KR101234479B1 - PVC secondary plasticizer, PVC sol composition containig the same and article thereof - Google Patents

Abstract

The present invention relates to a secondary plasticizer for PVC, a polyvinylchloride (PVC) composition containing the same, and a product thereof, more specifically, a distillation range of 285 to 340 ° C, an aromatic content of 1% by weight or less, and a kinematic viscosity of 4 Processed PVC sheet, film, and plate with excellent processability by using a dearomatic product of ~ 8 cSt and containing 55 to 80% by weight of paraffinic hydrocarbons as secondary plasticizers or diluents for PVC sol processing. The present invention relates to a secondary plasticizer for PVC, a PVC sol composition containing the same, and a product thereof, which have excellent physical properties such as) and a volatile organic compound (VOC) emission amount of 0.1 mg / m 2 · hr or less.

In the present invention, the amount of VOC emitted from the PVC flooring, wallpaper, and film produced by using the volatile organic compound while lowering the volatile organic compound release rate while using the dearomatic product to increase the viscosity decrease effect even if the filler content is increased is 0.1 mg / ㎡ · hr It has the effect of being below.

PVC, Flooring, Carpet Tile, VOC, Eco-Friendly

Description

Secondary plasticizer for PPC, PPC sol composition containing same and product thereof {PVC secondary plasticizer, PVC sol composition containig the same and article}

The present invention relates to a secondary plasticizer for polyvinylchloride (PVC), a PVC sol composition containing the same, and a product thereof. More specifically, a flooring material completed by gelling of the sol while lowering the viscosity of the PVC sol to improve processability, The present invention relates to a secondary plasticizer for PVC and a PVC sol composition using the same, and a product thereof, so that the VOC emission amount of wallpaper, film is very small.

In general, PVC products are widely used because they are cheaper than other materials, have excellent chemical resistance, weather resistance, flame retardancy, and good mechanical properties. Among them, the flooring material generally has a multi-layered configuration sequentially stacked from the bottom to the lower layer, the foam layer, the upper layer, the surface layer, and the like. In addition, the wallpaper has a composition of paper and PVC film by coating the PVC sol on the paper, the film is prepared by coating the sol on the release paper in a single layer or multi-layer and then gelled. In the previous process, volatile dearomatic products were used as secondary plasticizers or diluents to reduce the viscosity during sol processing, or TXIB ((2,2,4-triethyl-1), 2-ethyl-1-hexanol), DOS Secondary plasticizers such as (dioctyl sebacate) have been used.

PVC is a general-purpose product that uses a variety of additives such as primary and secondary plasticizers, UV and thermal stabilizers, fillers, and internal releasing agents to provide processability. Resin. Various uses of PVC include metal coatings, artificial leather, wallpaper, and gloves. In particular, the plasticizer added during the processing of the PVC resin is an essential additive that imparts various properties and functions, such as processability, flexibility, surface tackiness to the PVC resin.

The plasticizer has the function of lowering the viscosity in the working process to give workability and the control of physical properties as a finished product after processing. Representative plasticizers used in the processing of the PVC resins include phthalates, adipates, trimellitates, and the most widely used plasticizers are phthalates. Octylphthalate (DOP) and dinonylphthalate (DINP) are sometimes classified as primary plasticizers. Korean Patent Laid-Open Publication Nos. 2005-0026178 and 2003-0066039 describe the use of ester plasticizers, the acrylic polymers described in Korean Patent Laid-Open Publication No. 2003-0029528 and the styrene derivatives described in 2004-007616. It is also used as a plasticizer.

On the other hand, unlike primary plasticizers that remain in the product after processing to control their physical properties, they lower the viscosity during processing and do not remain after processing, so that they do not affect the properties such as tensile strength or elasticity in the product. It can be classified as a secondary plasticizer. Secondary plasticizers generally have lower plasticity than primary plasticizers, but have excellent properties of viscosity lowering ability and viscosity retention performance. In addition, the secondary plasticizer does not remain after the end of processing, thereby reducing the stickiness of the surface of the workpiece by reducing the amount of plasticizer in the workpiece.

Korean Unexamined Patent Publication No. 195-0003376 and US Patent Publication No. 2005-0182156 describe the use of TXIB as a secondary plasticizer. As such, although conventionally, secondary plasticizers such as volatile aromatic hydrocarbons and TXIB have been used to increase economic efficiency without considering environmental hazards, indoor VOC emissions are high.

Accordingly, in the present invention, as a result of the research to solve the problems of the prior art, a PVC sol composition using a low volatility hydrocarbon product having almost no aromatics as a secondary plasticizer for PVC, and developed a flooring material using the same, It has been found that wallpaper and film exhibit VOC (Volatile Organic Compounds) emissions of 0.1 mg / m 2 hr or less, and the present invention has been completed based on this.

Accordingly, it is an object of the present invention to provide a secondary plasticizer of a PVC sol composition which can produce a PVC product having a VOC emission amount of 0.1 mg / m 2 · hr or less for flooring, wallpaper and film.

Another object of the present invention is to provide a PVC sol composition for the flooring, wallpaper, film comprising the secondary plasticizer and can improve the workability by increasing the viscosity lowering effect in the manufacturing process.

Another object of the present invention to provide a PVC product made of the PVC sol composition.

PVC secondary plasticizer for achieving the object of the present invention has a distillation range of 285 ~ 340 ℃, aromatic content of 1% by weight or less, kinematic viscosity of 4 to 8 cSt, containing 55 to 80% by weight of paraffinic hydrocarbons It is characterized by a dearomatic product.

PVC sol composition for achieving another object of the present invention is a plasticizer 30 to 70 parts by weight relative to 100 parts by weight of one or two or more kinds of PVC resin; 3 to 20 parts by weight of the secondary plasticizer; And 0.1 to 150 parts by weight of an additive selected from the group consisting of a blowing agent, a filler, a stabilizer, a viscosity control agent, and a dispersant.

PVC products for achieving another object of the present invention is prepared using the PVC sol composition, characterized in that the VOC emission amount is 0.1 mg / ㎡ · hr or less.

Hereinafter, the present invention will be described in more detail.

As described above, in the present invention, a secondary plasticizer for PVC and a method of reducing the VOC emission amount of the flooring, wallpaper, and film completed by gelling of the sol while lowering the viscosity of the PVC sol to improve processability and using the same It relates to a PVC sol composition.

As the secondary plasticizer according to the present invention, a dearomatic product having a distillation range of 285 to 340 ° C, an aromatic content of 1% by weight or less, a kinematic viscosity of 4 to 8 cSt, and a paraffinic hydrocarbon of 55 to 80% by weight is conventionally used. It improves odor by replacing TXIB or low boiling point dearomatic product, which is mainly used, significantly lowers VOC emission amount of final product, lowers viscosity of sol, and makes processing easier and reduces stickiness according to plasticizer use.

Here, the distillation range of the secondary plasticizer is preferably 285 ~ 340 ℃, VOC emission amount is increased if the flow rate is less than 285 ℃, and if the kind point exceeds 340 ℃ may remain to cause bridging. The paraffinic hydrocarbon content in the dearomatic product is preferably 55 to 80% by weight, and less than 55% by weight increases the lead-sensing content and increases with time, and when it exceeds 80% by weight, bridging occurs due to incompatibility with the resin. do. In addition, if the distillation range and the carbon composition is satisfied, the kinematic viscosity has a value in the range of 4 to 8 cSt.

PVC sol composition according to the invention is a plasticizer 30 to 70 parts by weight based on 100 parts by weight of one or two or more kinds of PVC resin mixed; 3 to 20 parts by weight of the secondary plasticizer; And 0.1 to 150 parts by weight of an additive selected from the group consisting of a blowing agent, a filler, a stabilizer, a viscosity control agent, and a dispersant, more specifically 1 to 5 parts by weight of a blowing agent; 0 to 150 parts by weight of a filler; And / or 1 to 5 parts by weight of a stabilizer.

The PVC resin used according to the present invention is a commercially available product, and in the case of a multi-layer structure, it is preferable to use different kinds of resins alone or in combination.

In the present invention, the plasticizer facilitates the processing of the PVC resin and serves to provide flexibility to the final product, mainly phthalate-based 30 to 70 parts by weight based on 100 parts by weight of the resin. If the amount of the plasticizer is less than 30 parts by weight, the gelling flexibility is low, and if the amount exceeds 70 parts by weight, there is a problem that a stickiness occurs in the final product.

In addition, the secondary plasticizer is used 3 to 20 parts by weight based on 100 parts by weight of resin, less than 3 parts by weight has a low viscosity lowering effect, when the content exceeds 20 parts by weight has a problem of poor storage stability.

The additive of the PVC sol composition is selected from at least one selected from the group consisting of a blowing agent, filler, stabilizer, viscosity regulator, and dispersant, preferably 1 to 5 parts by weight of filler, preferably 0 to 150 parts by weight of stabilizer, preferably Preferably, 1 to 5 parts by weight may be added to the ultraviolet absorber, viscosity modifier, and / or dispersing agent to impart the functionality, but is not limited thereto.

The PVC product according to the present invention is prepared using the above PVC sol composition, and the VOC emission amount is preferably in the form of flooring material, wallpaper, film, plate and the like of 0.1 mg / m 2 · hr or less.

Here, the VOC emission amount refers to the total amount of volatile organic compounds (range of n-Hexane to n-Hexadecan) released from the test piece of 1㎡ size per hour, and high VOC emission is outside the standard of indoor air quality control method, and it is possible to cause sick house syndrome. I have a problem.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.

Example 1

50 parts by weight of DOP (LG Chemical), 150 parts by weight of OMYA, 15 parts by weight of SK-EPSOL RD (SK Corporation), barium zinc, based on 100 parts by weight of PVC resin (LG Chemical PB-1752) Three parts by weight of the stabilizer (Korean Daehyup) series was mixed and mixed in the mixer for 5 to 10 minutes. When the dispersion was uniform, the sol was coated on a release paper with a thickness of 50 microns and then gelled in an oven adjusted to 180 ° C.

[Example 2]

50 parts by weight of DOP (LG Chemical), 150 parts by weight of coal (OMYA), 15 parts by weight of SK-EPSOL RD (SK Corporation), based on 100 parts by weight of other kinds of PVC resin (LG Chemical LP-170), 3 parts by weight of a barium zinc-based stabilizer (Korean Daehyup) was mixed and mixed in a mixer for 5 to 10 minutes. The sol was coated on a release paper with a thickness of 50 microns and then gelled in an oven adjusted to 180 ° C.

[Example 3]

Prepared in the same manner as in Example 1, it was coated on paper and gelled to prepare a wallpaper.

Comparative Example 1

Prepared in the same manner as in Example 1, but used as a secondary plasticizer YK-D80.

Comparative Example 2

Prepared in the same manner as in Example 1, but used as a secondary plasticizer YK-D100.

The properties of the secondary plasticizers used in the Examples and Comparative Examples are shown in Table 1 below.

Secondary plasticizer Molecular Weight Viscosity (cSt) Distillation range (℃) Example 1 SK-EPSOL RD 243 5.2 285-340 Example 2 SK-EPSOL RD 243 5.2 285-340 Comparative Example 1 YK-D80 170 1.9 210 to 240 Comparative Example 2 YK-D100 186 2.5 235-265

Each component used in the Examples and Comparative Examples and the amount thereof used are shown in Table 2 below, the PVC sol consisting of the components were subjected to gelling in an oven adjusted to 180 ℃.

Example 1, 3 Example 2 Comparative Example 1 Comparative Example 2 Suzy 100 100 100 100 DOP 50 50 50 50 CaCO ₃ 150 150 150 150 Secondary plasticizer 15 ^① 15 ^① 15 ^② 15 ^③ stabilizator 3 3 3 3

However, ① is the secondary plasticizer, SK-EPSOL RD, ② is the secondary plasticizer, YK-D80, and ③ is the secondary plasticizer, YK-D100.

The flooring and the wallpaper of the present invention prepared by Examples 1 to 3 are measured by the flooring or wallpaper of Comparative Examples 1 and 2 and visual observation and conventional methods (tensile strength and elongation: ASTM D638) As shown. Example 3 is to prepare a wallpaper by coating the sol obtained in Example 1 on the paper and to confirm whether the secondary plasticizer is transferred to the paper, so the analysis results of the next gelling film is the same as in Example 1 and 3 The comparison in Table 3 is omitted.

Metrics Example 1 Example 2 Comparative Example 1 Comparative Example 2 Initial viscosity, cPs (20 rpm) 8138 14427 7255 7858 Pencil hardness 8B 8B 8B 8B Tensile strength, kg / ㎠ 60.9 77.1 59.6 58.4 Elongation,% 115 159 110 117 Bridding none - - - Blooming none - - - VOC emission amount, mg / m 2 · hr
(Small chamber method) 0.08 0.07 0.35 0.23

In Example 1 and Example 2 using SK-EPSOL RD as in the present invention from the results of Table 3, Comparative Example 1 using YK-D80 and YK-D100 with VOC emission of 0.1 mg / m 2 · hr or less and Compared with Comparative Example 2, the release rate of the volatile organic compound was significantly lower. As a result of comparing the physical properties of Example 1 and the physical properties of Comparative Example 1 and Comparative Example 2, Example 1 was slightly higher initial viscosity, but the difference is not large and the tensile strength and elongation were similar. Also, the result of visually confirming bleeding and blooming has not been observed and confirmed that it has stable performance.

As described above, in the present invention, the amount of VOC emitted from the PVC flooring, wallpaper, and film produced by using the non-aromatic product while lowering the volatile organic compound release rate while increasing the filler content to increase the viscosity drop effect is 0.1 mg. It has an effect to become below / m <2> * hr.

It will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention. Accordingly, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.

Claims (4)

In the secondary plasticizer used to prepare the PVC sol composition, A secondary plasticizer for PVC, having a distillation range of 285 to 340 ° C., an aromatic content of 1 wt% or less, a kinematic viscosity of 4 to 8 cSt, and a 55 to 80 wt% paraffinic hydrocarbon. 30 to 70 parts by weight of plasticizer, based on 100 parts by weight of PVC resin; 3 to 20 parts by weight of the secondary plasticizer for PVC according to claim 1; And 0.1 to 150 parts by weight of an additive selected from the group consisting of a blowing agent, a filler, a stabilizer, a viscosity control agent, and a dispersant. A PVC product prepared from the PVC sol composition according to claim 2, wherein the amount of VOC (Volatile Organic Compounds) released is 0.1 mg / m 2 · hr or less. 4. The PVC product of claim 3, wherein the product is in the form of a sheet, film or plate.