KR100762838B1 - High elastic polyvinyl chloride composition and objects prepared by the same - Google Patents

Abstract

The present invention includes polyvinyl chloride-rubber particles including polyvinyl chloride secondary particles and rubber particles formed by combining a plurality of polyvinyl chloride primary particles, wherein the rubber particles in the polyvinyl chloride-rubber particles are Provided is a high elastic polyvinyl chloride composition, characterized in that it is filled in the voids between the polyvinyl chloride primary particles forming the polyvinyl chloride secondary particles.

The film produced using the polyvinyl chloride composition of the present invention has excellent elasticity and excellent uniformity of rubber particles in the film. The polyvinyl chloride composition of the present invention is also excellent in elongation and high tensile strength by crosslinking pretreatment to the rubber particles, and excellent in workability because there is no increase in viscosity without increasing the amount of plasticizer used when forming a film.

Polyvinyl chloride, rubber particles, crosslinking treatment, high elasticity, processing viscosity

Description

High elastic polyvinyl chloride composition and objects prepared by using the same

1 is a scanning electron micrograph of polyvinyl chloride-rubber particles prepared according to Comparative Example 1 of the present invention.

2 is a scanning electron micrograph of polyvinyl chloride-rubber particles prepared according to Example 20 of the present invention.

Figure 3 is a transmission electron micrograph of the particle center of the cross section of the polyvinyl chloride-rubber particles prepared according to Example 20 of the present invention.

Figure 4 is a transmission electron micrograph of the particle surface portion of the cross section of the polyvinyl chloride-rubber particles prepared according to Example 20 of the present invention.

The present invention relates to a high-elastic polyvinyl chloride composition and a molded article prepared using the same, more particularly, having a good tensile strength and elongation, and when crosslinked, the processing viscosity is greatly reduced, so that the polyvinyl chloride composition has excellent workability. It relates to a film produced using this.

Polyvinyl chloride resin is produced by polymerizing a monomer such as vinyl chloride, and is commercialized through molding process such as extrusion process, calender process, injection process, dipping process after mixing various additives such as plasticizer, colorant, and heat stabilizer. . Soft polyvinyl chloride, including plasticizers, has been used for various purposes in many fields, including building materials, toys, artificial leather, shoes, and gloves, depending on its processing method.

On the other hand, in the past, soft resin molded articles have been widely used especially in the field of automobile interiors, and soft polyvinyl chloride in which foam layers such as polyolefins and polyurethane resins are disposed in order to provide cushioning properties has been used as the skin material. Film made of soft polyvinyl chloride used as the skin material has a problem that the elasticity is relatively low compared to the film made of natural rubber or other rubber.

Korean Patent Application No. 2001-52916 discloses an elastic foam layer comprising polyvinyl chloride and acrylonitrile butadiene rubber (NBR) or styrene butadiene rubber (SBR) as a technical configuration for increasing elasticity, and a floor decorative material including the same. However, since the method of mixing the polyvinyl chloride and NBR or butadiene rubber (BR) simply mixes each composition component in a powder state and kneads it under high temperature to finally produce a film, thermal energy consumption in the manufacturing process is increased. It is severe and the uniformity of the composition in the film is reduced, which has the disadvantage that the elongation and recovery rate is poor. In addition, the prepared composition is almost impossible to produce a film thickness of less than 300㎛ when manufacturing a film form product by an extrusion process or a calendering process, making a three-dimensional film form product such as vinyl gloves There was a problem that the process efficiency is difficult because of difficulty.

U.S. Patent No. 6,333,386 also includes NBR having an acrylonitrile content of 43-50% and polyvinyl chloride (PVC), which contains a plasticizer having a solubility coefficient (SP) of 8.8 or higher and an average molecular weight of 550. The rubber composition is disclosed, but since the PVC content is low as 25 to 40% and the NBR content is high, it is difficult to prepare a plastisol using a plasticizer because the particle size is too large when blending. There is a problem that it is not suitable and it is difficult to prepare a molded article in the form of a thin glove.

On the other hand, US Patent No. 6,043,318 is a polyvinyl chloride resin coated with a stabilizer to prepare a pre-coated PVC, after blending the pre-coated PVC and NBR resin, and then heated and pressurized NBR / PVC blend in a molten state Although a method of preparing the present invention is disclosed, the blended resin may form a film through an extrusion process or a calendering process, but it is difficult to form a uniform and thin film because it is difficult to prepare a plastisol.

In addition, polyvinyl chloride resins are compatible with plasticizers such as dioctylphthalate (DOP), dibutyl phthalate (DBP), dioctyl adipate (DOA), and diisononyl phthalate (DINP), in which the initially mixed rubber is mixed during processing. Too much plasticity has a problem that it is difficult to mold due to excessive increase in viscosity due to swelling of the rubber when molding the product, and to solve this problem, the amount of plasticizer must be increased.

The present invention is to solve the problems of the prior art as described above,

The first technical problem to be achieved by the present invention is to provide a high elastic polyvinyl chloride composition having excellent elongation and high tensile strength and excellent processability without increasing the viscosity even when the amount of plasticizer is increased when forming a film.

The second technical problem to be achieved by the present invention is to provide a molded article prepared using the high elastic polyvinyl chloride composition.

The present invention to achieve the first technical problem

A polyvinyl chloride-rubber particle comprising a polyvinyl chloride secondary particle and rubber particles formed by combining a plurality of polyvinyl chloride primary particles,

In the polyvinyl chloride-rubber particles, the rubber particles are filled in the voids between the polyvinyl chloride primary particles forming the polyvinyl chloride secondary particles.

In the polyvinyl chloride composition of the present invention, the polyvinyl chloride-rubber particles may be obtained by mixing 100 parts by weight of polyvinyl chloride particles in a water-dispersive latex state and 1 to 30 parts by weight of rubber particles in a water-dispersive latex state and then drying them. have.

In the polyvinyl chloride composition of the present invention, the average degree of polymerization of the polyvinyl chloride particles may be 100 to 3,000.

In the polyvinyl chloride composition of the present invention, the average particle diameter of the polyvinyl chloride primary particles may be 0.1 to 2 ㎛.

In addition, the polyvinyl chloride particles may be prepared from a vinyl chloride single monomer or from mixed monomers in which a vinyl chloride monomer and other monomers copolymerizable therewith are mixed.

On the other hand, the monomer copolymerizable with the vinyl chloride monomer is acrylic acid, etharyl acid, alpha-cyanoacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, cyanoethyl acrylate, vinyl acetate, methyl meth Methacrylate, ethyl methacrylate, butyl methacrylate, acrylonitrile, methacrylonitrile, methylacrylamide, N-methyl-acrylamide, N-butoxy methacrylamide, ethyl vinyl ether, chloroethyl vinyl ether, At least one selected from the group consisting of alpha-methylstyrene, vinyltoluene, chlorostyrene, vinylnaphthalene, vinylidene chloride, vinyl bromide, vinylchloroacetate, vinyl acetate, vinylpyridine and methylvinyl ketone.

In the polyvinyl chloride composition of the present invention, the rubber particles are at least one selected from the group consisting of styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR) and methacrylate-butadiene-styrene rubber (MBS). Can be.

In the polyvinyl chloride composition of the present invention, the content of butadiene in the styrene-butadiene rubber may be 60 to 90% by weight.

In addition, the content of butadiene in the acrylonitrile-butadiene rubber is 50 to 90% by weight. In addition, the acrylonitrile-butadiene rubber may further include 1 to 20 parts by weight of a monomer having a carboxyl group based on 100 parts by weight of the total content of acrylonitrile and butadiene.

Meanwhile, the methacrylate content in the methacrylate-butadiene-styrene rubber may be 5 to 30% by weight, and the content of butadiene may be 60 to 90% by weight.

In the polyvinyl chloride composition of the present invention, the average degree of polymerization of the rubber particles may be 100 to 3,000. In addition, the average particle diameter of the rubber particles may be 0.05 ㎛ to 1 ㎛.

The polyvinyl chloride composition of the present invention may include 100 parts by weight of the polyvinyl chloride-rubber particles and 80 to 100 parts by weight of a plasticizer.

In the present invention, the plasticizer may be composed of 70 to 90% by weight of the primary plasticizer and 10 to 30% by weight of the secondary plasticizer.

Meanwhile, the primary plasticizer is selected from the group consisting of dioctyl phthalate, diisononyl phthalate, and butylbenzyl phthalate, and the secondary plasticizer is 2,2,4-trimethyl-1,3-pentanediol di Isobutyrate (2,2,4-trimethyl-1,3-pentanediol diisobutyrate; TXIB), Hisol SAS 296 (mixture of 1-phenyl-1-xylethane and 1-phenyl-1-ethylphenylethane), BYK-331 (Polyether modified polydimethylsiloxane copolymer), dioctylphthalate (DOP) can be selected from one or more.

In the polyvinyl chloride composition of the present invention, the rubber particles may be crosslinked by a crosslinking agent. The crosslinking treatment may be performed by slowly adding and stirring 0.5 to 10 parts by weight of the crosslinking agent solids to 100 parts by weight of the rubber solids in the latex state while maintaining a temperature of 10 to 95 ° C.

On the other hand, the crosslinking agent is trimethylol propane trimethacrylate, triaryl cyanurate, triaryl isocyanurate, N, N'- methphenylene dimaleimide, ethylene glycol dimethacrylate, vinyl-1,2- Polybutadiene, 1,1-t-butylperoxy-3,3,5-trimethylcyclohexane, n-butyl-4,4-bisbutylpooxyvalerate, dicumylperoxide, benzoylperoxide, t-butylperoxide Oxybenzoate, di-t-butylperoxide, 2,5-dimethyl-2,5-di-t-butylperoxynucleic acid, paraquinonedioxine, dibenzoylparaquinonedioxine, tetrachloroparabenzoquinone, hexamethylenetetra Amine, acetaldehyde ammonia, butylaldehyde ammonia, butylaldehyde butyl aniline, acetaldehyde aniline, diphenylguanidine, diorthotolylguanidine, orthotolylbiguananidine, N, N'-diethylthiourea, dibutylthiourea, dilaurylurea Thiourea, Trimethyltea Urea, mercetobenzothiazole, dibenzothiazyl disulfide, sodium-2-mercetobenzothiazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, di Pentamethylene-thiuram tetrasulfide, sodium dimethyldithiocarbamate, sodium dibutyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, ferric dimethyldithiocarbamate, cooperdimethyldithiocarba To mate, zinc ethylphenyl-dithiocarbamate, zinc dibutyldithiocarbamate, zinc butyl xanthate, zinc isopropyl xanthate, zinc ethyl xanthate, sodium isopropyl xanthate, sodium ethyl xanthate, potassium Tilcanthate, potassium isopropyl xanthate, N-cyclohexyl-2-benzothiazoylsulfenamide, Nt-butyl-2-benzothiazoylsulfenamide, N-oxydiethylene-2-benzothiazoylsulfenamide, zinc oxide, zinc carbonate, magnesium oxide, lead monoxide, potassium hydroxide, stearic acid, oleic acid, lauric acid, zinc stearate, dibutylammonium oleate, vinyltrimethoxysilane , Vinyltriethoxysilane, vinyltri- (2-methoxyethoxysilane), vinyltriacetoxysilane, gammamerbutoxypropyltrimethoxysilane, gammamerbittotri- (2-methoxyethoxysilane), Consisting of gamma glycidylpropyltrimethoxysilane, gamma mertotopropyltriethoxysilane, gammaaminopropyltrimethoxysilane, gammaaminopropyltrimethoxysilane, aminoalkylsilicone, styreneoxazoline, 2-methyloxazoline It may be one or more selected from the group.

In addition, the viscosity of the high elastic polyvinyl chloride composition may be 500 to 6,000 cps at 25 ℃.

In addition, the average particle diameter of the polyvinyl chloride-rubber particles may be 10 ㎛ to 50 ㎛.

The present invention provides a molded article prepared using the high elastic polyvinyl chloride composition in order to achieve the second technical problem.

In the present invention, the molded body may be a film, sheet or tile.

Hereinafter, the present invention will be described in detail.

In order to provide a polyvinyl chloride composition having excellent tensile strength, elasticity and processing characteristics when processed by a dipping process, the rubber particles are mixed with polyvinyl chloride particles in a latex state prior to drying the polyvinyl chloride particles and dried. Polyvinyl chloride-rubber particles prepared by In this case, as the polyvinyl chloride-rubber particles are mixed in a latex state, the polyvinyl chloride primary particles (in the present invention, a single polyvinyl chloride particle dispersed in the latex state is called 'polyvinyl chloride primary particles'). It provides a new particle structure having a structure in which rubber particles are dispersed in fine pores of.

According to the present invention, a polyvinyl chloride secondary particle formed by combining a plurality of polyvinyl chloride primary particles (in the present invention, a polyvinyl chloride secondary particle formed by combining the polyvinyl chloride primary particles is referred to as 'polyvinyl chloride secondary particle'). Polyvinyl chloride-rubber particles comprising particles of rubber), wherein the rubber particles form the polyvinyl chloride secondary particles in the polyvinyl chloride-rubber particles. Provided is a high elastic polyvinyl chloride composition, characterized in that it is filled in the gap between them.

In general, the polyvinyl chloride particles are formed during the formation of the particles, and after the initial formation of the polymerization, after the polymerization, these domains form primary particles (about 0.5 to 2.0 μm) and are dispersed in the latex. These primary particles are reconstituted into secondary particles (about 200 ~ 100㎛) during the drying process. When the polyvinyl chloride secondary particle rubber particles are mixed by powder blending, the polyvinyl chloride-rubber particles thus prepared are not broken because the polyvinyl chloride secondary particles are pulverized during the blending process. Rubber particles are hard to enter into the secondary particles, and the rubber particles mainly exist only on the surface of the polyvinyl chloride secondary particles. In addition, even when the rubber particles enter the inside of the polyvinyl chloride double particles, it is difficult to uniformly distribute the inside of the polyvinyl chloride particles.

In contrast, in the case of the polyvinyl chloride-rubber particles of the present invention, since the polyvinyl chloride primary particle latex and the rubber particle latex are uniformly mixed and dried to form polyvinyl chloride secondary particles, the rubber in the polyvinyl chloride secondary particles The particles are uniformly distributed and have a structure mainly filled in the voids between the polyvinyl chloride primary particles.

This will be described in more detail with reference to the drawings.

1 and 2 are scanning electron microscope (SEM) images of the surface characteristics of the polyvinyl chloride-rubber particles prepared according to Comparative Example 1 and Example 20, respectively. 1, it can be seen that pores are seen between the polyvinyl chloride primary particles, and primary particles of about 0.5 to 2 μm gather to form secondary polyvinyl chloride particles of 20 μm or more. On the contrary, in FIG. 2, the voids between the polyvinyl chloride primary particles are hardly seen, and it is determined that the rubber particles of small size fill the voids between the polyvinyl chloride primary particles.

Figure 3 is a transmission electron micrograph of the particle center portion of the cross section of the polyvinyl chloride-rubber particles prepared according to Example 20 of the present invention, Figure 4 is a polyvinyl chloride-rubber prepared according to Example 20 of the present invention A transmission electron micrograph of the particle surface portion of the cross section of the particle. 3 and 4, it can be seen that the polyvinyl chloride (PVC) primary particle size is about 0.5 to 2 μm (gray particles in FIGS. 3 and 4). It can be observed that the size of the rubber particles NBR is 300 nm or less (black particles of FIGS. 3 and 4). It can also be observed that the rubber particles are evenly distributed between the polyvinyl chloride primary particles. Due to the distribution of the polyvinyl chloride primary particles and rubber particles, not only the uniformity of the composition is increased, but also the crosslinked rubber particles in the composition, and additives such as plasticizers and heat stabilizers. When mixed, it forms a low-viscosity plastisol, so that molding in various forms is possible, a thin film of 300 μm or less can be formed, and elasticity is very excellent.

The properties, working composition ratios and processing methods of the composition constituting the present invention will be described in detail below.

The polyvinyl chloride particles of the present invention may be prepared by polymerizing a single monomer of vinyl chloride or a mixed monomer obtained by mixing vinyl chloride and another monomer copolymerizable with vinyl chloride, and after the polymerization, various additives such as a plasticizer and a heat stabilizer may be used. The mixture may be formed into a film.

In the present invention, the average degree of polymerization of the polyvinyl chloride particles is preferably 100 to 3,000. When the average degree of polymerization of the polyvinyl chloride particles is less than 100, there is a problem that the strength during film forming is poor, and when the average degree of polymerization exceeds 3,000, polymerization is difficult due to the polymerization characteristics of the vinyl chloride monomer.

In the present invention, the average particle diameter of the polyvinyl chloride primary particles is preferably 0.1 to 2 ㎛. When the average particle diameter is less than 0.1 μm, there may be a problem in the latex stability when mixing with rubber water-dispersible latex, and when the average particle diameter exceeds 2 μm, there is a concern that a protrusion may be formed during film forming.

The polyvinyl chloride particles may be prepared through conventional suspension polymerization, emulsion polymerization, or fine suspension polymerization from a vinyl chloride single monomer or a mixed monomer obtained by mixing the vinyl chloride and other monomers copolymerizable therewith. It does not limit the invention.

In the above polymerization method, the fine suspension polymerization is one or more kinds dispersed in a water-soluble medium containing an emulsifier and a dispersant as a stabilizer in order to obtain a dispersion of particles having an average particle diameter of 5 μm or less as polymerization in a fine suspension by a powerful mechanical means (Homo mixer). It is to polymerize a monomer. Other copolymerizable monomers are not particularly limited as long as they are commonly used in the art, and specific examples thereof include acrylic acid, methacrylic acid, alpha cyanoacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate and octyl acryl. Rate, cyanoethyl acrylate, vinyl acetate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-methylol acrylamide, N Butoxymethacrylamide, ethyl vinyl ether, chloroethyl vinyl ether, alpha methyl styrene, vinyl toluene, chloro styrene, vinyl naphthalene, vinylidene chloride, vinyl bromide, vinyl chloroacetate, vinyl acetate, vinyl pyridine and methyl vinyl ketone It may be at least one selected from the group consisting of.

On the other hand, the rubber particles used in the present invention is selected from the group consisting of styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), methacrylate-butadiene-styrene rubber (MBS) or mixtures thereof It may be one or more, such rubber particles in the present invention serves to impart the surface characteristics such as elasticity when processed by a method such as dipping.

The content of the rubber particles is preferably 1 to 30 parts by weight, more preferably 10 to 20 parts by weight, still more preferably 15 to 20 parts by weight, based on 100 parts by weight of the polyvinyl chloride particle solids. When the content is less than 1 part by weight, there is little mixing effect, and when the content is more than 30 parts by weight, the strength of the film may be drastically lowered during film molding, which is not preferable.

When the rubber particles that can be used in the present invention is SBR rubber, the content of butadiene in the SBR rubber is preferably 60 to 90% by weight. When the content is less than 60% by weight, it is difficult to give sufficient elasticity, and when the content is more than 90% by weight, it is not preferable because the compatibility with PVC during film forming may be degraded and the mechanical strength may deteriorate.

In addition, when the rubber particles are NBR rubber, the content of butadiene in the NBR rubber is preferably 50 to 90% by weight. When the content is less than 50% by weight, it is difficult to give sufficient elasticity, and when the content is more than 90% by weight, compatibility with polyvinyl chloride during film molding may be degraded, which may deteriorate mechanical strength.

On the other hand, the NBR rubber may be prepared as a terpolymer by further comprising 1 to 20 parts by weight of a monomer having a carboxyl group with respect to 100 parts by weight of the total content of acrylonitrile and butadiene in the polymerization step. At this time, when the content of the monomer having a carboxyl group is less than 1 part by weight, there is no effect of addition, and when it exceeds 20 parts by weight, there is a problem that aggregation occurs when mixed with PVC latex, which is not preferable.

The monomer having a carboxyl group is not particularly limited, and specific examples thereof may include acrylic acid, methacrylic acid, maleic anhydride, and the like.

In addition, when the rubber particles are MBS rubber, the methacrylate content in the MBS rubber is preferably 5 to 30% by weight. If the content is less than 5% by weight, there is a fear that compatibility with polyvinyl chloride during the film molding is poor, and if it exceeds 30% by weight, it is not preferable because sufficient elasticity is difficult to be obtained .

On the other hand, the content of butadiene in the MBS rubber is preferably 60 to 90% by weight. When the content is less than 60% by weight, it is difficult to give sufficient elasticity, and when the content is more than 90% by weight, it is not preferable because there is a problem in that the compatibility with polyvinyl chloride falls and mechanical strength falls during film forming.

On the other hand, the average degree of polymerization of the rubber particles is preferably 100 to 3,000. When the average degree of polymerization is less than 100, it is difficult to obtain the expected elasticity, and when the average degree of polymerization exceeds 3,000, there is a problem in compatibility with polyvinyl chloride during film molding, which is not preferable.

In addition, the average particle diameter of the rubber particles is preferably 0.05 to 1 ㎛. When the average particle diameter is less than 0.05 µm, it is difficult to act as a domain for imparting elasticity, and when the average particle diameter is larger than 1 µm, it is not preferable because the mechanical strength may decrease during film forming.

The high-elastic polyvinyl chloride composition of the present invention can adjust the processing viscosity and make the moldability during processing easier by using the rubber particles crosslinked as the rubber particles.

In this case, the crosslinking agent used for the crosslinking treatment of the rubber particles is not particularly limited as long as it is commonly used in the art, and specific examples thereof include trimethylolpropane-trimethacrylate, triarylcyanurate, and triarylisocyanurate. Ethylene glycol, ethylene glycol dimethacrylate, vinyl-1,2-polybutadiene, 1,1-t-butylperoxy-3,3,5-trimethyl-cyclohexane, n-butyl-4,4-bis (t-butylperoxy) pivalate, dicumylperoxide, benzoyl peroxide, t-butylperoxybenzoate, di-t-butylperoxide, 2,5-dimethyl-2 , 5-di-t-butylperoxynucleic acid, paraquinonedioxine, dibenzoylparaquinonedioxine, tetrachloroparabenzoquinone, hexamethylenetetraamine, acetaldehyde ammonia, butylaldehyde ammonia, butylaldehyde butylaniline, acetaldehyde aniline, Diphenylguanidine, Diorthotolylguanidine, orthotolylbiguanide, N, N'-diethylthiourea, dibutylthiourea, dilaurylthiourea, trimethylthiourea, merchitobenzothiazole, dibenzothiazyl disulfide, sodium-2- Mercetobenzothiazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide, sodium dimethyldithiocarbamate, sodium dibutyldithi Ocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, ferric dimethyldithiocarbamate, cooperdimethyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc dibutyldithiocarbamate, zinc Butyl xanthate, zinc isopropyl xanthate, zinc ethyl xanthate, sodium isopropyl xanthate, sodium ethyl xanthate, potassium Xanthate, potassium isopropyl xanthate, N-cyclohexyl-2-benzothiazoylsulfenamide, Nt-butyl-2-benzothiazoylsulfenamide, N-oxydiethylene-2-benzothiazoylsulfenamide, zinc oxide , Zinc carbonate, magnesium oxide, lead monoxide, potassium hydroxide, stearic acid, oleic acid, lauric acid, zinc stearate, dibutylammonium oleate, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri- (2-methoxy- Methoxysilane), vinyltriacetoxysilane, gammameroxoxypropyltrimethoxysilane, gammameroctotri- (2-methoxyethoxysilane), gammaglycidylpropyltrimethoxysilane, gammamercetopropyltrie Oxysilane, gammaaminopropyltrimethoxysilane, gammaaminopropyltrimethoxysilane, aminoalkylsilicone, styreneoxazoline, 2-methyloxazoline may be one or more selected from the group consisting of.

The crosslinked rubber particles according to the present invention are prepared by preparing the crosslinking agent in an aqueous solution or an aqueous dispersion of 10% concentration and maintaining a temperature of 0.5 to 10 parts by weight of the crosslinking agent solids to 100 parts by weight of the rubber solids in the latex state. While slowly adding while stirring for about 30 minutes can be prepared by crosslinking treatment. At this time, the content of the crosslinking agent is hardly effective when the content is less than 0.5 parts by weight, and when the content is more than 10 parts by weight, the rubber is cured and the effect is reduced, which is not preferable.

The polyvinyl chloride-rubber particles of the present invention are prepared by mixing and drying the rubber particles in the water-dispersive latex state before the polyvinyl chloride primary particles in the water-disperse latex state in which the polymerization is completed are dried.

At this time, the drying method is not particularly limited as long as it is commonly used in the art, for example, it may be dried by a spray drying method, a nozzle spray drying method, or a freeze drying method.

In the present invention, the average particle diameter of the polyvinyl chloride-rubber particles is preferably 10 μm to 50 μm. If the average particle diameter is less than 10 μm, it is difficult to give sufficient elasticity and the processing viscosity is increased. If the average particle diameter is more than 50 μm, it is not preferable because protrusions may be formed during film molding.

The polyvinyl chloride composition according to the present invention may further include an additive such as a plasticizer and a heat stabilizer in addition to the polyvinyl chloride-rubber particles to form a plastisol.

The plasticizer that can be used is not particularly limited as long as it is commonly used in the art, and specific examples thereof include adipic acid, dimethyl adipate, diethyl adipate, di-n-butyl adipate, and diisobutyl adidiate. Pate, di-n-hexyl adipate, di (1,3-dimethylbutyl) adipate, di-2-ethylhexyl adipate, diisooctyl adipate, dicapryl adipate, heptyl nonyl adipate, diisononyl Adipate, di-n-octyl-n-decyl adipate, diisodecyl adipate, dicyclohexyl adipate, benzyl octyl adipate, dibutoxyethyl adipate, bis (2,2,4-trimethyl-1, Adipates including 3-pentanediol monoisobutyl) adipate, bis (4-chlorobutyl) adipate and diisohexyl adipate; 2,2,4-trimethyl-1,3-pentanedioldiisobutyrate, amide ester, azelate, benzoate, benzotriazole, ester and ether, brasylate, carbonate, citrate, epoxy compound, gluta Latex, glycerol ester, glycol ester, glycol, glycolate, hexahydrophthalate, hydrocarbon, isobutyrate, isophthalate, isosebacate, ketone, nitro compound, oleate, palmitate, pentaerythritol, phosphate, phosphite, phthalate , Polyester and polymeric plasticizers, pyromellitate, ricinolate, salicylate, sebacate, stearate, succinate, sucrose derivatives, sulfonamides, sulfonates, sulfones, tartrates, terephthalates, terehydro In the group consisting of phthalates, thianthrenes, trimellitates, terpenes and derivatives thereof It can taekdoel.

One or more of these plasticizers may be used. It is preferable to use phthalate-based plasticizers such as dioctyl phthalate, diisononyl phthalate, and butylbenzyl phthalate as primary plasticizers that act as softeners to give flexibility, and serve as viscosity reducing agents. 2,2,4-trimethyl-1,3-pentanedioldiisobutyrate, Hisol SAS 296 (a mixture of 1-phenyl-1-xylethane and 1-phenyl-1-ethylphenylethane), Preference is given to using BYK-331 (polyether modified polydimethylsiloxane copolymer).

The content of the plasticizer is preferably 80 to 100 parts by weight based on 100 parts by weight of the polyvinyl chloride-rubber particles, and specifically, 70 to 90 parts by weight of the primary plasticizer and 10 to 20 parts by weight of the secondary plasticizer.

If the content of the primary plasticizer is less than 70 parts by weight, the amount of plasticizer is not sufficient, so the viscosity of the plastisol is high during processing and the flexibility is reduced after film forming. If the content is greater than 90 parts by weight, the mechanical properties of the final film Not good enough. In addition, when the content of the secondary plasticizer is less than 10 parts by weight, the viscosity is high during the plastisol processing, and if it exceeds 30 parts by weight, the mechanical properties of the final film may be deteriorated, which is not preferable.

As the heat stabilizer used in the present invention, a conventionally known one can be used. Among them, metal salt heat stabilizers such as tin heat stabilizers, Ca-Zn heat stabilizers, hydrotalcite heat stabilizers, and zeolite and epoxy heat stabilizers. It can select and use 1 or more types from those, It is preferable that the usage-amount is 1-4 weight part with respect to 100 weight part of said polyvinyl chloride secondary particles.

In the present invention, when the polyvinyl chloride composition including the crosslinked rubber particles further includes 80 to 100 parts by weight of a plasticizer based on 100 parts by weight of polyvinyl chloride-rubber particles, the viscosity is preferably 500 to 6,000 cps at 25 ° C. . At this time, the plasticizer is 70 to 90 parts by weight of dioctylphthalate (DOP) as the primary plasticizer, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (2,2,4-trimethyl as the secondary plasticizer More preferably, 10 to 30 parts by weight of -1,3-pentanediol diisobutyrate (TXIB) is used. When the viscosity of the polyvinyl chloride composition is less than 500 cps at 25 ° C., it is difficult to control the thickness due to excessive flow during the dipping process for forming a film. When the polyvinyl chloride composition exceeds 6,000 cps, processing becomes impossible due to the decrease in flow. There is a problem and is undesirable.

The present invention provides a high elastic polyvinyl chloride molded article having improved tensile strength by using the high elastic polyvinyl chloride composition. In the present invention, the molded body includes a film, a sheet or a tile.

The high elastic film according to the present invention may be prepared in the form of a film using a dipping process of the polyvinyl chloride composition according to the present invention in a plastisol state.

In addition, the film is mixed with a mixer for 10 to 30 minutes by adding 80 to 120 parts by weight of a plasticizer and 1 to 4 parts by weight of a heat stabilizer to 100 parts by weight of dried high elastic polyvinyl chloride secondary particles to a thickness of 100 to 200 ㎛ By coating and drying at 180 to 200 ° C. for 3 to 7 minutes.

Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, the scope of the present invention is not limited to an Example.

Example

Example  One

Acrylonitrile-butadiene rubber (NBR) in an aqueous latex state of 60 wt% butadiene content and 1 μm average particle size, based on 100 parts by weight of polyvinyl chloride primary particles having an average degree of polymerization of 1,000 and an average particle diameter of 1 μm. After mixing 10 parts by weight, polyvinyl chloride secondary particles having an average particle diameter of 10 m were prepared by drying by the spray drying method. Next, 80 parts by weight of dioctylphthalate (DOP), which is a primary plasticizer, and 2,2,4-trimethyl-1,3-pentanediol di, which is a secondary plasticizer, based on 100 parts by weight of the polyvinyl chloride secondary particles. 20 parts by weight of isobutyrate (2,2,4-trimethyl-1,3-pentanediol diisobutyrate; TXIB), 3 parts by weight of a metal salt-based thermal stabilizer (Zinc Stearate, Songwon, SZ210) are uniformly mixed with a mixer for 10 minutes After the sol was prepared, it was coated on a release paper with a thickness of 0.2 mm. The coated mixture (plastisol) was baked in an oven at 200 ° C. for 1 minute to make a film.

Example  2

A film was prepared in the same manner as in Example 1, except that 100 parts by weight of the polyvinyl chloride primary particles having an average degree of polymerization of 100 and an average particle diameter of 0.1 μm were used.

Example  3

100 parts by weight of polyvinyl chloride primary particles having an average degree of polymerization of 2,000 and an average particle diameter of 2 μm were used, and 10 parts by weight of acrylonitrile-butadiene rubber (NBR) in an aqueous latex state having an average particle diameter of 0.05 μm was mixed. Then, a film was prepared in the same manner as in Example 1.

Example  4

Polyvinyl chloride secondary particles were prepared using 10 parts by weight of acrylonitrile-butadiene rubber (NBR) in an aqueous latex state having a butadiene content of 80% by weight, and based on 100 parts by weight of the polyvinyl chloride secondary particles. 90 parts by weight of a plasticizer, dioctylphthalate (DOP), a second plasticizer, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (2,2,4-trimethyl-1,3-pentanediol diisobutyrate; A film was prepared in the same manner as in Example 1, except that plastisol was prepared using 10 parts by weight of TXIB).

Example  5

A film was prepared in the same manner as in Example 1, except that 20 parts by weight of acrylonitrile-butadiene rubber (NBR) in an aqueous latex state was used.

Example  6

A film was prepared in the same manner as in Example 4, except that 20 parts by weight of acrylonitrile-butadiene rubber (NBR) in an aqueous latex state was used.

Example  7

A film was prepared in the same manner as in Example 1, except that 5 parts by weight of acrylonitrile-butadiene rubber (NBR) in an aqueous latex state was used.

Example  8

A film was prepared in the same manner as in Example 1, except that 30 parts by weight of acrylonitrile-butadiene rubber (NBR) in an aqueous latex state was used.

Example  9

Example 1 except that instead of acrylonitrile-butadiene rubber (NBR) butadiene content of 60 wt% and 10 parts by weight of styrene-butadiene rubber (SBR) in an aqueous latex state having an average particle diameter of 1㎛ Films were prepared in the same manner.

Example  10

Example 1 except that 10 parts by weight of styrene-butadiene rubber (SBR) in an aqueous latex state having a butadiene content of 80% by weight and an average particle diameter of 1 μm was used instead of acrylonitrile-butadiene rubber (NBR). Films were prepared in the same manner.

Example  11

Example 1 except that 20 parts by weight of styrene-butadiene rubber (SBR) in an aqueous latex state having a content of 60% by weight butadiene and an average particle diameter of 1 μm instead of acrylonitrile-butadiene rubber (NBR) Films were prepared in the same manner.

Example  12

Instead of acrylonitrile-butadiene rubber (NBR), polyvinyl chloride secondary particles were prepared using 20 parts by weight of styrene-butadiene rubber (SBR) in an aqueous latex state having an amount of butadiene of 80 wt% and an average particle diameter of 1 μm. 70 parts by weight of dioctylphthalate (DOP) as the primary plasticizer and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate as the secondary plasticizer (100 parts by weight of the polyvinyl chloride secondary particles) A film was prepared in the same manner as in Example 1, except that 30 parts by weight of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB) was used to prepare a plastisol.

Example  13

Example 1 except that 5 parts by weight of styrene-butadiene rubber (SBR) in an aqueous latex state having a butadiene content of 60% by weight and an average particle diameter of 1 μm was used instead of acrylonitrile-butadiene rubber (NBR). Films were prepared in the same manner.

Example  14

Instead of acrylonitrile-butadiene rubber (NBR) except that 10 parts by weight of methacrylate-butadiene-styrene rubber (MBS) in an aqueous latex state having a content of butadiene of 60% by weight and an average particle diameter of 1 µm was used. A film was prepared in the same manner as in Example 1.

Example  15

Instead of acrylonitrile-butadiene rubber (NBR) except that 10 parts by weight of methacrylate-butadiene-styrene rubber (MBS) in an aqueous latex state having a content of butadiene of 80% by weight and an average particle diameter of 1 µm was used. A film was prepared in the same manner as in Example 1.

Example  16

Instead of acrylonitrile-butadiene rubber (NBR), except that 20 parts by weight of methacrylate-butadiene-styrene rubber (SBR) in an aqueous latex state having a content of butadiene of 60% by weight and an average particle diameter of 1 µm was used. A film was prepared in the same manner as in Example 1.

Example  17

Instead of acrylonitrile-butadiene rubber (NBR) except that 20 parts by weight of methacrylate-butadiene-styrene rubber (SBR) in an aqueous latex state having a content of butadiene of 80% by weight and an average particle diameter of 1 µm was used. A film was prepared in the same manner as in Example 1.

Example  18

Instead of acrylonitrile-butadiene rubber (NBR) except that 5 parts by weight of methacrylate-butadiene-styrene rubber (SBR) in an aqueous latex state having a content of butadiene of 60% by weight and an average particle diameter of 1 µm was used. A film was prepared in the same manner as in Example 1.

Comparative example  One

A film was prepared in the same manner as in Example 1, except that no rubber particles were mixed with the polyvinyl chloride particles.

Comparative example  2

Butadiene content of 80 parts by weight of polyvinyl chloride having an average degree of polymerization of 1,000 25% by weight of acrylonitrile-butadiene rubber (NBR) by weight, 50 parts by weight of dioctylphthalate (DOP) as a primary plasticizer, 2,2,4-trimethyl-1,3-pentanediol as a secondary plasticizer 20 parts by weight of diisobutyrate (2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB), 3 parts by weight of a metal salt-based heat stabilizer (Zinc Stearate, Songwon Industries, SZ210) are mixed evenly using a mixer. Dispersed. Next, the mixed raw materials were kneaded in a 150 ° C. bamboo berry mixer and the kneaded raw materials were first and second mixed on a roll at 150 ° C., respectively, and a 0.4 mm thick film was produced using a calender. .

(Performance Evaluation-Evaluation of Elastic Properties)

Tensile strength and Elongation  Test

Tensile strength and elongation were measured for the films prepared in Examples 1 to 18 and Comparative Examples 1 and 2 based on the ASTM D 412-98a method. The results are shown in Table 1 below.

Resilience test

The films prepared in Examples 1 to 18 and Comparative Examples 1 to 2 were cut to a width of 1 cm and a length of 10 cm, and then maintained at 20 cm for 3 minutes, and then restored to their original state after 5 minutes. The results are shown in Table 1 below.

 Restoration Rate = (Initial Length (10cm) / Restored Length) X 100

division Resin composition Elastic properties Polyvinyl chloride content (parts by weight) Rubber type Rubber content (parts by weight) Butadiene content (% by weight) Tensile strength (Mpa) Elongation (%) % Recovery Example 1 100 NBR 10 60 12 600 95 Example 2 100 NBR 10 60 12 600 95 Example 3 100 NBR 10 60 12 580 92 Example 4 100 NBR 10 80 11 650 92 Example 5 100 NBR 20 60 10 700 96 Example 6 100 NBR 20 80 9 730 95 Example 7 100 NBR 5 60 13 480 85 Example 8 100 NBR 30 60 9 750 95 Example 9 100 SBR 10 60 13 550 93 Example 10 100 SBR 10 80 12 580 91 Example 11 100 SBR 20 60 11 610 94 Example 12 100 SBR 20 80 10 640 92 Example 13 100 SBR 5 60 13 440 82 Example 14 100 MBS 10 60 12 580 95 Example 15 100 MBS 10 80 12 620 93 Example 16 100 MBS 20 60 11 680 95 Example 17 100 MBS 20 80 10 700 94 Example 18 100 MBS 5 60 13 440 84 Comparative Example 1 100 - - - 14 400 80 Comparative Example 2 100 NBR 25 80 10 300 85

As can be seen in Table 1, the film produced using the composition according to the present invention can be confirmed that the elasticity is excellent because the elongation and recovery rate is very excellent, the elasticity can be controlled according to the butadiene content in the rubber You can make the right choice.

The reason why the elasticity is excellent is that the polyvinyl chloride and the rubber are not mixed with heat treatment in a powder or bulk state, but are mixed and prepared in an aqueous latex state, so that the uniformity is excellent.

In particular, when polyvinyl chloride and rubber are mixed in a powder state as in Comparative Example 2, the elongation and recovery rate are very low, whereas in the case of a film produced using the composition according to the present invention, the elongation is It can be seen that the maximum increase is up to 430% and the recovery rate is increased up to 11%.

Example  19 to 23

1, 2, 3, 4, 5 parts by weight of potassium ethyl xanthate (PEX) were added to 100 parts by weight of acrylonitrile-butadiene rubber (NBR) containing 36% by weight of butadiene and having an average particle diameter of 0.2 μm. Crosslinking treatment.

20 parts by weight of the crosslinked acrylonitrile-butadiene rubber (NBR) prepared by the above method with respect to 100 parts by weight of the polyvinyl chloride primary particle solids having an average polymerization degree of 1,000 and an average particle diameter of 1 μm, and spray-dried average particle diameter Polyvinyl chloride secondary particles of 10 to 50 μm were obtained. According to Examples 1 to 18 it can be seen that in the composition in which each rubber is dispersed in water, relatively excellent physical properties were shown at 20 parts by weight of a rubber content of 60% by weight of butadiene based on 100 parts by weight of polyvinyl chloride solids. The rubbers used in the Examples and Comparative Examples specified below are acrylonitrile-butadiene rubbers each containing 50 wt% butadiene, the same as in Examples 5, 11 and 16, based on Examples 1-18 above, The crosslinking agent addition effect was confirmed about the styrene-butadiene rubber and the methacrylate-butadiene-styrene rubber composition.

Thereafter, 100 parts by weight of the polyvinyl chloride secondary particles and 80 parts by weight of dioctylphthalate (DOP) as the primary plasticizer and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate as the secondary plasticizer ( 20 parts by weight of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB) and 3 parts by weight of a metallic thermal stabilizer (Zinc Stearate, Songwon Industries, SZ210) were mixed uniformly for 10 minutes with a mixer to prepare a plastisol. It was.

In addition, the film was prepared by coating the plastisol on a release paper with a thickness of 0.4 mm and thermally drying at 200 ° C. for 1 minute in an oven.

Example  24 to 28

Example 19 except that 1, 2, 3, 4, 5 parts by weight of gammamerbutoxypropyl-trimethoxysilane (MPTMS) was added to 100 parts by weight of acrylonitrile-butadiene rubber (NBR), respectively, to carry out crosslinking. Polyvinyl chloride secondary particles and a film using the same were prepared in the same manner.

Example  29 to 33

The film was prepared in the same manner as in Examples 19 to 23, except that 20 parts by weight of styrene-butadiene rubber (SBR) in an aqueous latex state having a butadiene content of 60% by weight instead of acrylonitrile-butadiene rubber (NBR) was used. Prepared.

Example  34 to 38

The film was prepared in the same manner as in Examples 24 to 28, except that 20 parts by weight of styrene-butadiene rubber (SBR) in an aqueous latex state having a butadiene content of 60% by weight instead of acrylonitrile-butadiene rubber (NBR) was used. Prepared.

Example  39 to 43

The same as in Examples 19 to 23 except that 20 parts by weight of methacrylate-butadiene-styrene rubber (MBS) in an aqueous latex state having a butadiene content of 60% by weight instead of acrylonitrile-butadiene rubber (NBR) was used. The film was prepared by the method.

Example  44 to 48

The same as in Examples 24 to 28, except that 20 parts by weight of methacrylate-butadiene-styrene rubber (MBS) in an aqueous latex state having a butadiene content of 60% by weight instead of acrylonitrile-butadiene rubber (NBR) was used. The film was prepared by the method.

Comparative example  3

The film was manufactured by the same method as Example 19 using 100 weight part of polyvinyl chloride secondary particles which mixed 20 weight part of acrylonitrile- butadiene rubber (NBR) particle | grains which were not crosslinked to the polyvinyl chloride primary particle.

Comparative example  4

The film was manufactured by the same method as Example 19 using 100 weight part of polyvinyl chloride secondary particles which mixed 20 weight part of styrene-butadiene rubber (SBR) particle | grains which were not crosslinked to the polyvinyl chloride primary particle.

Comparative example  5

A film was prepared in the same manner as in Example 19, using 100 parts by weight of polyvinyl chloride secondary particles in which 20 parts by weight of methacrylate-butadiene-styrene rubber (MBS) particles which had not been cross-linked to the polyvinyl chloride primary particles were mixed.

Comparative example  6

A film was prepared in the same manner as in Example 19, using 100 parts by weight of the polyvinyl chloride secondary particles without rubber particles mixed with the polyvinyl chloride primary particles.

(Performance Evaluation-Evaluation of Elastic Properties)

Tensile strength, elongation and recovery of the films prepared in Examples 19 to 48 and Comparative Examples 3 to 6 were measured in the same manner as described above.

(Performance Evaluation-Machinability Evaluation)

Processing viscosity test

The plastisols prepared in Examples 19 to 48 and Comparative Examples 3 to 6 were measured at room temperature (25 ° C) using a Brook Field viscometer LV type, # 3 spindle.

division Resin composition Elastic properties Machinability Polyvinyl chloride content (parts by weight) Rubber type Rubber content (part by weight) Rubber uncrosslinked species Crosslinking agent content (parts by weight) Tensile Strength (MPa) Elongation (%) Recovery rate (%) Processing viscosity (cps) Example 19 100 NBR 20 PEX 0.2 10 710 96 5500 Example 20 100 NBR 20 PEX 0.4 12 730 95 1600 Example 21 100 NBR 20 PEX 0.6 12 710 93 1500 Example 22 100 NBR 20 PEX 0.8 12 680 91 1500 Example 23 100 NBR 20 PEX 1.0 13 610 86 1500 Example 24 100 NBR 20 MPTMS 0.2 9 700 96 6000 Example 25 100 NBR 20 MPTMS 0.4 9 710 96 5400 Example 26 100 NBR 20 MPTMS 0.6 10 690 96 4800 Example 27 100 NBR 20 MPTMS 0.8 11 680 95 4500 Example 28 100 NBR 20 MPTMS 1.0 11 660 94 4200 Example 29 100 SBR 20 PEX 0.2 11 620 94 5200 Example 30 100 SBR 20 PEX 0.4 11 640 95 3800 Example 31 100 SBR 20 PEX 0.6 11 630 95 2700 Example 32 100 SBR 20 PEX 0.8 11 590 93 2000 Example 33 100 SBR 20 PEX 1.0 12 520 89 2100 Example 34 100 SBR 20 MPTMS 0.2 11 600 94 5900 Example 35 100 SBR 20 MPTMS 0.4 11 610 95 5500 Example 36 100 SBR 20 MPTMS 0.6 11 620 94 4900 Example 37 100 SBR 20 MPTMS 0.8 11 600 94 5200 Example 38 100 SBR 20 MPTMS 1.0 11 580 92 5100 Example 39 100 MBS 20 PEX 0.2 11 680 95 5800 Example 40 100 MBS 20 PEX 0.4 12 690 95 5600 Example 41 100 MBS 20 PEX 0.6 12 690 96 3200 Example 42 100 MBS 20 PEX 0.8 12 650 93 2700 Example 43 100 MBS 20 PEX 1.0 12 610 89 3000 Example 44 100 MBS 20 MPTMS 0.2 12 670 95 6000 Example 45 100 MBS 20 MPTMS 0.4 12 680 95 5800 Example 46 100 MBS 20 MPTMS 0.6 12 680 95 5300 Example 47 100 MBS 20 MPTMS 0.8 12 660 94 5200 Example 48 100 MBS 20 MPTMS 1.0 12 630 91 5200 Comparative Example 3 100 NBR 20 - 0 10 700 96 15000 Comparative Example 4 100 NBR 20 - 0 11 610 94 9500 Comparative Example 5 100 NBR 20 - 0 11 680 95 12000 Comparative Example 6 100 0 - 0 14 400 80 700

PEX: Potassium ethyl xanthate, MPTMS: gammamerbutoxypropyl trimethoxysilane

SO: styreneoxazoline, process viscosity: plastisol viscosity

As shown in Table 2, the films of Examples 19 to 48 using the polyvinyl chloride secondary particles prepared by mixing the rubber particles crosslinked to the polyvinyl chloride particles according to the present invention, the polyvinyl chloride primary particles The tensile strength was the same or improved as compared to Comparative Example 3 using polyvinyl chloride secondary particles prepared by mixing rubber particles not cross-linked.

The elongation and recovery of the films of Examples 19 to 48 were all improved in comparison with Comparative Example 6 without mixing the rubber particles, and nearly equivalent performances to the comparison with Comparative Examples 3 to 5 with the non-crosslinked rubber particles mixed. Improved performance.

In addition, Examples 20 to 23 are slightly higher than those of Comparative Example 6, which is polyvinyl chloride with no rubber particles in processing viscosity, but this is in a range that satisfies processing conditions of 500 to 2000 cps. Compared with Comparative Examples 3 to 5 using polyvinyl chloride secondary particles produced by mixing, the workability was greatly improved. The kind of crosslinking agent can be selected according to a use according to the kind of rubber particle, the kind of functional group contained, etc.

By using the polyvinyl chloride composition of the present invention, it is possible to prepare a highly elastic molded article having excellent elongation and high tensile strength, and the polyvinyl chloride composition according to the present invention does not increase the amount of plasticizer when molding a film to increase the viscosity. It is excellent in processing characteristics.

Claims (23)

A polyvinyl chloride-rubber particle comprising a polyvinyl chloride secondary particle and rubber particles formed by combining a plurality of polyvinyl chloride primary particles, In the polyvinyl chloride-rubber particles, the rubber particles are filled in the voids between the polyvinyl chloride primary particles forming the polyvinyl chloride secondary particles, The rubber particles are styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), methacrylate-butadiene-styrene rubber (MBS) or a mixture thereof. The method of claim 1, The polyvinyl chloride-rubber particles are obtained by mixing 100 parts by weight of polyvinyl chloride particles in a water-dispersive latex state and 1 to 30 parts by weight of rubber particles in a water-dispersive latex state, followed by drying. The method of claim 1, The high elastic polyvinyl chloride composition, characterized in that the average degree of polymerization of the polyvinyl chloride particles 100 to 3,000. The method of claim 1, The high elastic polyvinyl chloride composition, characterized in that the average particle diameter of the polyvinyl chloride primary particles is 0.1 to 2 ㎛. The method of claim 1, The polyvinyl chloride particles are prepared from a vinyl chloride single monomer or a mixed monomer obtained by mixing vinyl chloride and another monomer copolymerizable therewith. The method of claim 5, The other monomers are acrylic acid, etacrylic acid, alpha-cyanoacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, cyanoethyl acrylate, vinyl acetate, methyl methacrylate, ethyl methacrylate. Butyl methacrylate, acrylonitrile, methacrylonitrile, methylacrylamide, N-methyl-acrylamide, N-butoxy methacrylamide, ethyl vinyl ether, chloro-ethyl vinyl ether, alpha-methyl styrene, A high elastic polyvinyl chloride composition, characterized in that at least one selected from the group consisting of vinyl toluene, chlorostyrene, vinyl naphthalene, vinylidene chloride, vinyl bromide, vinyl chloroacetate, vinyl acetate, vinylpyridine and methyl vinyl ketone. delete The method of claim 1, The high elastic polyvinyl chloride composition, characterized in that the content of butadiene in the styrene-butadiene rubber (SBR) is 60 to 90% by weight. The method of claim 1, The content of butadiene in the acrylonitrile-butadiene rubber (NBR) is a high elastic polyvinyl chloride composition, characterized in that 50 to 90% by weight. The method of claim 9, The acrylonitrile-butadiene rubber (NBR) is a high elastic polyvinyl chloride composition, characterized in that it further comprises 1 to 10 parts by weight of a monomer having a carboxyl group with respect to 100 parts by weight of the total content of acrylonitrile and butadiene. The method of claim 1, A high elastic polyvinyl chloride composition, characterized in that the methacrylate content in the methacrylate-butadiene-styrene rubber (MBS) is 5 to 30% by weight and the content of butadiene is 60 to 90% by weight. The method of claim 1, The high elastic polyvinyl chloride composition, characterized in that the average degree of polymerization of the rubber particles 100 to 3,000. The method of claim 1, The high elastic polyvinyl chloride composition, characterized in that the average particle diameter of the rubber particles is 0.05 to 1 ㎛. The method of claim 1, A high elastic polyvinyl chloride composition, characterized in that it further comprises 80 to 100 parts by weight of a plasticizer based on 100 parts by weight of the polyvinyl chloride-rubber particles. The method of claim 14, The plasticizer is composed of 70 to 90 parts by weight of the primary plasticizer and 10 to 30 parts by weight of the secondary plasticizer, The primary plasticizer is at least one selected from the group consisting of dioctyl phthalate, diisononyl phthalate, and butylbenzyl phthalate, and the secondary plasticizer is 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (2,2,4-trimethyl-1,3-pentanediol diisobutyrate), a mixture of 1-phenyl-1-xylethane and 1-phenyl-1-ethylphenylethane, polyether modified polydimethylsiloxane copolymer, dioctylphthalate High elastic polyvinyl chloride composition, characterized in that at least one selected from the group consisting of. delete The method of claim 1, A high elastic polyvinyl chloride composition, wherein the rubber particles are crosslinked by a crosslinking agent. The method of claim 17, The crosslinking treatment is carried out by adding and stirring 0.5 to 10 parts by weight of the crosslinking agent solids at a temperature of 10 to 95 ° C. to 100 parts by weight of the rubber solids in the latex state and stirring. The method of claim 17, The crosslinking agent is trimethylolpropane-trimethacrylate, triarylcyanurate, triaryl isocyanurate, N, N'-methenphenylenedimaleimide, ethylene glycol dimethacrylate, vinyl-1,2-poly Butadiene, 1,1-t-butylperoxy-3,3,5-trimethylcyclohexane, n-butyl-4,4-bisbutylphosphoxyvalerate, dicumylperoxide, benzoylperoxide, t-butylperoxy Benzoate, di-t-butylperoxide, 2,5-dimethyl-2,5-di-t-butylperoxynucleic acid, paraquinonedioxine, dibenzoylparaquinonedioxine, tetrachloroparabenzoquinone, hexamethylenetetra Amine, acetaldehyde ammonia, butylaldehyde ammonia, butylaldehyde butyl aniline, acetaldehyde aniline, diphenylguanidine, diorthotolylguanidine, orthotolylbiguananidine, N, N'-diethylthiourea, dibutylthiourea, dilaurylurea Thiourea, Trimethyl-Thiou Ah, mercetobenzothiazole, dibenzothiazyl disulfide, sodium-2-merceto-benzothiazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, Dipentamethylene-thiuram tetrasulfide, sodium dimethyldithiocarbamate, sodium dibutyldithio-carbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, ferric dimethyldithiocarbamate, cooperdimethyldithi Okabamate, zinc ethylphenyldithiocarbamate, zinc dibutyldithiocarbamate, zinc butyl xanthate, zinc isopropyl xanthate, zinc ethyl xanthate, sodium isopropyl xanthate, sodium ethyl xanthate, potassium Ethyl xanthate, potassium isopropyl xanthate, N-cyclohexyl-2-benzothiazoylsulfenamide, Nt-butyl-2-benzothiazoyl-sulfenamide, N- Sidiethylene-2-benzothiazoylsulfenamide, zinc oxide, zinc carbonate, magnesium oxide, lead monoxide, potassium hydroxide, stearic acid, oleic acid, lauric acid, zinc stearate, dibutylammonium oleate, vinyltrimethoxysilane, vinyl tree -Ethoxysilane, vinyl-tri- (2-methoxyethoxysilane), vinyltriacetoxysilane, gammamerbutoxypropyltrimethoxysilane, gammamerpattotri- (2-methoxyethoxysilane), gamma Group consisting of glycidylpropyltrimethoxysilane, gammameroctopropyltriethoxysilane, gammaaminopropyltrimethoxysilane, gammaaminopropyltrimethoxysilane, aminoalkylsilicone, styreneoxazoline, 2-methyloxazoline High elastic polyvinyl chloride composition, characterized in that at least one selected from. The method of claim 17, The high-elastic polyvinyl chloride composition is characterized in that the viscosity of 500 to 6,000 cps at 25 ℃. The method of claim 1, The high elastic polyvinyl chloride composition, characterized in that the average particle diameter of the polyvinyl chloride-rubber particles is 10 to 50 ㎛. A molded article produced using the high elastic polyvinyl chloride composition according to any one of claims 1 to 6, 8 to 15, or 17 to 21. The molded article according to claim 22, wherein the molded article is a film, a sheet or a tile.

Images