipid sugar (TiO ₂ ). The lipid sugar may preferably be 1 to 20 parts by weight, more preferably 3 to 15 parts by weight based on 100 parts by weight of the vinyl chloride resin. If less than 3 parts by weight of fatty sugar is contained, the color does not come out properly after printing due to poor whiteness and concealability, and if it contains more than 15 parts by weight, there is a problem that the foam surface is deteriorated.

The vinyl chloride resin composition according to the present invention may be prepared by a method generally known in the art using a vinyl chloride resin, the plasticizer, and optionally an additive, and the method is not particularly limited.

The vinyl chloride resin composition or a molded article containing the same may be used as wallpaper, mat, flooring, tarpaulin, artificial leather, toys, automobile interior materials, or automobile lower coating materials, and in particular, the transition characteristics of the plasticizer are improved and the elongation is high, so that the wallpaper , In particular, it is advantageous to apply to eco-friendly decorative wallpaper.

According to one embodiment of the present invention, the vinyl chloride resin composition may have an elongation of 440% to 480% as measured according to ASTM D 638.

In addition, according to one embodiment of the present invention, the vinyl chloride resin composition may have a tensile strength of 165 to 180 kg/cm ² as measured according to ASTM D 638.

Hereinafter, the present invention will be described in more detail based on examples. However, the following examples are merely illustrative of the present invention, and the contents of the present invention are not limited by the following examples. In addition, "%" and "parts" indicating content in the following examples and comparative examples are based on weight unless otherwise noted.

< Example >

Example 1 to 4

A plasticizer composition was prepared by mixing DEHCH, a citrate compound, and an epoxidized oil in a weight ratio as shown in Table 1 below.

100 parts by weight of polyvinyl chloride, 60 parts by weight of plasticizer composition, 3 parts by weight of stabilizer (BZ-150T, Songwon Industries), 10 parts by weight of fat sugar (R902, Dupont) and 10 parts by weight of filler (Omya 1T, Omia Korea) Henschel mixer By mixing for 10 minutes to prepare a vinyl chloride resin composition.

Comparative example 1 to 9

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

Cyclohexane dicarboxylate compound (material name, parts by weight) Citrate compound
(Material name, parts by weight) Epoxidized oil
(Material name, parts by weight) Other Example 1 DEHCH, 70 TBC, 20 ESO, 10 Example 2 DEHCH, 75 TBC, 20 ESO, 5 Example 3 DEHCH, 80 TBC, 10 ESO, 10 Example 4 DEHCH, 85 TBC, 10 ESO, 5 Comparative Example 1 DEHCH, 100 - - Comparative Example 2 DEHCH, 80 TBC, 20 - Comparative Example 3 DEHCH, 90 ESO, 10 Comparative Example 4
- - - DOTP, 100 Comparative Example 5 DEHCH, 90 TBC, 10 - Comparative Example 6 TBC 100 Comparative Example 7 ESO 100

* In Table 1, parts by weight of each component are based on 100 parts by weight of a plasticizer composition to which a cyclohexane dicarboxylate compound, a citrate compound, an epoxidized oil, and other components are added.

* DEHCH: di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate))

* TBC: tributylcitrate

* DINP: diisononyl phthalate

* DOTP: dioctyl terephthalate

* ESO: epoxidized soybean oil

< Experimental example >

Transferability, elongation, tensile strength, weather resistance, and plasticization efficiency of the vinyl chloride resin compositions of Examples and Comparative Examples were evaluated as follows.

(1) Transitionability of plasticizer

The plasticizer was carried out by referring to ISO 177:1988 (Plastics - Determination of migration of Plasticizer). A molded sheet specimen with a diameter of 50 mm was prepared, and oil paper (PP porous film) and a glass plate were sequentially stacked above and below the specimen so that the plasticizer transferred from the specimen was absorbed by the oil paper. After 5 kg load was applied on the specimen and left in an oven at 70°C for 5 days, the weight change rate (%) of the specimen was measured to analyze the degree of plasticizer transition.

The rate of change in the weight of the specimen was calculated as [(Change in weight of the specimen/weight of the specimen before testing) *100], and the rate of change in the weight of the oil paper was calculated as [(Change in the weight of the oil paper/weight of the oil paper before testing) *100]. Calculated. The decrease in weight of the specimen was the same as the increase in the weight of the oil paper, and in this experiment, plasticizer migration was evaluated only with the rate of change in the weight of the specimen.

(2) Elongation and tensile strength

Tensile strength and elongation were measured at a rate of 500 mm/min in a UTM (Universal Test Machine) after the molding sheet was prepared as a dumbbell-shaped specimen according to ASTM D 638.

(3) weather resistance

It was carried out by the ASTM G154 Cycle 2 method, and the weather resistance (yellowness change) due to ultraviolet rays and moisture was evaluated as follows under conditions in which ultraviolet irradiation (70°C, 8 hours) and moisture condensation (50°C, 4 hours) are repeatedly cycled. I did. The test period was about 300 hours, and the yellow index (YI, yellowness) of the specimen was measured according to ASTM E313 standard.

(4) Plasticization efficiency (reduction in volatilization)

It was calculated using the hardness value. DEHP (DOP) was used as the standard (1.00, PVC Formulation (Tittow)), and the smaller the plasticization efficiency number, the better the physical properties.

The results are shown in [Table 2].

Elongation (%) The tensile strength
(kg/cm ² ) Weather resistance
(YI) Volatilization loss
(%) Migration
(%) Example 1 470 165 23.1 0.8 0.3 Example 2 452 172 26.5 0.7 0.2 Example 3 462 169 24.5 0.5 0.3 Example 4 440 178 13.2 0.6 0.4 Comparative Example 1 430 165 10.5 0.6 0.2 Comparative Example 2 425 168 22.1 0.8 0.3 Comparative Example 3 450 172 12.4 0.5 0.7 Comparative Example 4 451 192 35.2 0.4 1.2 Comparative Example 5 430 168 14.2 1.0 0.1 Comparative Example 6 385 177 19.2 2.9 0.1 Comparative Example 7 488 191 35.2 0.1 1.9

Referring to Table 2, Comparative Example 1, which is a plasticizer composed of only DEHCH, and Comparative Examples 2 and 5 including DEHCH and TBC, but not including epoxidized oil, had low elongation and did not meet the examples of the present application. In the case of Comparative Example 3 containing DEHCH and epoxidized oil but not containing TBC, the elongation was good, but the plasticizer migration property was found to be greater than that of the Example.

In addition, Comparative Example 6 consisting of only TBC is not suitable for use alone because of its elongation and loss of volatilization. Showed limits on. In addition, epoxidized oil has a disadvantage that it hardens in winter unlike other plasticizers, and many end-users are avoiding mass use due to storage problems. Comparative Example 4, which is a DOTP plasticizer, also had poor transferability and weather resistance.

Claims (13)

Cyclohexane dicarboxylate-based compound represented by the following formula (1);
A compound represented by the following formula (2); And
Plasticizer composition comprising epoxidized oil:
[Formula 1]

In Formula 1,
R ₁₁ and R ₁₂ are the same as each other and are C _4-20 alkyl,
[Formula 2]

In Chemical Formula 2,
R ₁ is hydrogen or acetyl,
R ₂ to R ₄ are each independently C _2-8 alkyl.
The method of claim 1,
The cyclohexane dicarboxylate-based compound represented by Formula 1 is one of the compounds represented by the following Formulas 1-1 to 1-3, a plasticizer composition:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3,
R ₁₁ and R ₁₂ are as defined in Chemical Formula 1.
The method of claim 1,
The compound represented by Formula 1 is di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate),
Plasticizer composition.
The method of claim 1,
The compound represented by Formula 2 is selected from the group consisting of tributyl citrate, tri(butyloctyl) citrate, trioctyl citrate, and acetyltributyl citrate,
Plasticizer composition.
The method of claim 1,
The epoxidized oil is epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearate. ), epoxidized oleate (epoxidized oleate), epoxidized tall oil (epoxidized tall oil) and epoxidized linoleate (epoxidized linoleate) containing any one or more selected from the group consisting of,
Plasticizer composition.
The method of claim 1,
50 to 90 parts by weight of the cyclohexane dicarboxylate-based compound represented by Formula 1;
10 to 50 parts by weight of the compound represented by Formula 2;
Containing 5 to 10 parts by weight of the epoxidized oil,
Plasticizer composition.
The method of claim 1,
The weight ratio of the cyclohexane dicarboxylate-based compound represented by Formula 1 and the compound represented by Formula 2 is 9:1 to 1:1,
Plasticizer composition.
100 parts by weight of a vinyl chloride resin, and
A vinyl chloride resin composition comprising 10 to 120 parts by weight of the plasticizer composition of any one of claims 1 to 7.
The method of claim 8,
A stabilizer, a foaming agent, a filler, and a lipid (TiO ₂ ) further comprising any one or more selected from the group consisting of,
Vinyl chloride resin composition.
The method of claim 9,
A vinyl chloride resin composition having an elongation of 440% to 480% as measured according to ASTM D 638.
The method of claim 9,
A vinyl chloride resin composition having a tensile strength of 165 to 180 kg/cm ² as measured according to ASTM D 638.
A molded article comprising the vinyl chloride resin composition of claim 8.
The method of claim 12,
Molded articles, which are wallpaper, mats, flooring, tarpaulin, artificial leather, toys, automobile interiors, or automobile undercarriage.