WO2021132870A1 - Vinyl chloride resin composition - Google Patents

Abstract

The present invention relates to a vinyl chloride resin composition suitable for producing environment-friendly and highly elastic gloves, the composition having superb processability and allowing mechanical properties of the produced product to be enhanced.

Description

Vinyl chloride resin composition

Cross-Citation with Related Application(s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0175549 on December 26, 2019, and all contents disclosed in the literature of the Korean patent application are incorporated as a part of this specification.

The present invention relates to a vinyl chloride resin composition capable of producing a product with improved mechanical properties with excellent processability.

Vinyl chloride-based resin is a homopolymer of vinyl chloride and a hybrid polymer containing 50% or more of vinyl chloride, and is one of five general-purpose thermoplastic resins manufactured by suspension polymerization and emulsion polymerization. Among them, the polyvinyl chloride resin produced by emulsion polymerization is a homopolymer of vinyl chloride or a hybrid polymer containing 50% or more of vinyl chloride, and through coating molding and mold coating molding processing methods, flooring, wallpaper, tarpaulin, artificial leather, toys, It is used in a wide range of fields such as automobile undercoating materials, baby toys, and miscellaneous goods such as gloves.

In order to be used as a material for various products, polyvinyl chloride resin is a plasticizer, a stabilizer, a filler, a blowing agent, a pigment, a viscosity depressant, and a fat sugar. (TiO ₂ ) and additives having a special function are supplied as a vinyl chloride resin composition in the form of a mixed plastisol (Plastisol). In particular, plasticizers are widely used to impart processability to vinyl chloride-based resins and to improve physical properties such as adhesion and electrical insulation.

However, in the case of phthalate-based plasticizers such as diethylhexyl phthalate (DOP) and diisononyl phthalate (DINP), which have been widely used so far, endocrine disruptors that interfere with or disrupt human hormone action It is suspected of being an endocrine disrupter, so there is a movement to regulate its use. Moreover, it is essential to use an eco-friendly plasticizer that is environmentally friendly and harmless to health without the generation of such environmental hormones in the vinyl chloride resin composition applied to the medical field, toys, toys for children, and food.

These eco-friendly plasticizers include phthalate-based plasticizers or dioctyl terephthalate (DOTP) with a low content of volatile organic compounds (VOCs), and vegetable oil-based eco-friendly plasticizers that are non-phthalate-based plasticizers epoxidized soybean. Epoxidized soybean oil (ESO), 1,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH), and the like are used.

In particular, Chinese Patent No. 105400106 discloses a vinyl chloride resin composition using DOTP as a plasticizer in order to provide a highly elastic glove with improved tensile strength. However, when using the DOTP plasticizer, it is necessary to use a large amount of additives for lowering the viscosity to lower the viscosity of the composition. These additives for lowering viscosity not only generate volatile organic compounds when used in excess, but also reduce the quality of the final product. can

Accordingly, there is still a need for the development of a vinyl chloride resin composition that is environmentally friendly because it does not generate environmental hormones and has a low viscosity even when using a small amount of a viscosity reducing agent and has excellent processability.

[Prior art literature]

[Patent Literature]

(Patent Document 0001) Chinese Patent Registration No. 105400106

An object of the present invention is to provide a vinyl chloride resin composition suitable for manufacturing eco-friendly high-elastic gloves by improving the mechanical properties of manufactured products while having excellent processability.

In addition, the present invention is to provide an industrial or medical glove manufactured by molding the vinyl chloride resin composition.

In order to solve the above problems, the present invention provides a vinyl chloride resin composition comprising:

(a) 100 parts by weight of a vinyl chloride resin having a degree of polymerization of 1,300 or more;

(b) 50 to 90 parts by weight of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate;

(c) 5 to 30 parts by weight of tributylcitrate;

(d) 0.5 to 3 parts by weight of a stabilizer; and

(e) greater than 1 part by weight and less than 20 parts by weight of a viscosity reducing agent.

For the manufacture of eco-friendly, high-elastic gloves used for industrial or medical purposes, research on additives that can be added to plastisol containing vinyl chloride resin is continuously being conducted. However, when using a generally known eco-friendly plasticizer, the processing speed There has been a problem that productivity is low because of the slow speed. In addition, due to the deterioration of physical properties of the final product due to the use of a large amount of the viscosity reducing agent for lowering the viscosity of the plastisol, there was a demand for a plastisol having excellent processability while using a minimum viscosity reducing agent.

Accordingly, the present inventors have prepared a vinyl chloride resin composition obtained by adding a combination of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate and tributylcitrate in a specific content to a high polymerization degree vinyl chloride resin as a plasticizer. In this case, it was confirmed that the plastisol having excellent processability can be prepared even if only a small amount of the viscosity reducing agent is used, and the present invention has been completed.

In addition, the gloves manufactured by molding the vinyl chloride resin composition did not employ a plasticizer of a combination of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate and tributylcitrate in the specific content. Compared to gloves manufactured by molding the composition, it has excellent mechanical properties, particularly tensile strength, and is environmentally friendly because environmental hormones are not generated by plasticizers, so it is suitable for industrial as well as medical use.

Meanwhile, the term "vinyl chloride polymer (vinyl chloride polymer)" used herein may be understood as a material such as vinyl chloride resin or polyvinyl chloride paste resin (PSR).

In addition, as used herein, the term "plastisol" refers to a mixture of a resin and a plasticizer so that it can be molded, molded or molded into a continuous film by heating, for example, a vinyl chloride polymer and a plasticizer. It can be seen that it represents a mixed paste form.

In addition, the term "plasticizer" as used herein may refer to an organic additive material that serves to improve the moldability of the resin at a high temperature by adding it to the thermoplastic resin to increase the thermoplasticity.

Also, in this specification, terms such as first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.

In addition, the terminology used herein is only used to describe exemplary embodiments, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present specification, terms such as "comprise", "comprising" or "have" are intended to designate the presence of an embodied feature, number, step, element, or a combination thereof, but one or more other features or It should be understood that it does not preclude the possibility of the presence or addition of numbers, steps, elements, or combinations thereof.

Further, in the present invention, when it is said that each layer or element is formed "on" or "over" each layer or element, it means that each layer or element is formed directly on each layer or element, or It means that other layers or elements may additionally be formed between each layer, on the object, on the substrate.

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

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

(a) a vinyl chloride resin with a degree of polymerization of 1,300 or more

The vinyl chloride resin composition according to an embodiment includes a vinyl chloride resin having a polymerization degree of 1,300 or more. 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. can be used for

Examples of the comonomer copolymerizable with the vinyl chloride monomer include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl stearate; vinyl ethers having an alkyl group such as methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether, and launyl vinyl ether; Halogenated vinylidene, such as a 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; or a crosslinkable monomer such as diallyl phthalate, and the like, and any one or a mixture of two or more thereof may be used. Among them, it may be more preferable to use vinyl acetate or the like as the comonomer in view of excellent compatibility with the vinyl chloride monomer and improving compatibility with the plasticizer constituting the resin composition after polymerization. .

Such a vinyl chloride resin may be prepared in the form of particles by polymerization reaction of a vinyl chloride monomer alone or a vinyl chloride monomer and a comonomer copolymerizable therewith, wherein the polymerization method is not particularly limited, and fine suspension polymerization, emulsion polymerization or seed emulsion polymerization It may be carried out according to a conventional polymerization method known in the art to which the present invention pertains. Among them, when prepared by emulsion polymerization or fine suspension polymerization, the average particle size of the vinyl chloride resin produced is small and uniform compared to the case prepared 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 As may be 1 to 10 μm, by having a particle size in the above range, excellent dispersibility can be exhibited, and fluidity of the plasticized vinyl chloride resin composition can be further improved. When the average particle size (D ₅₀ ) of the vinyl chloride resin exceeds 40 μm, the dispersibility of the vinyl chloride resin particles itself is low, and when it is less than 1 μm, there is a risk of lowering the dispersibility due to aggregation between the vinyl chloride resin particles. have. At this time, the average particle size (D ₅₀ ) of the vinyl chloride resin means the particle size at 50% of the cumulative distribution of the number of particles according to the particle size, and ordinary particles such as optical microscopy, light scattering, and laser diffraction It can be measured according to a size distribution measuring method. More specifically, it can be measured using a particle size analyzer, specifically, a laser diffraction particle size analyzer (Malvern Mastersizer, manufactured by Malvern Instruments).

On the other hand, the vinyl chloride resin has a polymerization degree of 1,300 or more. Here, the degree of polymerization indicates the number of repeated units (units or monomers) constituting the polymer, and can be measured in accordance with the 　 standard JIS K6720-2. When the degree of polymerization of the vinyl chloride resin is less than 1,300, it may be difficult to manufacture a high-elastic glove due to insufficient elasticity.

More specifically, the vinyl chloride resin may have a polymerization degree of 1,300 or more and 2,000 or less. When the polymerization degree of the vinyl chloride resin exceeds 2,000, compatibility and dispersibility with a plasticizer may be reduced. For example, the vinyl chloride resin may have a polymerization degree of 1,400 to 2,000, 1,450 to 1,800, or 1,500 to 1,700.

(b) di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate and (c) tributylcitrate

The vinyl chloride resin composition according to an embodiment, based on 100 parts by weight of the vinyl chloride resin, contains 50 to 90 parts by weight of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate and 5 to 90 parts by weight as a plasticizer component. 30 parts by weight of a combination of tributylcitrate.

The "di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, hereinafter abbreviated as 'DEHCH')") is represented by the following Chemical Formula 1 As a compound represented, the IUPAC name is Bis(2-ethylhexyl)cyclohexane-1,4-dicarboxylate:

[Formula 1]

.

In addition, the "tributyl citrate (hereinafter abbreviated as 'TBC')" is a compound represented by the following formula 2, and the IUPAC name is 2-Hydroxypropane-1,2,3-tricarboxylate:

[Formula 2]

.

The DEHCH minimizes the generation of volatile organic compounds compared to conventionally used phthalate-based plasticizers, and at the same time has a very low viscosity and a faster gelling rate than dioctyl terephthalate (DOTP), which is known as an eco-friendly plasticizer, so that vinyl chloride Processability and productivity of the resin composition can be improved.

However, in DEHCH, some of the plasticizer mixed with the polymer resin may migrate to the outside of the polymer resin. Since the surface of the product may become slippery or the physical properties of the product may be deteriorated due to the migration of the plasticizer, the migration of the plasticizer should be suppressed as much as possible.

In order to suppress the migration of DEHCH as much as possible, TBC can be used together. Specifically, the migration of DEHCH may be suppressed due to an interaction such as a hydrogen bond between an ester group and an ester group of DEHCH present in the TBC represented by Formula 2 above. In addition, the gelling rate of the vinyl chloride resin composition is increased by the combination of DEHCH and TBC, so that productivity can be improved when manufacturing products using the composition.

In particular, when TBC represented by Formula 2 among citrate-based compounds is used together with DEHCH, the migration of DEHCH can be further suppressed while the gelling rate of the composition is improved compared to when other citrate-based compounds are used together. have. Accordingly, the physical properties of the product manufactured using the composition, in particular, the tensile strength of the product can be improved.

On the other hand, the vinyl chloride resin composition according to an embodiment contains the DEHCH in an amount of 50 to 90 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content of DEHCH in the composition is less than 50 parts by weight, the viscosity of the vinyl chloride resin composition increases and processability may decrease or the flexibility of the manufactured product may decrease, and if the content of DEHCH exceeds 90 parts by weight, DEHCH is a molded article It is easy to cause a bleeding effect that leaks to the surface of the product, which causes surface stickiness, which may cause problems in processing and finished products. Specifically, the DEHCH may be included in 50 to 80 parts by weight, 55 to 70 parts by weight, or 55 to 65 parts by weight based on 100 parts by weight of the vinyl chloride resin in the vinyl chloride resin composition.

In addition, the vinyl chloride resin composition according to an embodiment contains 5 to 30 parts by weight of the TBC based on 100 parts by weight of the vinyl chloride resin. If the content of TBC in the composition is less than 5 parts by weight, the effect of inhibiting the migration of DEHCH may be insignificant, and the gelling rate of the composition is not fast enough, so there is a risk of lowering productivity during product manufacturing. In addition, when the content of TBC exceeds 30 parts by weight, the content of TBC compared to DEHCH is increased, so that the effect of lowering the viscosity by DEHCH is not large, and the viscosity of the composition is not sufficiently lowered, so that the processability of the composition may be reduced. Specifically, the TBC may be included in 7 to 25 parts by weight, 10 to 25 parts by weight, or 15 to 25 parts by weight based on 100 parts by weight of the vinyl chloride resin in the vinyl chloride resin composition.

Considering the effect of reducing the viscosity and the fast gelling rate according to the control of the plasticizer content in the vinyl chloride resin composition, the sum of DEHCH and TBC is preferably included in an amount of 70 to 90 parts by weight relative to 100 parts by weight of the vinyl chloride resin.

In addition, the weight ratio of DEHCH and TBC in the vinyl chloride resin composition may be 90:10 to 65:35. When the weight ratio of DEHCH and TBC is less than 90:10, the amount of TBC in the composition is too small, so the gelling rate of the composition may not be sufficiently fast, and when the weight ratio of DEHCH and TBC exceeds 65:35, the content of TBC This excessive amount may increase the viscosity of the composition, making it unsuitable for processing. Specifically, the weight ratio of DEHCH and TBC in the vinyl chloride resin composition may be 80:10 to 70:30.

(d) stabilizers

The vinyl chloride resin composition according to an embodiment contains 0.5 to 3 parts by weight of a stabilizer based on 100 parts by weight of the vinyl chloride resin.

The stabilizer is added for the purpose of preventing that HCl separated from the vinyl chloride resin forms a polyene structure, which is a chromophore, and causes changes in physical properties such as cleavage and crosslinking of the main chain, Ca-Zn-based compound, K-Zn compound, Ba-Zn-based compound, organic tin-based compound; At least one selected from the group consisting of a metallic soap-based compound, a phenol-based compound, a phosphoric acid ester-based compound, and a phosphorous acid ester-based compound may be used.

More specific examples of the stabilizer include a Ca-Zn-based compound; K-Zn-based compounds; Ba-Zn-based compounds; an organic tin-based compound 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-based compound, and the like, and is optionally included depending on the purpose of use. In consideration of compatibility with the double resin and environment-friendly aspects, a Ca-Zn-based compound or a K-Zn-based compound may be used.

In addition, the vinyl chloride resin composition according to an embodiment contains the stabilizer in an amount of 0.5 to 3 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content of the stabilizer in the composition is less than 0.5 parts by weight, there is a problem that thermal stability is lowered, and if the content of the stabilizer exceeds 3 parts by weight, more than necessary thermal stability may be expressed, which is not suitable. Accordingly, in consideration of appropriate thermal stability, the stabilizer is more specifically 1 part by weight or more, or 1.5 parts by weight or more, and 2.7 parts by weight or less, 2.5 parts by weight or less, or 2.3 parts by weight or less based on 100 parts by weight of the vinyl chloride resin. may be included as

(e) viscosity reducing agents

The vinyl chloride resin composition according to an embodiment contains more than 1 part by weight and less than 20 parts by weight of the viscosity reducing agent based on 100 parts by weight of the vinyl chloride resin. The viscosity reducing agent serves to lower the viscosity of the liquid plastisol type vinyl chloride resin composition to facilitate the manufacture of the product.

The viscosity reducing agent may include an aliphatic hydrocarbon-based compound, a carboxylic acid ester-based compound, or a combination thereof. Among them, the carboxylic acid ester compound is preferable because it has excellent compatibility with the above-described plasticizer and vinyl chloride resin, and can reduce the amount of volatile organic compounds generated when used in a vinyl chloride resin composition due to low volatility.

Specifically, the carboxylic acid ester-based compound may be a compound represented by the following formula (3) prepared by ester-reacting a carboxylic acid having 8 to 22 carbon atoms with an alcohol having an alkyl group having 8 to 22 carbon atoms.

[Formula 3]

In Formula 3,

R _a and R _b are each independently a linear or branched alkyl group having 8 to 22 carbon atoms.

More specifically, in Formula 3, R _a and R _b may each independently be n-octyl, t-butyl, n-nonyl, or n-decyl.

In addition, commercially available products as the carboxylic acid ester compound, BYK LP-R 22274®, Viscobyk® 5025, 5125 and 5050, Jayflex® 615 or Exxsol® D100, etc. may be used, among them, BYK LP-R 22274®, which has excellent compatibility with a plasticizer, has low migration and has a fast gelling rate, can be used more preferably.

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

In addition, the vinyl chloride resin composition according to an embodiment contains the viscosity reducing agent in an amount of more than 1 part by weight and less than 20 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content of the viscosity reducing agent in the composition is 1 part by weight or less, the viscosity of the composition is high, so that the coating thickness of the plastisol becomes thick in the dipping process, there is a risk of leveling defects on the product surface, 20 weight If it exceeds the part, the coating thickness may become very thin or the gelling rate may be slowed due to excessive decrease in viscosity. Therefore, in consideration of the remarkable effect of preventing occurrence of defects and molding deterioration due to the control of the content of the viscosity reducing agent for the vinyl chloride resin, the viscosity reducing agent is more specifically 2 parts by weight or more, 3 parts by weight or more based on 100 parts by weight of the vinyl chloride resin. , or 4 parts by weight or more, and 15 parts by weight or less, 10 parts by weight or less, 8 parts by weight or less, or 6 parts by weight or less.

dispersant

In addition, the vinyl chloride resin composition according to an embodiment of the present invention may further include a dispersing agent in order to improve the dispersibility between the vinyl chloride resin particles in the composition. The dispersant is adsorbed to the surface to reduce the attractive force between particles and prevent re-agglomeration, thereby facilitating movement of the particles and stabilizing the viscosity and behavior of the resin composition.

As the dispersant, at least one acidic ester-based compound having excellent dispersibility may be used. The acidic ester-based compound may exhibit excellent dispersibility in the vinyl chloride resin as well as exhibit an additional viscosity lowering effect due to the property of lowering the viscosity of the formulation.

Specifically, the acid ester-based compound includes a phosphoric acid ester-based compound such as a phosphoric acid ester; or Stearyl Cetyl Stearates (CETS), Ethylene Glycol Distearate (EGDS), GlycerylMonoOleate (GMO), PentaErythritol Distearate (PEDS) ), pentaerythritol tetrastearate (PentaErythritol Tetrastearate; PETS), glyceryl monostearate (GMS), or fatty acid esters such as Stearyl Stearate and Distearyl Pthalate (fatty acid estr) and the like, and any one or two or more compounds of these may be used. Among them, a phosphoric acid ester-based compound may be preferable. Also, commercially available BYK-LP W 21809 or the like may be used.

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

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

When the dispersant is added to the vinyl chloride resin composition, the dispersant may be included in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content of the dispersant is less than 0.5 parts by weight, there is a risk of poor dispersibility of the formulation, and if it exceeds 5 parts by weight, there is a risk that the physical properties of the final product may be reduced.

On the other hand, the vinyl chloride resin composition according to an embodiment of the present invention can be prepared by a method generally known in the art using the above-described vinyl chloride resin, DEHCH, TBC, a stabilizer, a viscosity reducing agent and optionally an additive, , the method is not particularly limited.

The vinyl chloride resin composition having the above composition uses a combination of DEHCH and TBC in a specific amount as a plasticizer in a vinyl chloride resin having a high degree of polymerization, so that even with a small amount of a viscosity reducing agent, a low viscosity and a fast gelling rate can be exhibited. .

Specifically, the vinyl chloride resin composition has a viscosity of 400 cPs to 1,000 cPs as measured by a Brookfield viscometer (spindle #6, 20 RPM) after aging in a constant temperature oven at 25° C. for 1 hour according to ASTM D 2196 standard. . When the vinyl chloride resin composition has a viscosity within the above-mentioned range, the processing speed is fast, so that productivity can be improved, and a product of a certain quality can be stably produced during product molding.

In addition, the vinyl chloride resin composition exhibits excellent physical properties after molding, in particular, it is possible to manufacture a product excellent in tensile strength. For example, products such as artificial leather, toys, automobile undercoatings, infant toys, and miscellaneous goods can be manufactured by molding the vinyl chloride resin composition. In particular, the vinyl chloride resin composition is environmentally friendly and requires high elasticity. It may be useful for use in the manufacture of industrial or medical gloves.

The vinyl chloride resin composition according to the present invention contains a specific amount of a combination of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate and tributylcitrate as a plasticizer to exhibit excellent processability to improve product productivity. can be improved In addition, by using such a vinyl chloride resin composition, it is possible to manufacture an environmentally friendly glove exhibiting high elasticity.

Hereinafter, the present invention will be described in more detail by way of Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto. In addition, in the following examples and comparative examples, "%" and "part" indicating the content are by weight unless otherwise specified.

Example 1

Based on 100 parts by weight of vinyl chloride resin (KH-31G™, manufactured by Hanwha Chemical, polymerization degree 1600±50), 64 parts by weight of DEHCH, 16 parts by weight of TBC, 2 parts by weight of a liquid stabilizer (LTX248H™, manufactured by KD Chem), carboxyl 5 parts by weight of an acid ester compound, a viscosity reducing agent (BYK LP-R 22274™, manufactured by BYK, 20°C density=0.879g/cm ³ , solidification point: <-13°C, flash point: >140°C) and a dispersant (BYK-21809) ™, manufactured by BYK, 20° C. density = 1.092 ^{g/cm 3} , acid value: about 100 mgKOH/g, flash point: >100° C.) 1 part by weight) was mixed in a Mathis mixer for 10 minutes to prepare a plastisol-type vinyl chloride resin composition did.

Example 2

A vinyl chloride resin composition in the form of plastisol was used in the same manner as in Example 1, except that 56 parts by weight of DEHCH and 24 parts by weight of TBC were used instead of 64 parts by weight of DEHCH and 16 parts by weight of TBC in Example 1 was prepared.

Comparative Example 1

A plastisol-type vinyl chloride resin composition was prepared in the same manner as in Example 1, except that 80 parts by weight of DOTP was used as a plasticizer instead of 64 parts by weight of DEHCH and 16 parts by weight of TBC in Example 1. .

Comparative Example 2

Example 1, except that in Example 1, 80 parts by weight of DOTP was used as a plasticizer and 10 parts by weight of a viscosity reducing agent (BYK LP-R 22274™) was used instead of 64 parts by weight of DEHCH and 16 parts by weight of TBC. A vinyl chloride resin composition in the form of plastisol was prepared by using the same method as described above.

Comparative Example 3

A plastisol-type vinyl chloride resin composition using the same method as in Example 1, except that 48 parts by weight of DEHCH and 32 parts by weight of TBC were used instead of 64 parts by weight of DEHCH and 16 parts by weight of TBC in Example 1 was prepared.

Comparative Example 4

A plastisol-type vinyl chloride resin composition using the same method as in Example 1, except that 76 parts by weight of DEHCH and 4 parts by weight of TBC were used instead of 64 parts by weight of DEHCH and 16 parts by weight of TBC in Example 1 was prepared.

Comparative Example 5

A plastisol-type vinyl chloride resin composition was prepared in the same manner as in Example 1, except that 1 part by weight of the viscosity reducing agent (BYK LP-R 22274™) was used in Example 1.

Comparative Example 6

A plastisol-type vinyl chloride resin composition was prepared in the same manner as in Example 1, except that 20 parts by weight of the viscosity reducing agent (BYK LP-R 22274™) was used in Example 1.

Comparative Example 7

In Example 1, instead of the vinyl chloride resin (KH-31G™, Hanwha Chemical Co., Ltd., degree of polymerization 1600±50), a vinyl chloride resin (KL-31™, Hanwha Chemical Co., Ltd., degree of polymerization 1,000±50) was used, except that A plastisol-type vinyl chloride resin composition was prepared using the same method as in Example 1.

Comparative Example 8

A plastisol-type vinyl chloride resin composition was prepared in the same manner as in Example 1, except that acetyltributylcitrate (ATBC) was used instead of TBC in Example 1.

Experimental example

The viscosity and gelling rate of the vinyl chloride resin compositions prepared in Examples and Comparative Examples, and the tensile strength of the specimen prepared by curing the plastisol were evaluated as follows.

1) Viscosity

The viscosity was measured using a Brookfield viscometer (spindle #6, 20 RPM) after aging each of the prepared vinyl chloride resin compositions in a constant temperature oven at 25° C. for 1 hour according to ASTM D 2196 standard, The results are shown in Table 1 below.

2) Gelling speed

The gelling rate was measured at 110° C. for each of the prepared vinyl chloride resin compositions using SVNC equipment. As the gelling progresses in the SVNC equipment, the amplitude decreases. The gelling rate was compared and measured using the decreasing rate, and then the gelling rate was scored and shown in Table 1 below (excellent 10>9>8>7> 6>5>4>3>2>1 very inferior).

3) Tensile strength

The vinyl chloride resin composition prepared in Examples and Comparative Examples was coated to a thickness of 0.2 mm and then heated at 200° C. for 3 minutes to prepare a specimen, and the tensile strength of the specimen was measured using UTM according to ASTM D 638 standard. It was measured under the condition of cross head speed 200mm/min.

	PSR degree of polymerization	plasticizer			Viscosity lowering agent (parts by weight)	Physical property evaluation
		DEHCH (parts by weight)	TBC (parts by weight)	DEHCH:TBC weight ratio		Viscosity (cPs)	gelling speed	Seal burglar (kgf/mm 2 )
Example 1	1,600	64	16	80:20	5	565	8	1.758
Example 2	1,600	56	24	70:30	5	680	9	1.802
Comparative Example 1	1,600	DOTP 80			5	1100	4	1.680
Comparative Example 2	1,600	DOTP 80			10	715	3	1.571
Comparative Example 3	1,600	48	32	60:40	5	1050	10	1.743
Comparative Example 4	1,600	76	4	95:5	5	470	6	1.740
Comparative Example 5	1,600	64	16	80:20	One	1200	8	1.780
Comparative Example 6	1,600	64	16	80:20	20	385	6	1.563
Comparative Example 7	1,000	64	16	80:20	5	575	9	1.589
Comparative Example 8	1,600	64	16 (ATBC)	80:20	5	550	6	1.723

As shown in Table 1, the vinyl chloride resin composition of the above Examples, the vinyl chloride resin composition of Comparative Examples 1 and 2 and the TBC content of Comparative Examples 3 and 4 in which the plasticizer composition of the present application is not employed, and the content of TBC are too small or too much Chloride of Comparative Examples 3 and 4 It can be confirmed that, compared to the vinyl resin composition, it has a low viscosity and a fast gelling speed, so that the processability is excellent, and the tensile strength of the specimen prepared by molding can be improved.

In addition, unlike the vinyl chloride resin compositions of Comparative Examples 5 and 6 in which the content of the viscosity reducing agent is too small or too large, the vinyl chloride resin composition of the above example can exhibit a low viscosity and a fast gelling rate at the same time, so that it has excellent processability. Able to know.

In addition, the vinyl chloride resin composition of the above example can improve the tensile strength of the specimen prepared by molding compared to the vinyl chloride resin composition of Comparative Example 7 using a vinyl chloride resin having a low polymerization degree, and using a citrate compound other than TBC It was confirmed that it was possible to improve the tensile strength of the specimen prepared by molding at the same time while exhibiting a faster gelling rate compared to the vinyl chloride resin composition of Comparative Example 8.

Claims (11)

1. (a) 100 parts by weight of a vinyl chloride resin having a degree of polymerization of 1,300 or more;

   (b) 50 to 90 parts by weight of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate;

   (c) 5 to 30 parts by weight of tributylcitrate;

   (d) 0.5 to 3 parts by weight of a stabilizer; and

   (e) greater than 1 part by weight and less than 20 parts by weight of a viscosity reducing agent;

   A vinyl chloride resin composition.
2. According to claim 1,

   The vinyl chloride resin has a polymerization degree of 1,400 to 2,000,

   A vinyl chloride resin composition.
3. According to claim 1,

   The sum of the di (2-ethylhexyl) cyclohexane-1,4-dicarboxylate and the tributyl citrate is included in an amount of 70 to 90 parts by weight based on 100 parts by weight of the vinyl chloride resin,

   A vinyl chloride resin composition.
4. According to claim 1,

   The weight ratio of the di (2-ethylhexyl) cyclohexane-1,4-dicarboxylate and the tributyl citrate is 90:10 to 65:35,

   A vinyl chloride resin composition.
5. According to claim 1,

   The stabilizer is selected from the group consisting of Ca-Zn-based compounds, K-Zn-based compounds, Ba-Zn-based compounds, organic tin-based compounds, metallic soap-based compounds, phenol-based compounds, phosphoric acid ester-based compounds, and phosphorous acid ester-based compounds. one or more of the

   A vinyl chloride resin composition.
6. According to claim 1,

   The viscosity reducing agent comprises an aliphatic hydrocarbon-based compound, a carboxylic acid ester-based compound, or a combination thereof,

   A vinyl chloride resin composition.
7. According to claim 1,

   The viscosity reducing agent has a density of 0.85 to 0.9 g/cm ³ at 20 ° C., a solidification point of -7 ° C. or less, and a flash point of 120 ° C. or more,

   A vinyl chloride resin composition.
8. According to claim 1,

   further comprising a dispersant;

   A vinyl chloride resin composition.
9. 9. The method of claim 8,

   The dispersant is included in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the vinyl chloride resin,

   A vinyl chloride resin composition.
10. According to claim 1,

    The vinyl chloride resin composition has a viscosity of 400 cPs to 1,000 cPs as measured by a Brookfield viscometer (spindle #6, 20 RPM) after aging in a constant temperature oven at 25° C. for 1 hour according to ASTM D 2196 standard,

    A vinyl chloride resin composition.
11. An industrial or medical glove manufactured by molding the vinyl chloride resin composition according to any one of claims 1 to 10.