KR101533408B1 - Method for preparing polyvinyl chloride based paste resin and polyvinyl chloride based paste resin prepared by the same - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a method for producing a vinyl chloride paste resin and a vinyl chloride paste resin produced by the method. More particularly, the present invention relates to a vinyl chloride resin paste resin comprising a rubber component and two kinds of emulsifiers, Vinyl-based paste resin which is capable of producing a molded article having excellent elastic recovery rate at the time of processing and which does not significantly increase in viscosity and is easy to process, and a vinyl chloride-based paste resin produced by the method.

Description

METHOD FOR PREPARING POLYVINYL CHLORIDE BASED PASTE RESIN AND POLYVINYL CHLORIDE BASED PASTE RESIN PREPARED BY THE SAME Technical Field [1] The present invention relates to a vinyl chloride-

TECHNICAL FIELD The present invention relates to a method for producing a vinyl chloride paste resin and a vinyl chloride paste resin produced by the method. More particularly, the present invention relates to a vinyl chloride resin paste resin comprising a rubber component and two kinds of emulsifiers, To a vinyl chloride-based paste resin which is capable of producing a molded article having excellent elastic recovery rate at the time of processing and which is not easily increased in viscosity and which can be easily processed, and a method for producing the same.

Polyvinyl Chloride based Resin is a kind of general-purpose resin widely used for daily necessities and industries such as building materials, wallpaper, artificial leather, woven fabric, sheet, film and the like.

The vinyl chloride resin may be prepared by mixing a vinyl chloride monomer alone, or a mixture of a vinyl chloride monomer and a comonomer copolymerizable therewith, an emulsifier, a buffering agent, and a polymerization initiator, etc. and mixing them by a method such as micro suspension polymerization, emulsion polymerization, Can be obtained in the form of fine particles by drying a polyvinyl chloride resin latex.

The vinyl chloride resin thus obtained may be used as a plastisol in various applications including plasticizers, stabilizers, fillers and the like. Particularly, a vinyl chloride copolymer resin containing vinyl chloride chloride as a copolymerizable monomer can be used for an adhesive layer of a car sealer (Under Body Coat, Body Sealer), a tile carpet and a tarpaulin. In order to increase the adhesive strength, It may also be included as a monomer.

The vinyl chloride paste resin is generally classified into a foamed product which is used by adding a foaming agent and a non-foamed product which does not contain a foaming agent when the plastisol is produced. Foamed products are mainly applied to wallpaper, artificial leather field, sink mats, automobile interior materials and so on, and Kofudo foam products require excellent resilience.

In general, a polyurethane resin is widely used for a product requiring excellent elastic restoring force. However, polyurethane resin is expensive compared with a vinyl chloride resin, and therefore, it is relatively inferior in the field where a vinyl chloride resin can be used.

In addition, a method of adding acrylonitrile-butadiene rubber (NBR) is used to improve the elasticity of a product using a vinyl chloride resin, but in general, it should be manufactured by a calendering method , There is a limitation in applying it to a vinyl chloride-based paste resin used in the form of a plastisol.

KR 2007-0019533 A KR 2009-0129530 A KR 2013-0120629 A

An object of the present invention is to provide a method for producing a vinyl chloride-based paste resin which is capable of producing a molded article having excellent elastic recovery rate at the time of plastisol processing, and which does not significantly increase viscosity and is easy to process.

Further, the present invention is to provide a vinyl chloride-based paste resin obtained by the above-mentioned method for producing a vinyl chloride-based paste resin.

The present invention also provides a molded article produced using the vinyl chloride-based paste resin.

The present invention relates to a resin composition comprising a latex resin, an anionic emulsifier, and a nonionic emulsifier mixed with a vinyl chloride resin and an acrylonitrile-butadiene rubber (NBR) in a weight ratio of 99: 1 to 90:10, Preparing a composition; And spray-drying the vinyl chloride resin composition to obtain a vinyl chloride paste resin.

In addition, the present invention relates to a resin composition obtained by the above-described method, wherein a vinyl chloride resin and an acrylonitrile-butadiene rubber (NBR) are mixed in a weight ratio of 99: 1 to 90:10, And a vinyl chloride resin having a particle diameter of less than 0.5 to 10 mu m.

Further, the present invention provides a molded article produced using the vinyl chloride-based paste resin.

The vinyl chloride-based paste resin obtained by the production method of the present invention can be obtained by using the anionic emulsifier and the nonionic emulsifier together, so that the paste resin to be produced has a proper particle diameter range and viscosity It is possible to provide a resin having an excellent elastic recovery rate without lowering the processability. In addition, since the use amount of the plasticizer required for the processing can be reduced by using two kinds of emulsifiers, it is possible to reduce the occurrence of environmental hormone problems caused by the plasticizer in the final molded product to be produced, and to produce a molded article having excellent elastic recovery rate .

The method for producing a vinyl chloride paste resin of the present invention is a method for producing a vinyl chloride paste resin, which comprises mixing a vinyl chloride resin and an acrylonitrile-butadiene rubber (NBR) in a weight ratio of 99: 1 to 90:10, Mixing a system emulsifier to prepare a vinyl chloride resin composition; And spray drying the vinyl chloride resin composition.

The vinyl chloride-based paste resin of the present invention is obtained by the above-mentioned production method, and is composed of vinyl chloride resin and acrylonitrile-butadiene rubber (NBR) in a weight ratio of 99: 1 to 90:10, And the average particle diameter of the base paste resin particles is less than 0.5 to 10 mu m.

Further, the molded article of the present invention is produced using the vinyl chloride-based paste resin.

In the present invention, the terms first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.

Moreover, the terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the present invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprising," "comprising," or "having ", and the like are intended to specify the presence of stated features, But do not preclude the presence or addition of one or more other features, integers, steps, components, or combinations thereof.

Also in the present invention, when referring to each layer or element being "on" or "on" each layer or element, it is meant that each layer or element is formed directly on each layer or element, Layer or element may be additionally formed between each layer, the object, and the substrate.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Throughout the present specification, the vinyl chloride resin refers to a (co) polymer obtained by copolymerizing a vinyl chloride monomer alone, or a vinyl chloride monomer and a comonomer copolymerizable therewith. In this case, the polyvinyl chloride may be used alone as a vinyl chloride monomer, or may be polymerized by a mixture of a vinyl chloride monomer and other comonomers copolymerizable therewith. In addition, a suspension, a buffer, a polymerization initiator, May be prepared by a polymerization method such as suspension polymerization, fine suspension polymerization, emulsion polymerization, or miniemulsion polymerization.

Other monomers copolymerizable with the above-mentioned vinyl chloride monomer include, for example, a vinyl ester monomer including an ethylene vinyl acetate monomer and a vinyl propionate monomer; Olefinic monomers including ethylene, propylene, isobutyl vinyl ether, and halogenated olefins; A methacrylic acid ester monomer containing a methacrylic acid alkyl ester; Maleic anhydride monomers; Acrylonitrile monomers; Styrene monomers; And halogenated polyvinylidene. One or more of these may be mixed to prepare a copolymer with a vinyl chloride monomer. However, the present invention is not limited to the above-mentioned monomers. In the technical field to which the present invention pertains, depending on physical properties and applications of the vinyl chloride resin composition required, The monomers used for the formation can be used without any particular limitation.

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

The vinyl chloride resin paste resin according to one aspect of the present invention comprises a latex resin in which a vinyl chloride resin and acrylonitrile-butadiene rubber (NBR) are mixed in a weight ratio of 99: 1 to 90:10, an anionic emulsifier , And a nonionic emulsifier to prepare a vinyl chloride resin composition; And spray drying the vinyl chloride resin composition.

The vinyl chloride based paste resin according to one embodiment of the present invention uses a latex resin in which a vinyl chloride resin and acrylonitrile-butadiene rubber (NBR) are mixed in a weight ratio of 99: 1 to 90:10 .

The vinyl chloride resin refers to a (co) polymer obtained by copolymerizing a vinyl chloride monomer alone or a vinyl chloride monomer and a comonomer copolymerizable with the vinyl chloride monomer.

The vinyl chloride resin is processed and can be produced as an everyday household goods such as building materials, wallpaper, artificial leather, woven fabric, sheet, film, etc. The vinyl chloride resin itself is processed by foaming products , It is difficult to provide sufficient elastic recovery force.

Therefore, in the method for producing a vinyl chloride-based paste resin of the present invention, a vinyl chloride resin component and an acrylonitrile-butadiene rubber (NBR) component are used. The vinyl chloride-based paste resin produced by the production method of the present invention may contain sufficient acrylonitrile-butadiene rubber (NBR) component so as to have sufficient resilience required for foamed products during processing.

The vinyl chloride resin and acrylonitrile-butadiene rubber (NBR) are mixed in a weight ratio of about 99: 1 to about 90:10. When the acrylonitrile-butadiene rubber (NBR) component is contained in an amount less than the above range, it may be difficult to provide a sufficient elastic recovery force in a molded article produced using such a resin, and the acrylonitrile-butadiene rubber (NBR) , The adhesion of the vinyl chloride resin and the latex resin containing the rubber component increases during the production process of the vinyl chloride paste resin, and during the drying process, the latex resin is sprayed onto the sprayer wheel, There is a problem that it is difficult to be formed into a small particle in the pulverization process after drying, so that it may be difficult to produce a paste resin having a uniform powder form, The viscosity of the sea plastisol is greatly increased, It may be difficult to use it as a general processing method of plastisol such as knife coating.

The vinyl chloride resin may be one prepared by suspension polymerization, micro suspension polymerization, emulsion polymerization or mini-emulsion polymerization, more preferably by micro suspension polymerization.

The average degree of polymerization of the vinyl chloride resin may preferably be about 500 to about 3,000. If the average degree of polymerization is less than about 500, there may arise a problem that the mechanical strength of a molded article to be produced later is lowered, and a polyvinyl chloride resin having a degree of polymerization of more than about 3,000 may be difficult to produce due to polymerization characteristics .

The acrylonitrile-butadiene rubber (NBR) particles of the above embodiment may also be prepared by suspension polymerization, micro suspension polymerization, emulsion polymerization, or miniemulsion polymerization, more preferably by mini-emulsion polymerization Lt; / RTI >

The acrylonitrile-butadiene rubber (NBR) component may be crosslinked by a crosslinking agent. Such a crosslinking treatment may be carried out by adding about 0.1 to 10 parts by weight of a crosslinking agent solid component to about 100 parts by weight of a solid component of acrylonitrile-butadiene rubber (NBR) in a latex state and stirring at a temperature of about room temperature to about 100 캜.

The cross-linking agent can be used without any particular limitation, and the cross-linking agent generally used for the cross-linking treatment of rubber in the technical field of the present invention is, for example, trimethylolpropane trimethacrylate, triallyl cyanurate, 1,1-t-butylperoxy-3,3,5-trimethylcyclohexyl methacrylate, isocyanurate, N, N'-metaphenylenediimaleimide, ethylene glycol dimethacrylate, vinyl-1,2-polybutadiene, Hexyl peroxide, t-butyl peroxybenzoate, di-t-butyl peroxide, 2,5-dimethyl-2,5 Di-t-butylperoxy nucleic acid, paraquinone dioxin, dibenzoyl paraquinone dioxin, tetrachloroparaffequinone quinone, hexamethylenetetramine, acetaldehyde ammonia, butylaldehyde ammonia, butylaldehydebutyl aniline, acetaldehyde aniline, diphenyl Guanie Dianthraquinone, dianthraquinone, dianthraquinone, dianthraquinone, dianthraquinone, dianthraquinone, dianthraquinone, dianthraquinone,

By using the crosslinked acrylonitrile-butadiene rubber (NBR) as the rubber component as described above, the viscosity can be easily controlled during the processing and the molding property in the processing can be further facilitated.

On the other hand, an anionic emulsifier is used in the vinyl chloride-based paste resin manufacturing method of the present invention. Anionic emulsifiers are used for imparting excellent interfacial properties in the production of vinyl chloride resin compositions, and are easily available and relatively inexpensive.

The anionic emulsifier can be used without any particular limitation. Examples of the anionic emulsifier include sodium lauryl sulfate and ammonium lauryl sulfate, which are commonly used in the art to which the present invention belongs. Alkyl sulphate salts including sodium dodecyl benzene sulfonate, linear or branched chain fatty acid salts having 6 to 20 carbon atoms, alkyl sulfonic acid salts, alkyl aryl sulfonic acid salts, Sulfosuccinic acid ester salt, and alkyldisulfonic acid diphenyl oxide salt may be used alone or in admixture of one or more, but the present invention is not limited thereto.

The anionic emulsifier may be included in an amount of about 0.1 part by weight to about 1 part by weight based on 100 parts by weight of the latex resin. When the anionic emulsifier is contained in an amount less than the above range, latex stability is lowered during the production of the vinyl chloride-based paste resin, and the latex particles are clustered together to form large particles having a large particle size. When the anionic emulsifier is contained in an amount exceeding about 1 part by weight , The average particle size of the particles in the latex resin formed becomes small, and when the plastisol is processed later, the viscosity of the sol is increased and the workability is lowered.

On the other hand, in the method for producing a vinyl chloride-based paste resin of the present invention, a nonionic emulsifier is used together with the anionic emulsifier. The nonionic emulsifier does not have a hydrophilic ionization group in the molecule, but has a hydrophilic group that does not ionize, and can suppress the viscosity increase of the latex resin.

The non-ionic emulsifier may be a nonionic emulsifier generally used in the art to which the present invention belongs. Examples of the nonionic emulsifier include polyethylene glycol, polyoxyethylene alkyl ether, It is possible to use polyethylene oxide, polypropylene oxide, ethyleneglycol monoaurate or polyoxyethylene nonylphenyl ether alone or in combination of one or more kinds thereof However, the present invention is not limited thereto.

The nonionic emulsifier may be included in an amount of about 0.01 part by weight to about 1 part by weight based on 100 parts by weight of the latex resin. When the nonionic emulsifier is contained in an amount lower than the above range, the viscosity increase suppressing effect obtained by adding the nonionic emulsifier may not be exhibited. If the nonionic emulsifier is contained in an amount exceeding the above range, the foamability and heat resistance are deteriorated Can occur.

As described above, the vinyl chloride-based paste resin of the present invention, by using the anionic emulsifier and the nonionic emulsifier together, shows a proper range of particle diameter and viscosity of the paste resin to be produced despite the rubber component having strong adhesive force, It is possible to provide a resin having an excellent elastic recovery rate without lowering the elasticity. In addition, since the use amount of the plasticizer required for processing can be reduced by using two kinds of emulsifiers, it is possible to reduce the occurrence of an environmental hormone problem due to the plasticizer in the final molded product to be produced.

The production method of the vinyl chloride-based paste resin will be described in detail as follows.

First, a vinyl chloride resin and an acrylonitrile-butadiene rubber (NBR) are dispersed on distilled water to form a water-dispersed latex state, followed by mixing. At this time, the content ratio of the vinyl chloride resin and the acrylonitrile-butadiene rubber (NBR) is as described above.

A vinyl chloride resin in a water-dispersed latex state and an acrylonitrile-butadiene rubber (NBR) in a water-dispersed latex state are mixed, and then an anionic emulsifier and a nonionic emulsifier are added thereto.

Thereafter, the mixture in which the vinyl chloride resin in the water dispersion latex state, the acrylonitrile-butadiene rubber (NBR) in the water dispersion latex state, the anionic emulsifier, and the nonionic emulsifier are mixed is dried. The drying method is not particularly limited as long as it is generally used in the technical field of the present invention. For example, it can be dried by a spray drying method, a nozzle spray drying method, or a freeze drying method, May be preferable for producing a resin in the form of a paste having a certain size and shape.

In drying, generally, since no separate filtration step such as dehydration filtration is performed, the substances contained in the additive such as an emulsifier remain in the resin.

In addition, the manufacturing method according to an embodiment of the present invention may further include a pulverizing step after the spray drying step. Through the pulverization process, a vinyl chloride paste resin can be obtained in the form of particles.

According to another aspect of the present invention, a vinyl chloride resin and an acrylonitrile-butadiene rubber (NBR), which are obtained by the above production method, are mixed in a weight ratio of about 99: 1 to about 90:10 , And a vinyl chloride-based paste resin having an average particle diameter of the vinyl chloride-based paste resin particles of about 0.5 to less than about 10 mu m.

The average particle diameter of the vinyl chloride-based paste resin particles may be about 0.5 to less than about 10 mu m, and preferably about 4 to less than about 10 mu m. When the average particle diameter of the resin particles is less than about 0.5 占 퐉, the viscosity of the paste resin itself is increased to limit the increase in addition amount of acrylonitrile-butadiene rubber (NBR), thereby satisfying the elastic recovery required for foamed products There is a problem that can not be done. If the average particle diameter is 10 탆 or more, the cell size of the foamed product may not be precise, resulting in a problem that the value of the product as a product is deteriorated.

Other latex resins, anionic emulsifiers, nonionic emulsifiers, and other additives are as described above in the production method of the vinyl chloride-based paste resin.

The vinyl chloride-based paste resin that can be obtained by such a method can further be processed into a plastisol by further including additives such as plasticizers, stabilizers, fillers, scoring agents, and foaming agents, and specifically, Foam products, or non-foam products that do not contain a blowing agent.

The plasticizer that can be used herein may be any plasticizer commonly used in the art to which the present invention belongs. For example, adipic acid, dimethyl adipate, diethyl adipate, diisobutyl adipate, Adipic acid plasticizers including dialkyl adipates such as di-n-hexyl adipate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, amide esters, azelate, benzoate, The plasticizers such as sol, glutarate, glycerol ester, glycol ester, glycol, glycolate, hexahydrophthalate, isobutyrate and isophthalate may be used alone or in admixture.

By adding such a plasticizer, flexibility can be imparted to the produced plastisol, and the viscosity can be adjusted to be suitable for processing. In the production method of the present invention, the viscosity of the paste resin to be produced can be easily controlled by using two kinds of emulsifiers together, and the use of less plasticizer is advantageous, thereby reducing the occurrence of environmental hormone problems. For example, the vinyl chloride-based paste resin of the present invention can exhibit a sufficient viscosity for processing even when a plasticizer is used in an amount of less than about 70 parts by weight based on 100 parts by weight of the vinyl chloride-based paste resin.

The stabilizer may be any one generally used in the technical field of the present invention without any particular limitations. For example, a stabilizer such as a tin stabilizer, a calcium-zinc stabilizer, a barium stabilizer, a hydrotalcite stabilizer, ; Zeolitic stabilizers; And an epoxy stabilizer may be used alone or in combination of one or more.

In addition, the foaming agent may be a conventional blowing agent used in the foaming of a vinyl chloride resin in the technical field of the present invention without any particular limitation. For example, an azodicarbonamide based foaming agent may be used.

According to another aspect of the present invention, there is provided a molded article produced using the vinyl chloride-based paste resin. The production of such a molded product can be carried out by a sol-gelation reaction of the plastisol containing the vinyl chloride-based paste resin, and the plastisol can be knife coated, roll coated, screen coated (Release paper or the like), and then the gelation reaction and foaming are conducted while passing through a hot air oven at 160 to 250 DEG C, and the resulting product is subjected to a cooling roll to final product.

Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through specific examples of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

< Example >

Vinyl chloride series  Manufacture of paste resin

[Example 1]

A latex resin was prepared by mixing polyvinyl chloride on a water-dispersed latex and a crosslinked acrylonitrile-butadiene rubber (NBR) on a water-dispersed latex prepared by emulsion polymerization in a weight ratio of 97: 3, 0.5 part by weight of sodium lauryl sulfate as an anionic emulsifier and 0.3 part by weight of polyoxypropylene oxyethylene as a nonionic emulsifier were added based on 100 parts by weight of the latex resin.

The mixture was spray-dried at 160 DEG C with a spray drier (trade name: Spray Dryer, manufactured by GEA Niro) and then pulverized in the same machine to prepare a vinyl chloride-based paste resin in the form of particles.

[Example 2]

A vinyl chloride-based paste resin was prepared in the same manner as in Example 1, except that 0.5 part by weight of polyoxypropyleneoxyethylene was added as a nonionic emulsifier.

[Example 3]

A vinyl chloride paste resin was prepared in the same manner as in Example 1, except that 1.0 part by weight of polyoxypropyleneoxyethylene was added as a nonionic emulsifier.

[Example 4]

A vinyl chloride based paste resin was prepared in the same manner as in Example 1 except that latex polyvinyl chloride and acrylonitrile-butadiene rubber (NBR) were mixed in a weight ratio of 94: 6.

[Example 5]

A vinyl chloride paste resin was prepared in the same manner as in Example 1, except that latex polyvinyl chloride and acrylonitrile-butadiene rubber (NBR) were mixed in a weight ratio of 90:10.

[Comparative Example 1]

A vinyl chloride paste resin was prepared in the same manner as in Example 1, except that latex polyvinyl chloride and acrylonitrile-butadiene rubber (NBR) were mixed in a weight ratio of 80:20.

[Comparative Example 2]

No acrylonitrile-butadiene rubber (NBR) was used,

A vinyl chloride paste resin was prepared in the same manner as in Example 1, except that 0.5 part by weight of sodium lauryl sulfate as an anionic emulsifier and 0.7 part by weight of polyoxypropyleneoxyethylene as a nonionic emulsifier were used.

[Comparative Example 3]

A mixture of polyvinyl chloride on latex and acrylonitrile-butadiene rubber (NBR) in a weight ratio of 85:15 was used,

A vinyl chloride paste resin was prepared in the same manner as in Example 1 except that 0.5 part by weight of sodium lauryl sulfate as an anionic emulsifier and 0.5 part by weight of polyoxypropyleneoxyethylene as a nonionic emulsifier were used.

[Comparative Example 4]

A polyvinyl chloride on a latex and acrylonitrile-butadiene rubber (NBR) in a weight ratio of 94: 6 were used,

A vinyl chloride paste resin was prepared in the same manner as in Example 1 except that an anionic emulsifier was not used and 0.5 part by weight of polyoxypropyleneoxyethylene was used as a nonionic emulsifier.

[Comparative Example 5]

A polyvinyl chloride on a latex and acrylonitrile-butadiene rubber (NBR) in a weight ratio of 94: 6 were used,

A vinyl chloride paste resin was prepared in the same manner as in Example 1 except that 0.5 part by weight of sodium lauryl sulfate was used as an anionic emulsifier and a nonionic emulsifier was not used.

[Comparative Example 6]

A polyvinyl chloride on a latex and acrylonitrile-butadiene rubber (NBR) in a weight ratio of 94: 6 were used,

A vinyl chloride paste resin was prepared in the same manner as in Example 1, except that an anionic emulsifier and a nonionic emulsifier were not used.

Plastisol  Manufacture and manufacture of foamed molded parts

70 parts by weight of dioctyl phthalate (DOP) as a plasticizer, 3 parts by weight of a barium stabilizer as a stabilizer, and 3 parts by weight of an azo type foaming agent as a foaming agent were added to 100 parts by weight of the vinyl chloride-based paste resin prepared in the above- And then mixed in a vacuum condition for 15 minutes to prepare a plastisol.

The plastisol prepared above was coated to a thickness of 0.8 mm by a knife coating method, followed by foaming at 230 DEG C for 3 minutes using a Matis oven, followed by foaming at a magnification of 350% to produce a foamed molded article .

The compositions of the materials used in the above Examples and Comparative Examples are summarized in Table 1 below.

Latex resin Anionic emulsifier
(Parts by weight based on 100 parts by weight of latex resin) Nonionic emulsifier
(Parts by weight based on 100 parts by weight of latex resin) Polyvinyl chloride
(Parts by weight) NBR
(Parts by weight) Example 1 97 3 0.5 0.3 Example 2 97 3 0.5 0.5 Example 3 97 3 0.5 1.0 Example 4 94 6 0.5 0.3 Example 5 90 10 0.5 0.3 Comparative Example 1 80 20 0.5 0.3 Comparative Example 2 100 - 0.5 0.7 Comparative Example 3 85 15 0.5 0.5 Comparative Example 4 94 6 - 0.5 Comparative Example 5 94 6 0.5 - Comparative Example 6 94 6 - -

In Table 1, Comparative Example 2 does not include NBR, and the amounts of the anionic emulsifier and the nonionic emulsifier are based on 100 parts by weight of the latex resin.

< Experimental Example >

Dry processability evaluation experiment

When there is no particular problem in spray drying in the vinyl chloride paste resin manufacturing process of the above Examples and Comparative Examples, the atomizer is stopped due to the improvement of adhesion of O and latex, and the spray drying can not proceed further In the case of X,

Particle size measurement experiment

The average particle diameter of the vinyl chloride-based paste resin prepared in the above Examples and Comparative Examples was measured using a particle size analyzer (Mastersizer 3000, manufacturer: Melbourne).

Viscosity measurement experiment

The viscosity of the plastisol prepared in the above Examples and Comparative Examples was measured with a Brookfield viscometer at 25 ° C and 20 rpm in a No. 6 spindle after 1 hour from the production.

Foamability evaluation experiment

The foamed molded articles prepared in the above Examples and Comparative Examples were visually observed in terms of the state of the foamed cells and when the size and uniformity of the foamed cells were excellent on the basis of the size and uniformity, When the sex was low, it was evaluated as bad.

Elastic recovery rate  Evaluation experiment

The elastic recovery rate of the foamed molded article produced in the above Examples and Comparative Examples was measured using an elastic recovery rate meter (manufacturer: Instron model: 5900).

The foamed molded article was subjected to a load of 22.68 kgf for 5 minutes, and after the relaxation time elapsed for 5 minutes, the thickness deviation was measured, and the elastic recovery rate was calculated by the following equation.

(T ₀ : initial thickness of molded foam article, T ₁ : thickness measured after application of load to sheet)

The tensile strength  Measurement experiment

Tensile strengths of foamed molded articles prepared in Examples and Comparative Examples were measured using a measuring machine (Crosshead Speed 200 mm / min, manufactured by Instron).

Elongation  Measurement experiment

The elongations of the foamed molded articles prepared in the above Examples and Comparative Examples were measured using a measuring machine (Crosshead Speed 200 mm / min, manufactured by Instron).

The results of the viscosity measurement, foamability evaluation and elastic recovery rate evaluation are summarized in Table 2 below.

Dry processability Particle size
(탆) Viscosity
(cps) Foaming Elastic recovery rate
(%) The tensile strength
(kg / cm2) Elongation
(%) Example 1 O 7.2 14,500 Good 97.3 275 116 Example 2 O 6.8 11,000 Good 98.1 281 120 Example 3 O 5.1 9,700 Good 97.6 286 128 Example 4 O 7.8 48,000 Good 97.5 304 131 Example 5 O 9.6 64,000 Good 98.7 320 142 Comparative Example 1 X 35.1 198,000 Bad 99.1 181 90 Comparative Example 2 O 4.2 6,900 Good 82.5 215 96 Comparative Example 3 X 24.5 105,000 Bad 98.6 179 88 Comparative Example 4 X 21.4 102,300 Bad 97.2 166 91 Comparative Example 5 O 15.2 83,100 Bad 97.5 180 98 Comparative Example 6 X 27.7 132,500 Bad 98.1 164 85

In the case of the above example in which the ratio of polyvinyl chloride and acrylonitrile-butadiene rubber (NBR) was included in the range of 99: 1 to 9: 1 with respect to the dry formability evaluation, there was no significant problem in the spray drying process, In Comparative Examples 1 and 3 in which rhenitrile-butadiene rubber (NBR) was excessively contained and in Comparative Examples 4 and 6 in which only one type of emulsifier was used or in which no emulsifier was used, Atomizer was stopped and spray drying could not proceed.

Further, in the case of the examples, it was confirmed that the average particle size of the particles was distributed in the range of about 5 to about 10 mu m. Accordingly, it was predicted that the working property was excellent and the size of the foamed cell was proper when the paste resin was processed.

From the viewpoint of viscosity, the higher the content ratio of acrylonitrile-butadiene rubber (NBR) was, the higher the viscosity was also generally increased. In particular, Comparative Examples 1, 3 and 4, in which acrylonitrile-butadiene rubber (NBR) In Comparative Examples 4 to 6 in which only one type of emulsifier was used, or when no emulsifier was used, the viscosity was higher than those in Examples 1 to 5, and thus, it was predicted that the processability during processing was not very good.

In addition, in the case of Examples, there was no significant problem in terms of the uniformity of size and size of the foamed cells. However, in the case of Comparative Example 1 and Comparative Example 3 in which acrylonitrile-butadiene rubber (NBR) , The use of only one kind of emulsifier or the use of Comparative Examples 4 to 6 in which no emulsifier was used was observed, and the uniformity of foam cell size was also lowered.

From the viewpoint of the elastic recovery rate, in the case of the embodiment containing acrylonitrile-butadiene rubber (NBR) at a certain ratio, an excellent value of about 97% or more was generally obtained and a comparative example 2 containing no acrylonitrile-butadiene rubber (NBR) Which is superior to that of 82.5%.

In terms of tensile strength, in Examples, the tensile strengths in the range of about 270 to about 320 kg / cm 2 were very excellent, and Comparative Example 1 and Comparative Example 1 in which acrylonitrile-butadiene rubber (NBR) 3 and the acrylonitrile-butadiene-free Comparative Example 2, it was confirmed that the tensile strength was much lower than that of the Examples, and the use of only one type of emulsifier or the use of Comparative Examples 4 to 6 It was confirmed that the tensile strength was also greatly decreased.

In addition, from the viewpoint of elongation, in the case of the embodiment, it was shown that it has a very good elongation at about 115 to about 140%, but Comparative Example 1 and Comparative Example 3 in which acrylonitrile-butadiene rubber (NBR) And the acrylonitrile-butadiene-free Comparative Example 2, the elongation was much lower than that of the Example. In the case of using only one type of emulsifier or Comparative Examples 4 to 6 , And the elongation was found to be generally decreased.

Taken together, in Examples 1 to 5, it has been found that, while exhibiting excellent mechanical properties such as elastic recovery rate, tensile strength and elongation, including an appropriate amount of acrylonitrile-butadiene rubber (NBR) and two kinds of emulsifiers , There was no particular problem in the spray drying process, and it was confirmed that the viscosity, processing, and foamability were generally good.

In contrast, Comparative Example 2, which did not contain acrylonitrile-butadiene rubber (NBR), showed no significant problems in terms of dryness, viscosity, workability, and foamability, In Comparative Examples 1 and 3 containing acrylonitrile-butadiene rubber (NBR) above the standard, the elastic recovery rate was high, but it was confirmed that it was inferior to the examples in terms of the dry state, viscosity and workability. Comparative Examples 4 to 6 in which only one type of emulsifier was used or none were also inferior to those in Examples in terms of the drying state, viscosity and workability as compared with Examples, and mechanical properties such as tensile strength and elongation It was confirmed that it was not better than the example.

Claims (12)

A vinyl chloride resin composition is prepared by mixing a latex resin, an anionic emulsifier, and a nonionic emulsifier in which a vinyl chloride resin and an acrylonitrile-butadiene rubber (NBR) are mixed in a weight ratio of 99: 1 to 90:10 ; And
Spray-drying the vinyl chloride resin composition;
Wherein the anionic emulsifier comprises a lauryl sulfate salt;
A method for producing a vinyl chloride paste resin.
The method according to claim 1,
Wherein the vinyl chloride resin is produced by suspension polymerization, micro suspension polymerization, emulsion polymerization, or mini-emulsion polymerization.
The method according to claim 1,
Wherein the vinyl chloride resin has an average polymerization degree of 500 to 3,000.
The method according to claim 1,
Wherein the acrylonitrile-butadiene rubber (NBR) is prepared by suspension polymerization, micro suspension polymerization, emulsion polymerization, or mini-emulsion polymerization.
The method according to claim 1,
The latex resin is prepared by mixing a vinyl chloride resin in a water-dispersed latex state and an acrylonitrile-butadiene rubber (NBR) in a water-dispersed latex state with 99% by weight, based on the content of the vinyl chloride resin and acrylonitrile-butadiene rubber : 1 to 90:10 by weight, based on the total weight of the vinyl chloride resin.
The method according to claim 1,
Wherein the anionic emulsifier is contained in an amount of 0.1 to 1 part by weight based on 100 parts by weight of the latex resin.
The method according to claim 1,
Wherein the lauryl sulfate salt comprises at least one member selected from the group consisting of sodium lauryl sulfate and ammonium lauryl sulfate.
The method according to claim 1,
Wherein the nonionic emulsifier is contained in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the latex resin.
The method according to claim 1,
The nonionic emulsifier may be selected from the group consisting of polyethylene glycol, polyoxyethylene alkyl ether, polyethylene oxide, polypropylene oxide, ethyleneglycol monolaurate, And polyoxyethylene nonylphenyl ether. 2. A method for producing a vinyl chloride paste resin, comprising the steps of:
The method according to claim 1,
The method of producing a vinyl chloride paste resin further comprising a pulverizing step after spray drying.
A process for the preparation of a compound according to any one of claims 1 to 10,
Vinyl chloride resin and acrylonitrile-butadiene rubber (NBR) are mixed in a weight ratio of 99: 1 to 90:10, and the average particle diameter of the particles is 0.5 占 퐉 or more and less than 10 占 퐉 Vinyl chloride resin.
A molded article produced using the vinyl chloride-based paste resin according to claim 11.