KR20200015197A - Vinyl chloride resin comprising di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate having excellent UV stability - Google Patents

Abstract

The present invention relates to a vinyl chloride resin composition in which a UV stabilizer is added to a plasticizer obtained by mixing a di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (DEHCH) plasticizer or a DEHCH plasticizer with a citrate plasticizer in a vinyl chloride resin in order to improve weather resistance. The present invention can be used in a vinyl chloride resin composition used for tarpaulin, deco sheet, flooring, wallpaper, etc. which are exposed to light for a long time.

Description

Vinyl chloride resin composition comprising di (2-ethylhexyl) cyclohexane-1,4-dicarboxylate having excellent UV stability stability}

The present invention relates to a technique for producing a vinyl chloride resin composition excellent in weather resistance, which can not be realized only by the existing plasticizer.

Vinyl chloride-based resins are a homopolymer of vinyl chloride and a hybrid polymer containing 50% or more of vinyl chloride, and are one of five general-purpose thermoplastic resins produced by suspension polymerization and emulsion polymerization. Polyvinyl chloride resins include plasticizers, stabilizers, fillers, blowing agents, pigments, viscosity depressants, fat sugars (TiO ₂ ) and subsidiary materials with special functions. It is mixed and processed into plastisol or granule form and is widely used in coating, extrusion, injection molding, and calender molding. It is used for.

In particular, flooring, wallpaper, tarpaulin, decor sheet, etc. require flexibility in the characteristics of the product, a plasticizer is added during production. Recently, an example of using a non-phthalate plasticizer instead of a phthalate plasticizer suspected of environmental hormone has been reported.

For example, Korean Laid-Open Patent Publication No. 2008-0105341 discloses that DOTP, which is a non-phtalate plasticizer, is used alone or in combination with DIN-IsoNonyl Phthalate (DINP).

In addition to DOTP, there is di (2-ethylhexyl) cyclohexane-1,4-dicarboxylate (hereinafter referred to as DEHCH) among non-phthalate plasticizers, which can realize excellent coating properties due to low temperature and low temperature viscosity and gelling speed. It is fast, and has excellent foaming properties, plasticization efficiency, early indexing (Yellow Index), haze, migration resistance, etc., and there are almost no environmental problems such as phthalate-based plasticizers. I am getting it.

Meanwhile, tarpaulins, decor sheets, flooring, and wallpaper among the vinyl chloride resin products are more exposed to light than other vinyl chloride resin products. Ultraviolet rays emitted from sunlight have a short wavelength and high energy, causing discoloration, warping and cracking of products, and degrading mechanical properties. In order to prevent this, UV stabilizers are added during the production of vinyl chloride resin.

UV stabilizers include benzophenones, amines, benzotriazoles, and the like, and are selectively used depending on the processing method. Among these, benzophenone-based UV stabilizers are widely used because of their excellent UV absorption ability and compatibility with the most vulnerable range of vinyl chloride resin (280-340 nm).

However, as the addition amount increases due to the natural color of the UV stabilizer (yellow), the color of the vinyl chloride composition tends to be yellow, and when an excessive amount of the UV stabilizer is added, dispersibility decreases and irregularities are generated. Can cause. For this reason, UV stabilizers need to be minimized.

The present inventors, while studying the synthesis of vinyl chloride resin using an ultraviolet stabilizer to improve the weather resistance of the vinyl chloride composition, as described in the specification of the present invention, DEHCH and citrate-based to minimize the amount of ultraviolet stabilizer When the compounds were used independently or together, it was confirmed that the above problems were solved to complete the present invention.

The present invention relates to a vinyl chloride resin composition comprising a plasticizer and an ultraviolet stabilizer, which can improve weather resistance of a vinyl chloride resin composition.

In order to solve the above problems,

The present invention is 100 parts by weight of vinyl chloride resin; 30 to 70 parts by weight of a plasticizer comprising di (2-ethylhexyl) cyclohexane-1,4-dicarboxylate; And it provides a vinyl chloride resin composition comprising 0.5 to 5.0 parts by weight of an ultraviolet stabilizer.

The vinyl chloride resin of the present invention is a hybrid polymer containing at least 50% by weight of vinyl chloride homopolymer and vinyl chloride, and is one of five general-purpose thermoplastic resins produced by suspension polymerization and emulsion polymerization.

Preferably, the vinyl chloride resin is polyvinyl chloride (PVC) or PVC paste resin (PSR).

The plasticizer of the present invention is an additive added to add flexibility to the vinyl chloride resin. The plasticizer includes dioctyl terephthalate (DOTP) and di (2-ethylhexyl) cyclohexane-1,4-dicarboxylate.

Preferably, the plasticizer is contained in an amount of 30 to 70 parts by weight based on 100 parts by weight of the vinyl chloride resin in the vinyl chloride resin composition. More preferably, when the vinyl chloride resin is PVC, the plasticizer includes 30 to 50 parts by weight.

Di (2-ethylhexyl) cyclohexane-1,4-dicarboxylate of the present invention can realize excellent coating properties with low viscosity at room temperature and low temperature, fast gelling speed, excellent foaming properties, especially phthalate type There is almost no environmental problem such as a plasticizer, and is a compound that is in the spotlight as a plasticizer of a vinyl chloride resin. The structure is as follows, also called the English abbreviation DEHCH.

Preferably, the plasticizer comprising di (2-ethylhexyl) cyclohexane-1,4-dicarboxylate further comprises a citrate compound.

The citrate compound of the present invention is an additive added to the vinyl chloride resin to act as a plasticizer, and when used together with a plasticizer including DEHCH, it is possible to solve migration while maintaining the properties of DEHCH as a plasticizer. The migration refers to a phenomenon in which the plasticizer is present in the vinyl chloride resin and gradually flows out of the vinyl chloride resin over time. The structure of a citrate compound is as follows.

Where

R ₁ is hydrogen or acetyl,

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

Preferably, the citrate compound is selected from the group consisting of tributyl citrate (TBC), triisobutyl citrate (TIBC), trioctyl citrate (TOC), and acetyltributyl citrate (ATBC). Which is more than one.

More preferably, the citrate compound further included is tributyl citrate (TBC). It is because the processability of DEHCH level is maintained even if it mixes small molecular weight of TBC.

Preferably, the mixing weight ratio of the di (2-ethylhexyl) cyclohexane-1,4-dicarboxylate and the citrate compound is 90:10 to 70:30. When the weight ratio is less than 70:30, the thermal stability deteriorates, the yellowing degree of the vinyl chloride resin composition is severe, and the volatilization loss characteristics are inferior. When the weight ratio is more than 90:10, the effect of the addition of the citrate compound is insignificant.

The ultraviolet stabilizer of this invention is an additive added in order to prevent damage by the light of a vinyl chloride resin composition, and to improve weather resistance. UV stabilizers include benzophenones, amines, benzotriazoles, and the like, and are selectively used depending on the processing method. Among these, benzophenone-based UV stabilizers are widely used because of their excellent UV absorption ability and compatibility with the most vulnerable range of vinyl chloride resin (280-340 nm). As an example of a benzophenone type ultraviolet stabilizer, 2-hydroxy-4-methoxy benzophenone, 2,2'- dihydroxy-4- methoxy benzophenone, 2-hydroxy-4- octyloxy benzophenone, 2 '-Dihydroxy-4,4'-di-methoxybenzophenone, 2,2'-dihydroxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,2'- Dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-diethoxybenzophenone, 2,2'-dihydroxy-4,4'-dipropoxy Benzophenone, 2,2'-dihydroxy-4,4'-dibutoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-ethoxybenzophenone, 2,2'-di To hydroxy-4-methoxy-4'-propoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-butoxybenzophenone, 2,2'-dihydroxy-4- Methoxy-4'-propoxybenzophenone, 2,2'-dihydroxy-4-ethoxy-4'-butoxybenzophenone, 2,3'-dihydroxy-4,4'-dimethoxybenzophenone , 2,3'-dihydroxy-4-methoxy-4'-butoxybenzophenone, 2-hydroxy-4,4 ', 5'-trimethoxybenzophenone, 2-hydroxy-4 , 4 ', 6'-tributoxybenzophenone, 2-hydroxy-4-butoxy-4', 5'-dimethoxybenzophenone, 2-hydroxy-4-ethoxy-2 ', 4'- Dibutylbenzophenone, 2-hydroxy-4-propoxy-4 ', 6'-dichlorobenzophenone, 2-hydroxy-4-propoxy-4', 6'-dibromobenzophenone, 2,4 -Dihydroxybenzophenone, 2-hydroxy-4-ethoxybenzophenone, 2-hydroxy-4-propoxybenzophenone, 2-hydroxy-4-butoxybenzophenone, 2-hydroxy-4- Methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxy-4'-ethylbenzophenone, 2-hydroxy-4-methoxy-4'-propylbenzophenone, 2-hydroxy-4 -Methoxy-4'-butylbenzophenone, 2-hydroxy-4-methoxy-4'-tert-butylbenzophenone, 2-hydroxy-4-methoxy-4'-chlorobenzophenone, 2-hydroxy Hydroxy-4-methoxy-2'-chlorobenzophenone, 2-hydroxy-4-methoxy-4'-bromobenzophenone, 2-hydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy Hydroxy-4,4'-dimethoxy-3-methylbenzophenone, 2-hydroxy-4,4'-dimethoxy-2'-ethylbenzophene Non, 2-hydroxy-4,4 ', 5'-trimethoxybenzophenone, 2-hydroxy-4-ethoxy-4'-methylbenzophenone, 2-hydroxy-4-ethoxy-4' -Ethylbenzophenone, 2-hydroxy-4-ethoxy-4'-propylbenzophenone, 2-hydroxy-4-ethoxy-4'-butylbenzophenone, 2-hydroxy-4-ethoxy-4 '-Methoxybenzophenone, 2-hydroxy-4,4'-diethoxybenzophenone, 2-hydroxy-4-ethoxy-4'-propoxybenzophenone, 2-hydroxy-4-ethoxy- 4'-butoxybenzophenone, 2-hydroxy-4-ethoxy-4'-chlorobenzophenone, 2-hydroxy-4-ethoxy-4'-bromobenzophenone and the like.

Preferably, the UV stabilizer is 2-hydroxy-4-octyloxybenzophenone, the structure of which is as follows.

Preferably, the UV stabilizer is contained in an amount of 0.5 to 5.0 parts by weight based on 100 parts by weight of the vinyl chloride resin in the vinyl chloride resin composition. When the content of the UV stabilizer is less than 0.5 parts by weight, there is a problem that the effect of improving the weather resistance of the vinyl chloride resin composition is insignificant. In addition, when the content of the UV stabilizer is greater than 5.0 parts by weight, the color (yellow) of the UV stabilizer itself is severely changed in color of the vinyl chloride resin composition, there is a problem that the dispersibility is lowered to cause irregularities.

More preferably, the UV stabilizer is contained in an amount of 0.5 to 3.0 parts by weight based on 100 parts by weight of the vinyl chloride resin in the vinyl chloride resin composition.

The vinyl chloride resin composition of the present invention is a resin composition prepared by emulsion polymerization or suspension polymerization, and includes a plasticizer, a stabilizer, a filler, a blowing agent, a pigment, and a pigment, TiO _2. Flooring, wallpaper, tarpaulin, decor sheet, man-made by mixing the viscosity depressant and the special functions of the subsidiary materials through coating molding and mold coating molding in the form of plastisol or granule. It is used in a wide range of fields such as leather, toys and undercarriage coatings.

The stabilizer includes a heat stabilizer. The heat stabilizer may be added for the purpose of preventing various physical property changes caused by cleavage and crosslinking of the main chain by forming a polyene structure that is a chromophore by HCl is separated from the vinyl chloride resin. Such thermal stabilizers include Ca-Zn-based compounds, K-Zn-based compounds, Ba-Zn-based compounds, organic Tin-based compounds, metallic soap-based compounds, phenolic compounds, phosphate ester compounds or phosphorous acid ester compounds. One or more selected may be used. More specific examples of thermal stabilizers that can be used in the present invention include Ca-Zn-based compounds; K-Zn compound; Ba-Zn compound; Organic Tin compounds such as mercaptide compounds, maleic acid compounds or carboxylic acid compounds; Metallic soap-based compounds such as Mg-stearate, Ca-stearate, Pb-stearate, Cd-stearate, or Ba-stearate; Phenolic compounds; Phosphoric acid ester compounds; Or phosphorous acid ester compounds, and the like, and are optionally included depending on the intended use. In the present invention, it is particularly preferable to use a Ba-Zn compound, preferably a Ba-Zn compound.

An auxiliary heat stabilizer may be further used to improve the heat resistance and weather resistance of the heat stabilizer.

Preferably, the auxiliary heat stabilizer may be an epoxy auxiliary heat stabilizer. Epoxy auxiliary heat stabilizer refers to epoxidized soybean oil (ESO), and is used to maximize the effects of Ca-Zn-based compounds, K-Zn-based compounds and Ba-Zn-based compounds.

The blowing agent includes at least one selected from chemical blowing agents, physical blowing agents or mixtures thereof.

The chemical blowing agent is not particularly limited as long as it decomposes above a specific temperature to generate a gas, and may be azodicarbonamide, azodiisobutyro-nitrile, benzenesulfonylhydrazide, or 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 mentioned. Examples thereof include sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium carbonate, ammonium carbonate and the like. In addition, the physical blowing agent may be inorganic foaming agents such as carbon dioxide, nitrogen, argon, water, air, helium or aliphatic hydrocarbons containing 1 to 9 carbon atoms, and aliphatic alcohols containing 1 to 3 carbon atoms. alcohols) and organic foaming agents such as halogenated aliphatic hydrocarbons containing 1 to 4 carbon atoms.

Specific examples of such compounds include aliphatic hydrocarbon compounds such as methane, ethane propane, normal butane, isobutane, normal pentane, isopentane and neopentane, and as aliphatic alcohols such as methanol, ethanol, normal propanol and isopropanol. As the halogenated aliphatic hydrocarbon compound, methyl fluoride, perfluoromethane, ethyl fluoride, 1,1-difluoroethane, HFC-152a ), 1,1,1-trifluoroethane (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), penta Fluoroethane, difluorome (difluoromethane), perfluoroethane, 2,2-difluoropropane, 1,1,1-trifluoropropane, 1,1,1-trifluoropropane, perfluoro Perfluoropropane, dichloropropane, difluoropropane, difluoropropane, perfluorobutane, perfluorocyclobutane, methyl chloride, methylene chloride , Ethyl chloride, 1,1,1-trichloroethane, 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 (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), triclo Trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-113), 1,1,1-trifluoroethane (1 1,1-trifluoroethane, pentafluoroethane, dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane, dichlorohexafluoropropane, and the like. have. The content of the blowing agent is preferably about 0.5 to about 5 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. When the content of the blowing agent is too small, the amount of gas for foaming is too small, so that the foaming effect is insignificant or not at all. It cannot be expected, and in too many cases, the amount of gas generated is too high to expect the required physical properties.

The filler is used for the purpose of improving the productivity of the vinyl chloride resin composition, dry touch (dry touch), and is selected from the group consisting of calcium carbonate, talc, titanium dioxide, kaolin, silica, alumina, magnesium hydroxide or clay. It may include one or more. Titanium dioxide may be included as a type of filler, or may be included as a type of additive other than the filler.

As the pigment, a white pigment may be used. The white pigment is added to color the mixture by mixing the vinyl chloride resin composition, it can be used as a method of coloring the surface of the object by making a paint, ink, etc. by mixing with a colorant in white or colored. Pigments include inorganic pigments, organic pigments, and Lake pigments. In the present invention, TiO ₂ inorganic pigments having excellent durability by light were used.

The vinyl chloride resin composition according to the present invention can improve weather resistance by including DEHCH or a mixture of DEHCH and citrate plasticizer, and an ultraviolet stabilizer, and also solves problems such as flexibility, yellowing, tarpaulin, decor sheet, It can be used as flooring, wallpaper and the like.

1 is a weather resistance evaluation results for each amount of UV stabilizer added.
2 is a result of measuring the volatilization characteristics and the yellow index for each mixing ratio of the plasticizer mixed with DEHCH and TBC.

Hereinafter, the operation and effects of the invention will be described in more detail with reference to specific examples of the invention. However, these embodiments are only presented as an example of the invention, whereby the scope of the invention is not limited.

Example: Preparation of Vinyl Chloride Resin Composition

Example 1

4.0 parts by weight of Ba-Zn-based heat stabilizer (100 parts by weight of BZ-150T, 1.5 parts by weight of BP-251S) and epoxy auxiliary heat stabilizer (E-700 of Songwon) 2 By weight, 8 parts by weight of a white pigment (Dupont's R-902) and 40 parts by weight of DEHCH were weighed and mixed with a mixer, and kneaded using a roll mill.

Example 2

0.5 parts by weight of an ultraviolet stabilizer (Solvay UV-531) was added to Example 1 and mixed with a mixer, followed by kneading using a roll mill.

Example 3

1 part by weight of a UV stabilizer (Solvay UV-531) was added to Example 1 and mixed with a mixer, followed by kneading using a roll mill.

Example 4

2 parts by weight of a UV stabilizer (Solvay UV-531) was added to Example 1 and mixed with a mixer, followed by kneading using a roll mill.

Example 5

3 parts by weight of a UV stabilizer (Solvay UV-531) was added to Example 1, mixed with a mixer, and kneaded using a roll mill.

Example 6

4 parts by weight of an ultraviolet stabilizer (Solvay UV-531) was added to Example 1 and mixed with a mixer, followed by kneading using a roll mill.

Example 7

5 parts by weight of a UV stabilizer (Solvay UV-531) was added to Example 1 and mixed with a mixer, followed by kneading using a roll mill.

Example 8

6 parts by weight of a UV stabilizer (Solvay UV-531) was added to Example 1 and mixed with a mixer, followed by kneading using a roll mill.

Example 9

7 parts by weight of an ultraviolet stabilizer (Solvay UV-531) was added to Example 1 and mixed with a mixer, followed by kneading using a roll mill.

Example 10

8 parts by weight of an ultraviolet stabilizer (Solvay UV-531) was added to Example 1 and mixed with a mixer, followed by kneading using a roll mill.

Example 11

It was prepared in the same manner as in Example 1 except that 32 parts by weight of DEHCH and 8 parts by weight of TBC were used instead of 40 parts by weight of DEHCH.

Example 12

It was prepared in the same manner as in Example 2 except that 32 parts by weight of DEHCH and 8 parts by weight of TBC were used instead of 40 parts by weight of DEHCH.

Example 13

It was prepared in the same manner as in Example 3 except that 32 parts by weight of DEHCH and 8 parts by weight of TBC were used instead of 40 parts by weight of DEHCH.

Example 14

It was prepared in the same manner as in Example 4 except that 32 parts by weight of DEHCH and 8 parts by weight of TBC were used instead of 40 parts by weight of DEHCH.

Example 15

It was prepared in the same manner as in Example 5 except that 32 parts by weight of DEHCH and 8 parts by weight of TBC were used instead of 40 parts by weight of DEHCH.

Example 16

It was prepared in the same manner as in Example 6, except that 32 parts by weight of DEHCH and 8 parts by weight of TBC were used instead of 40 parts by weight of DEHCH.

Example 17

It was prepared in the same manner as in Example 7, except that 32 parts by weight of DEHCH and 8 parts by weight of TBC were used instead of 40 parts by weight of DEHCH.

Example 18

It was prepared in the same manner as in Example 8 except that 32 parts by weight of DEHCH and 8 parts by weight of TBC were used instead of 40 parts by weight of DEHCH.

Example 19

It was prepared in the same manner as in Example 9 except that 32 parts by weight of DEHCH and 8 parts by weight of TBC were used instead of 40 parts by weight of DEHCH.

Example 20

It was prepared in the same manner as in Example 10 except that 32 parts by weight of DEHCH and 8 parts by weight of TBC were used instead of 40 parts by weight of DEHCH.

Example 21

A specimen was prepared in the same manner as in Example 1 except that DEHCH 24 parts by weight and TBC 16 parts by weight were used instead of 40 parts by weight of DEHCH.

Example 22

Specimens were prepared in the same manner as in Example 2, except that DEHCH 24 parts by weight and TBC 16 parts by weight were used instead of 40 parts by weight of DEHCH.

Example 23

A specimen was prepared in the same manner as in Example 3, except that DEHCH 24 parts by weight and TBC 16 parts by weight were used instead of 40 parts by weight of DEHCH.

Example 24

Specimens were prepared in the same manner as in Example 4 except that DEHCH 24 parts by weight and TBC 16 parts by weight were used instead of 40 parts by weight of DEHCH.

Example 25

A specimen was prepared in the same manner as in Example 5 except that DEHCH 24 parts by weight and TBC 16 parts by weight were used instead of 40 parts by weight of DEHCH.

Example 26

A specimen was prepared in the same manner as in Example 6 except that DEHCH 24 parts by weight and TBC 16 parts by weight were used instead of 40 parts by weight of DEHCH.

Example 27

A specimen was prepared in the same manner as in Example 7, except that DEHCH 24 parts by weight and TBC 16 parts by weight were used instead of 40 parts by weight of DEHCH.

Example 28

A specimen was prepared in the same manner as in Example 8 except that DEHCH 24 parts by weight and TBC 16 parts by weight were used instead of 40 parts by weight of DEHCH.

Example 29

A specimen was prepared in the same manner as in Example 9 except that DEHCH 24 parts by weight and TBC 16 parts by weight were used instead of 40 parts by weight of DEHCH.

Example 30

It was prepared in the same manner as in Example 10, except that 24 parts by weight of DEHCH and 16 parts by weight of TBC were used instead of 40 parts by weight of DEHCH.

Example 31

A specimen was prepared in the same manner as in Example 1 except that 36 parts by weight of DEHCH and 4 parts by weight of TBC were used instead of 40 parts by weight of DEHCH.

Example 32

A specimen was prepared in the same manner as in Example 1 except that 28 parts by weight of DEHCH and 12 parts by weight of TBC were used instead of 40 parts by weight of DEHCH.

Example 33

A specimen was prepared in the same manner as in Example 1 except that 20 parts by weight of DEHCH and 20 parts by weight of TBC were used instead of 40 parts by weight of DEHCH.

Example 34

A specimen was prepared in the same manner as in Example 1 except that 16 parts by weight of DEHCH and 24 parts by weight of TBC were used instead of 40 parts by weight of DEHCH.

Example 35

A specimen was prepared in the same manner as in Example 1 except that 12 parts by weight of DEHCH and 28 parts by weight of TBC were used instead of 40 parts by weight of DEHCH.

Example 36

A specimen was prepared in the same manner as in Example 1 except that 8 parts by weight of DEHCH and 32 parts by weight of TBC were used instead of 40 parts by weight of DEHCH.

Example 37

A specimen was prepared in the same manner as in Example 1 except that 4 parts by weight of DEHCH and 36 parts by weight of TBC were used instead of 40 parts by weight of DEHCH.

Example 38

Specimens were prepared in the same manner as in Example 1 except that 40 parts by weight of TBC was used instead of 40 parts by weight of DEHCH.

Example 39

4.0 parts by weight of Ba-Zn-based heat stabilizer (100 parts by weight of BZ-150T, 1.5 parts by weight of BP-251S) and epoxy auxiliary heat stabilizer (E-700 of Songwon) 2 Parts by weight, 50 parts by weight of DEHCH, 0.5 parts by weight of UV stabilizer (Solvay UV-531) were weighed and mixed with a mixer, and kneaded using a roll mill.

Example 40

It was prepared in the same manner as in Example 39 except that DEHCH 40 and TBC 10 parts by weight were used instead of 50 parts by weight of DEHCH.

Example 41

It was prepared in the same manner as in Example 39 except that 47 parts by weight of DEHCH was used instead of 50 parts by weight of DEHCH.

Example 42

It prepared in the same manner as in Example 39 except that DEHCH 37.6, TBC 9.4 parts by weight instead of 50 parts by weight of DEHCH.

Comparative Example 1

4.0 parts by weight of Ba-Zn-based heat stabilizer (100 parts by weight of BZ-150T, 1.5 parts by weight of BP-251S) and epoxy auxiliary heat stabilizer (E-700 of Songwon) 2 By weight, 8 parts by weight of a white pigment (Dupont's R-902) and 40 parts by weight of DOTP were weighed, mixed with a mixer, and kneaded using a roll mill.

Comparative Example 2

0.5 parts by weight of a UV stabilizer (Solvay UV-531) was added to Comparative Example 1 and mixed with a mixer, followed by kneading using a roll mill.

Comparative Example 3

1 part by weight of a UV stabilizer (Solvay UV-531) was added to Comparative Example 1 and mixed with a mixer, followed by kneading using a roll mill.

Comparative Example 4

2 parts by weight of a UV stabilizer (Solvay UV-531) was added to Comparative Example 1 and mixed with a mixer, followed by kneading using a roll mill.

Comparative Example 5

3 parts by weight of a UV stabilizer (Solvay UV-531) was added to Comparative Example 1 and mixed with a mixer, followed by kneading using a roll mill.

Comparative Example 6

4 parts by weight of a UV stabilizer (Solvay UV-531) was added to Comparative Example 1 and mixed with a mixer, followed by kneading using a roll mill.

Comparative Example 7

5 parts by weight of a UV stabilizer (Solvay UV-531) was added to Comparative Example 1 and mixed with a mixer, followed by kneading using a roll mill.

Comparative Example 8

6 parts by weight of a UV stabilizer (Solvay UV-531) was added to Comparative Example 1 and mixed with a mixer, followed by kneading using a roll mill.

Comparative Example 9

7 parts by weight of a UV stabilizer (Solvay UV-531) was added to Comparative Example 1 and mixed with a mixer, followed by kneading using a roll mill.

Comparative Example 10

8 parts by weight of a UV stabilizer (Solvay UV-531) was added to Comparative Example 1 and mixed with a mixer, followed by kneading using a roll mill.

Comparative Example 11

It was prepared in the same manner as in Comparative Example 1 except that 40 parts by weight of DINP instead of 40 parts by weight of DOTP.

Comparative Example 12

It was prepared in the same manner as in Comparative Example 2 except that 40 parts by weight of DINP instead of 40 parts by weight of DOTP.

Comparative Example 13

It was prepared in the same manner as in Comparative Example 3 except that 40 parts by weight of DINP instead of 40 parts by weight of DOTP.

Comparative Example 14

It was prepared in the same manner as in Comparative Example 4 except that 40 parts by weight of DINP instead of 40 parts by weight of DOTP.

Comparative Example 15

It was prepared in the same manner as in Comparative Example 5 except that 40 parts by weight of DINP instead of 40 parts by weight of DOTP.

Comparative Example 16

It was prepared in the same manner as in Comparative Example 6 except that 40 parts by weight of DINP instead of 40 parts by weight of DOTP.

Comparative Example 17

It was prepared in the same manner as in Comparative Example 7 except that 40 parts by weight of DINP instead of 40 parts by weight of DOTP.

Comparative Example 18

It was prepared in the same manner as in Comparative Example 8 except that 40 parts by weight of DINP instead of 40 parts by weight of DOTP.

Comparative Example 19

It was prepared in the same manner as in Comparative Example 9 except that 40 parts by weight of DINP instead of 40 parts by weight of DOTP.

Comparative Example 20

It was prepared in the same manner as in Comparative Example 10 except that 40 parts by weight of DINP instead of 40 parts by weight of DOTP.

Comparative Example 21

4.0 parts by weight of Ba-Zn-based heat stabilizer (100 parts by weight of BZ-150T, 1.5 parts by weight of BP-251S) and epoxy auxiliary heat stabilizer (E-700 of Songwon) 2 Part by weight, 0.5 part by weight of lubricant, 50 parts by weight of DOTP, 0.5 part by weight of UV stabilizer (Solvay UV-531) were weighed, mixed with a mixer, and kneaded using a roll mill.

Comparative Example 22

It was prepared in the same manner as in Comparative Example 21 except that 50 parts by weight of DEHP (DOP) was used instead of 50 parts by weight of DOTP.

Experimental Example 1. Evaluation of weather resistance by the amount of UV stabilizer added

1) Specimen Fabrication

Samples for evaluating weather resistance were prepared for Examples 1 to 30 and Comparative Examples 1 to 20. After weighing the raw materials according to the above Examples and Comparative Examples was mixed for 10 to 20 minutes by dispersing the additive while increasing the temperature to 120 ℃ at room temperature using a Mixer, and then at 160 to 180 ℃ using a roll mill Kneading for 3-8 minutes. 8 at 170-190 ° C by hot press compression After the press working for 12 minutes, the specimen was prepared by cutting to meet the weather resistance evaluation standard (ASTM G154 CYCLE 2) and the composition color evaluation standard (ASTM E313).

2) Weatherability Assessment

The ASTM G154 Cycle 2 method was used to evaluate the weather resistance due to UV and moisture by repeated cycles of ultraviolet irradiation (70 ° C., 8 hours) and water condensation (50 ° C., 4 hours). The weatherability was evaluated by measuring the yellow index (YI, yellowness) according to ASTM E313, which is a composition color evaluation standard. The smaller the yellow index value, the better the weatherability. The results are shown in FIG.

From the results of FIG. 1, it can be seen that the weather resistance of Examples 1 to 30 is superior to Comparative Examples 1 to 20. In addition, the yellow index decreases rapidly as the amount of UV stabilizer is increased, but when the amount of the UV stabilizer is larger than 5 phr, the decrease is insignificant, that is, there is almost no difference in the effect of the UV stabilizer.

In particular, in the case of Example 12, even when only 0.5 phr of the UV stabilizer appeared yellow index was about 5.0.

Therefore, when considering only the weather resistance improving effect, it was found that it is preferable to add 0.5 to 5 phr UV stabilizers.

Experimental Example 2. Evaluation of composition color and volatilization loss by mixing ratio of DEHCH and TBC

1) Specimen Fabrication

Specimens were prepared for Examples 1, 11, 21 and 31 to 38. After weighing the raw materials according to the above Examples and Comparative Examples was mixed for 10 to 20 minutes by dispersing the additives while increasing the temperature to 120 ℃ at room temperature using a Mixer, and then at 160 to 180 ℃ using a roll mill Kneading for 3-8 minutes. Then press processing for 8 to 12 minutes at 170 to 190 ℃ by hot press compression, and then cut to meet the composition color evaluation standard (ASTM E313) to prepare a specimen.

2) product color evaluation

Product color was evaluated by measuring the yellow index (YI, yellowness) according to ASTM E313 standard. The smaller the yellow index value, the higher the physical properties. The results are shown in FIG.

3) Volatility loss assessment

Volatilization loss was evaluated by measuring the amount of plasticizer volatilized for 1 hour at 200 ℃. The results are shown in FIG.

From the above results, it was found that the composition color and volatilization amount according to the DEHCH and TBC mixing ratios were most suitable when the mixing ratio was 90:10 to 70:30. If the mixing ratio is less than 70:30, there is a problem that the yellow index is increased and the volatilization decreases rapidly.

Experimental Example 3. Evaluation of Dispersibility and Composition Color According to UV Stabilizer Content

1) Dispersibility Assessment

For Examples 1 to 20 and Comparative Examples 1 to 10 prepared above, dispersibility was evaluated by observing the appearance of the extrudate produced by extruding the mixed PVC composition in the Mixer. Extrusion was performed using a single screw type extruder, the extrusion temperature was 100 to 140 ℃, the rpm of the screw was carried out to 30 to 40. It was evaluated that dispersibility was excellent as there was no protrusion on the extrusion appearance. The results are shown in the following [Table 1] (very good ◎> ○> Δ> X very poor).

2) Specimen Fabrication

Specimens were prepared for Examples 1 to 20 and Comparative Examples 1 to 10. After weighing the raw materials according to the above Examples and Comparative Examples was mixed for 10 to 20 minutes by dispersing the additives while increasing the temperature to 120 ℃ at room temperature using a Mixer, and then at 160 to 180 ℃ using a roll mill Kneading for 3-8 minutes. Then press processing for 8 to 12 minutes at 170 to 190 ℃ by hot press compression, and then cut to meet the composition color evaluation standard (ASTM E313) to prepare a specimen.

3) composition color evaluation

For the specimens of Examples 1 to 20 and Comparative Examples 1 to 10 prepared above, the composition color was evaluated by measuring the yellow index (YI, yellowness). The smaller the yellow index value, the better the physical properties. The results are shown in the following [Table 1] (very good ◎> ○> Δ> X very poor).

Color Change by UV Stabilizer Content
(The less change, the better) Dispersibility UV stabilizer
Content (phr) DOTP DEHCH DEHCH / TBC
(8: 2) DOTP DEHCH DEHCH / TBC
(8: 2) 0 ◎ ◎ ◎ ◎ ◎ ◎ 0.5 ◎ ◎ ◎ ◎ ◎ ◎ 1.0 ○ ○ ○ ○ ○ ○ 2.0 ○ ○ ○ ○ ○ ○ 3.0 ○ ○ ○ ○ ○ ○ 4.0 △ △ △ △ △ △ 5.0 △ △ △ △ △ △ 6.0 X X X X X X 7.0 X X X X X X 8.0 X X X X X X

From the above results, it was found that when the content of the UV stabilizer exceeds 5.0 phr, the color change of the composition is severe and the dispersibility is inferior, which may cause product defects. Considering only the color change and dispersibility, the content of the UV stabilizer is most preferably 0.5 phr or less.

However, when considering together with the weather resistance evaluation of Experimental Example 1, the addition of 0.5 to 3 phr UV stabilizers can be prepared a vinyl chloride resin composition with less change in physical properties (color and dispersibility) and improved weatherability.

Experimental Example 4. Evaluation of Plasticization Efficiency and Physical Properties by Plasticizer

1) Specimen Fabrication

In Examples 39 to 42 and Comparative Examples 21 and 22, specimens for physical property evaluation were prepared. After weighing the raw materials according to the above Examples and Comparative Examples was mixed by dispersing the additive for 15 minutes at 110 ℃ using a Mixer, and then kneaded for 3 minutes at 170 ℃ using a roll mill, Hot Press Press process for 10 minutes at 180 ℃ by compression. Since the press-processed plate was cut and manufactured according to each property evaluation standard.

2) hardness evaluation

After the specimen was prepared in a size of 5cm x 5cm x 4mm, the hardness was measured by Shore A hardness meter. The smaller the hardness value, the greater the flexibility of the product. The results are shown in [Table 2].

3) Evaluation of plasticization efficiency

Calculation was made using the hardness value. DEHP (DOP) was used as the reference (1.00), and the smaller the plasticization efficiency number, the better the physical properties. The results are shown in [Table 2].

4) Evaluation of tensile strength and elongation

It was carried out by the ASTM D638 method, the larger the number was evaluated as excellent physical properties. The results are shown in [Table 2].

5) Weatherability Assessment

It was carried out by ASTM G154 Cycle 2 method, and the ultraviolet radiation (70 ℃, 8 hours) and the water condensation (50 ℃, 4 hours) was repeated repeatedly to evaluate the weather resistance due to ultraviolet rays and moisture. Yellow index (YI, yellowness) is measured by ASTM E313 standard. The results are shown in [Table 2].

DEHCH
Example 39 DEHCH / TBC
(8: 2)
Example 40 DOTP
(Comparative Example 21) DEHP (DOP)
(Comparative Example 22) DEHCH
Example 41 DEHCH / TBC
(8: 2)
Example 42 Plasticizer content
(phr) 50 47 47 UV stabilizer content (phr) 0.5 Hardness
(Shore A) 79.2 79.7 82.1 78.5 82.0 82.2 Plasticization efficiency
(Based on hardness) 1.01 1.02 1.06 1.00 1.06 1.06 The tensile strength
(Kgf / cm ² ) 179 182 193 181 188 190 Elongation
(%) 338 329 346 291 320 321 Weather resistance
(Yellow Index) 5.93 5.0 17.0 8.2 5.63 4.7

From the above results, the vinyl chloride resin compositions (Examples 39 and 40) to which DEHCH and DEHCH / TBC (8: 2) Blend plasticizers were added (Examples 39 and 40) were harder than the vinyl chloride resin compositions (Comparative Example 21) to which the same amount of DOTP plasticizer was added. Low flexibility was found to be excellent. Thus, when using DEHCH and DEHCH / TBC (8: 2) Blend plasticizer (Examples 41 and 42), the content of the plasticizer can be reduced by 4 to 5% to improve the weather resistance.

Claims (10)

100 parts by weight of vinyl chloride resin;
A plasticizer comprising di (2-ethylhexyl) cyclohexane-1,4-dicarboxylate 30 to 70 parts by weight; And
UV stabilizer containing 0.5 to 5.0 parts by weight,
Vinyl chloride resin composition.
The method of claim 1,
The plasticizer further comprises a citrate compound,
Vinyl chloride resin composition.
The method of claim 2,
The citrate compound is at least one selected from the group consisting of tributyl citrate, triisobutyl citrate, trioctyl citrate, and acetyl tributyl citrate,
Vinyl chloride resin composition.
The method of claim 1,
The vinyl chloride resin is polyvinyl chloride,
Vinyl chloride resin composition.
The method of claim 1,
The plasticizer is included in 30 to 50 parts by weight,
Vinyl chloride resin composition.
The method of claim 1,
The vinyl chloride resin is a polyvinyl chloride paste resin,
Vinyl chloride resin composition.
The method of claim 2,
The weight ratio of the di (2-ethylhexyl) cyclohexane-1,4-dicarboxylate and the citrate compound is 90:10 to 70:30,
Vinyl chloride resin composition.
The method of claim 1,
The ultraviolet stabilizer is 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2'-dihydroxy -4,4'-di-methoxybenzophenone, 2,2'-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4 , 4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-diethoxybenzophenone, 2,2'-dihydroxy-4,4'-dipropoxybenzophenone, 2, 2'-dihydroxy-4,4'-dibutoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-ethoxybenzophenone, 2,2'-dihydroxy-4- Methoxy-4'-propoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-butoxybenzophenone, 2,2'-dihydroxy-4-ethoxy-4'- Propoxybenzophenone, 2,2'-dihydroxy-4-ethoxy-4'-butoxybenzophenone, 2,3'-dihydroxy-4,4'-dimethoxybenzophenone, 2,3 '-Dihydroxy-4-methoxy-4'-butoxybenzophenone, 2-hydroxy-4,4 ', 5'-trimethoxybenzophenone, 2-hydroxy-4,4', 6'- Tributok Benzophenone, 2-hydroxy-4-butoxy-4 ', 5'-dimethoxybenzophenone, 2-hydroxy-4-ethoxy-2', 4'-dibutylbenzophenone, 2-hydroxy- 4-propoxy-4 ', 6'-dichlorobenzophenone, 2-hydroxy-4-propoxy-4', 6'-dibromobenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy Hydroxy-4-ethoxybenzophenone, 2-hydroxy-4-propoxybenzophenone, 2-hydroxy-4-butoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxy-4'-ethylbenzophenone, 2-hydroxy-4-methoxy-4'-propylbenzophenone, 2-hydroxy-4-methoxy-4'-butylbenzophenone , 2-hydroxy-4-methoxy-4'-tert-butylbenzophenone, 2-hydroxy-4-methoxy-4'-chlorobenzophenone, 2-hydroxy-4-methoxy-2'- Chlorobenzophenone, 2-hydroxy-4-methoxy-4'-bromobenzophenone, 2-hydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4,4'-dimethoxy- 3-methylbenzophenone, 2-hydroxy-4,4'-dimethoxy-2'-ethylbenzophenone, 2-hydroxy- 4,4 ', 5'-trimethoxybenzophenone, 2-hydroxy-4-ethoxy-4'-methylbenzophenone, 2-hydroxy-4-ethoxy-4'-ethylbenzophenone, 2- Hydroxy-4-ethoxy-4'-propylbenzophenone, 2-hydroxy-4-ethoxy-4'-butylbenzophenone, 2-hydroxy-4-ethoxy-4'-methoxybenzophenone, 2-hydroxy-4,4'-diethoxybenzophenone, 2-hydroxy-4-ethoxy-4'-propoxybenzophenone, 2-hydroxy-4-ethoxy-4'-butoxybenzophenone , At least one selected from the group consisting of 2-hydroxy-4-ethoxy-4'-chlorobenzophenone, and 2-hydroxy-4-ethoxy-4'-bromobenzophenone,
Vinyl chloride resin composition.
An article comprising the vinyl chloride resin composition of claim 1.
The method of claim 9,
The article is a flooring, wallpaper, tarpaulin, decor sheet, artificial leather, toys, or automotive undercoat;
article.

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