KR20210001092A - Vinyl chloride polymer latex, preparation method thereof and plastisol comprising the same - Google Patents

Abstract

The present invention relates to vinyl chloride-based polymer latex, a method for preparing the same, and plastisol comprising the same. The vinyl chloride-based polymer latex of the present invention has a trimodal particle size distribution curve having three peaks, and by adjusting the content ratio for each particle size range, glossiness can be significantly lowered without a large increase in viscosity. The present invention can also form a very dense and uniform foaming cell even during plastisol foaming.

Description

Vinyl chloride polymer latex, preparation method thereof and plastisol comprising the same

The present invention relates to a vinyl chloride-based polymer latex having excellent viscosity properties, foaming properties, and low gloss properties when blending plastisols, a method for preparing the same, and a plastisol comprising the same.

Vinyl chloride-based polymers are resins containing 50% or more of vinyl chloride, and are inexpensive, easy to control hardness, and can be applied to most processing equipment, so their application fields are diverse. In addition, it is possible to provide a molded article having excellent physical and chemical properties, such as mechanical strength, weather resistance, chemical resistance, etc., and thus has been widely used in various fields.

These vinyl chloride-based polymers are prepared in different ways depending on the application. For example, a vinyl chloride-based polymer for straight processing such as an extrusion process, a calendar process, and an injection process is generally prepared by suspension polymerization, and a vinyl chloride-based polymer for paste processing such as dipping, spraying, and coating is prepared by emulsion polymerization. At this time, the prepared vinyl chloride-based polymer is formed in the form of a vinyl chloride polymer latex, and can be used after drying the vinyl chloride-based polymer latex through processing and molding processes.

The paste processing is generally dried by spray drying a vinyl chloride-based polymer latex for paste processing obtained by emulsion polymerization to form final resin particles, and the particles are dispersed in a solvent or plasticizer to form a coating (reverse roll-coating, knife). coating, screen coating, spray coating), gravure and screen printing, rotation casting, shell casting and dipping through processes such as flooring, wallpaper, tarpaulin, raincoat, It is applied to products such as gloves, automobile underbody coatings, sealants, and carpet tiles.

The vinyl chloride-based polymer for paste processing may require excellent foam cell properties and matte properties of the foam sheet surface, depending on the application, especially when applied to products such as flooring and wallpaper. Specifically, the vinyl chloride-based polymer is commonly used by manufacturing a semi-finished sheet pregelling by applying heat after mixing the plastisol in a roll state, and to make the final finished product after storage in this state, unroll the roll again and print, It can go through the process of proceeding foaming. At this time, if the glossiness of the semi-finished sheet is high, the surface of the semi-finished sheet is sticky when dismantling the roll, and thus the quality of the product may be damaged, such as tearing the sheet due to adhesion between sheets or between rolls and sheets. In addition, if the glossiness of the finished product sheet after foaming is high, it is difficult to implement the primary color of the ink on the surface during printing, so that a molded product of a desired quality may not be obtained.

Accordingly, various studies have been conducted to improve the surface matting properties of semi-finished sheets and finished sheets made of vinyl chloride-based polymers. Among them, studies to realize matteness by adding inorganic particles such as titanium dioxide, silica, and calcium carbonate. Is the most widely known. However, since these inorganic particles have poor dispersibility in the polymer matrix, there is a problem that the surface of the molded article is formed unevenly due to non-uniform dispersion, and the viscosity of the molded product increases in the high shear region due to the addition of inorganic particles. When blending, the viscosity properties are lowered, the foaming ratio is lowered, and thus foaming properties may deteriorate.

Accordingly, there is a need to develop a vinyl chloride-based polymer capable of improving matte properties and foam cell properties while preventing other physical properties from deteriorating.

KR 10-0785172 B1 (2007.12.05)

The present invention has been devised to solve the problems of the prior art, and an object of the present invention is to provide a vinyl chloride-based polymer latex capable of having low glossiness and excellent foaming properties without a large increase in viscosity when blending plastisols.

Another object of the present invention is to provide a method for producing the above vinyl chloride-based polymer latex.

Another object of the present invention is to provide a vinyl chloride polymer powder prepared by drying the vinyl chloride polymer latex.

Another object of the present invention is to provide a plastisol containing the vinyl chloride-based polymer powder.

In order to solve the above problems, the vinyl chloride-based polymer latex according to an embodiment of the present invention has a first peak having a peak top particle diameter of 0.20 µm to 0.32 µm, a second peak having a peak top particle diameter of 0.33 µm to 1.39 µm, and It has a trimodal particle size distribution curve having a third peak having a peak top particle diameter of 1.40 µm to 2.00 µm, and exists between the first peak and the second peak based on the weight of the vinyl chloride-based polymer latex in the particle size distribution curve. 40% to 70% by weight of particles having a particle diameter of less than or equal to the minimum particle diameter, 5% to 52 by weight of particles having a particle diameter of less than or equal to the second minimum particle diameter, which exceeds the first minimum particle size, and exists between the second peak and the third peak It provides a vinyl chloride-based polymer latex comprising 8% by weight to 25% by weight of particles having a particle diameter exceeding the weight% and the second minimum particle diameter.

In addition, in the particle size distribution curve of the vinyl chloride-based polymer latex, the first minimum particle diameter is 0.30 µm to 0.80 µm, and the second minimum particle diameter is 1.40 µm to 1.75 µm.

In addition, by preparing the vinyl chloride-based polymer latex, the average particle diameter (D ₅₀ ) of a vinyl chloride-based polymer latex comprising the step of polymerizing a vinyl chloride-based monomer in the presence of at least three seed particles different from each other. Provides a manufacturing method.

In addition, it provides a method for producing a vinyl chloride-based polymer latex, wherein at least one of the seed particles is produced through polymerization of two or more times.

In addition, it provides a vinyl chloride-based polymer powder prepared by drying the vinyl chloride-based polymer latex.

In addition, a plastisol including the vinyl chloride-based polymer powder is provided, in which case the plastisol may include 40 to 180 parts by weight of a plasticizer based on 100 parts by weight of the vinyl chloride-based polymer powder.

The vinyl chloride-based polymer latex according to the present invention has a trimodal particle size distribution curve and adjusts the peak top particle size range and the distribution ratio of the particles to a specific range, thereby greatly increasing the viscosity and foaming of the foam sheet when mixing plastisol. By implementing remarkably low glossiness without cell collapse, it is possible to greatly improve the mattness of molded products.

In addition, the vinyl chloride-based polymer latex of the present invention can prevent deterioration of dispersibility of plastisol by excluding the addition of inorganic particles that implement matteness, and can improve surface properties of molded products.

In addition, the vinyl chloride-based polymer latex of the present invention exhibits excellent matte properties when blending plastisols, thereby suppressing the surface stickiness of the molded sheet when it is applied to wallpaper, flooring, etc., thereby dissolving the adhesion phenomenon between sheets. Can increase the ease of storage and handling. In addition, since the matte property is excellent, the primary color of the ink can be better implemented when the sheet surface is processed.

Accordingly, the vinyl chloride-based polymer latex and its manufacturing method according to the present invention can be easily applied to an industry that requires it, for example, a vinyl chloride-based resin industry for paste processing.

Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.

The terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

In this specification, the peak top particle diameter (D _p ) represents a particle diameter corresponding to a peak (maximum value) in the particle size distribution curve of the latex. The particle size distribution curve of the present invention shows a trimodal particle size distribution, so that three peaks (maximum values) may appear, and the particle size at each peak may be expressed as a peak top particle size. In addition, in the present specification, the first peak, the second peak, and the third peak may be specific according to the order in which the peaks appear, and the first peak, the second peak, and the third peak appear in each specific particle size range in the present invention. It may represent a peak.

In addition, in the present specification, the particle size distribution curve may represent the ratio of particles according to the particle size (particle diameter) of the particles in the latex, and specifically, the weight fraction (relative weight; %) of the particles according to the particle size It may be something to indicate.

In the present specification, the average particle diameter (D ₅₀ ) may be defined as a particle diameter corresponding to 50% of the cumulative amount of particle weight in the particle size distribution curve of the latex. The average particle diameter (D ₅₀ ) can be measured using, for example, a laser diffraction method. In general, the laser diffraction method can measure a particle diameter of about several mm from a submicron region, and high reproducibility and high resolution results can be obtained.

In the present specification, the first and second minima values represent the smallest values that exist between any one local maximum value corresponding to the peak top and the other maximum value in the particle size distribution curve of the latex, which increases when the particle weight ratio decreases. It may be a value at the time of transition to the state. The first and second may represent an order, for example, a minimum value existing between the first peak having the smallest peak top particle diameter and the second peak having the middle peak top particle diameter may be referred to as a first minimum value, and the second The minimum value existing between the peak and the third peak having the largest peak top particle diameter may be referred to as a second minimum value. In addition, the particle diameter at the first minimum value can be expressed as the first minimum value particle diameter, and the particle size at the second minimum value can be expressed as the second minimum value particle size.

According to an embodiment of the present invention, a first peak having a peak top particle diameter of 0.20 µm to 0.32 µm, a second peak having a peak top particle diameter of 0.33 µm to 1.39 µm, and a third peak having a peak top particle diameter of 1.40 µm to 2.00 µm Particles having a particle size distribution curve of trimodal having a particle size less than or equal to the first minimum particle diameter present between the first peak and the second peak based on the weight of the vinyl chloride-based polymer latex in the particle size distribution curve 40% to 70% by weight Particles having a particle diameter of 5% to 52% by weight exceeding the first minimum particle diameter and less than or equal to the second minimum particle diameter existing between the second peak and the third peak, and having a particle diameter exceeding the second minimum particle diameter It is possible to provide a vinyl chloride-based polymer latex containing 8% to 25% by weight of particles.

The vinyl chloride-based polymer latex according to an embodiment of the present invention may exhibit a trimodal particle size distribution having trimodality, and the trimodal particle size distribution may have three peaks. In the present specification, the first, second, and third peaks may represent peaks belonging to the specified particle diameter ranges, respectively, and may be displayed in order in a direction in which the peak top particle diameter increases.

According to an embodiment of the present invention, the range of the peak top particle diameter of the first peak may be 0.20 µm to 0.32 µm, and preferably 0.23 µm to 0.28 µm. If the peak top particle diameter of the first peak is less than 0.20 µm, the viscosity of the plastisol may increase rapidly when the plastisol is compounded due to excessively large particles with relatively small particle diameters, and there are many particles with small particle diameters. Therefore, as the surface smoothness is relatively high and the ratio of specular reflection increases, excellent low gloss characteristics are not exhibited. In addition, when the peak-top particle diameter range of the first peak exceeds 0.32 µm, the ratio of forming an open cell is greatly increased when the plastisol is foamed to form a foam cell, so the uniformity and compactness of the cell This may cause a problem of deteriorating foaming properties such as falling.

In addition, the range of the peak top particle diameter of the second peak may be 0.33 µm to 1.39 µm, and preferably 1.00 µm to 1.25 µm.

In addition, the range of the peak top particle diameter of the third peak may be 1.40 µm to 2.00 µm, preferably 1.55 µm to 1.90 µm, and more preferably 1.60 µm to 1.90 µm. When the peak top particle diameter of the third peak is less than 1.40 μm, the particle diameter of the relatively large particles in the polymer latex is not large enough to sufficiently realize the low gloss characteristics, so there is little effect of improving the low gloss characteristics, and the peak top particle diameter of the third peak is 2.00 μm. If it exceeds, the low-gloss characteristics may be improved, but the foamed cell becomes very large when the foam sheet is manufactured, and an open cell is observed due to the collapse of the cell, and the surface of the foam sheet is uneven, resulting in a large quality of the molded product. A worsening problem can occur.

In addition, according to an embodiment of the present invention, particles having a particle diameter less than or equal to the first minimum particle diameter present between the first peak and the second peak contain 40% by weight to 70% by weight based on the weight of the vinyl chloride-based polymer latex. It may be, preferably 45% by weight to 65% by weight, more preferably 45% by weight to 55% by weight. In the present invention, a particle having a particle diameter less than or equal to the first minimum particle diameter may represent a region including particles of peaks in which the first peak is formed in the particle size distribution curve. When particles having a particle diameter of the first minimum particle diameter or less are included in an amount of less than 40% by weight, the number of particles having a particle diameter exceeding the first minimum particle diameter becomes relatively larger, so that the overall particle size of the polymer latex increases and thus the foam sheet During manufacture, a problem of deteriorating foaming properties may occur.

In addition, particles having a particle diameter exceeding the first minimum particle diameter and less than or equal to the second minimum particle diameter present between the second peak and the third peak may contain 5% to 52% by weight based on the weight of the vinyl chloride-based polymer latex. It may be, preferably 20% by weight to 45% by weight, more preferably may include 30% by weight to 40% by weight. Particles having a particle diameter greater than the first minimum particle diameter and less than or equal to the second minimum particle diameter existing between the second peak and the third peak may represent a region including particles of peaks in which the second peak is formed in the particle size distribution curve. .

In addition, particles having a particle diameter exceeding the second minimum particle diameter may contain 8% to 25% by weight based on the weight of the vinyl chloride-based polymer latex, preferably 8% to 23% by weight, more preferably It may contain 10% to 20% by weight. Particles having a particle diameter exceeding the second minimum particle diameter may indicate a region including particles of peaks in which the third peak is formed in the particle size distribution curve. When particles having a particle diameter exceeding the second minimum particle diameter are included in an amount of less than 8% by weight, the proportion of particles contributing to realizing the low gloss characteristic is too small, so that the improvement of low gloss characteristics may occur. If it is contained in excess of 25% by weight, there may be a problem of deteriorating foaming properties when manufacturing a foam sheet.

In addition, according to an embodiment of the present invention, the first minima particle diameter in the particle size distribution curve may have any value without limitation as long as it is a particle diameter value between the peak top particle diameter at the first peak and the peak top particle diameter at the second peak. , Preferably it may be 0.30 µm to 0.80 µm, more preferably 0.35 µm to 0.65 µm, and even more preferably 0.45 µm to 0.55 µm. In addition, the second minimum particle diameter may have any value without limitation as long as it is a particle diameter value between the peak top particle diameter at the second peak and the peak top particle diameter at the third peak, but preferably 1.40 µm to 1.75 µm, more preferably Specifically, it may be 1.50 µm to 1.70 µm, and even more preferably 1.55 µm to 1.65 µm. When the first minimum particle diameter or the second minimum particle diameter satisfies the above particle diameter range, the excellent foaming properties desired in the present invention can be secured and the low gloss improvement effect can be further improved.

In the present invention, the particle size distribution and peak top particle diameter may be measured using a particle size meter (DC24000 UHR, CPS Instrument) after preparing a sample by diluting a vinyl chloride-based polymer latex in deionized water to 1% by weight.

In addition, the vinyl chloride-based polymer latex of the present invention has a trimodal particle size distribution (curve) as described above, and the peak top particle diameter of each peak has the particle diameter range as described above, and the particles in the region including each peak When the content ratio of is adjusted to a specific range, low gloss characteristics can be realized without a large increase in viscosity and collapse of the foam cells when the plastisol is blended.

Meanwhile, the vinyl chloride-based polymer latex may be prepared by a method described later using a vinyl chloride-based monomer, and thus a vinyl chloride-based polymer latex having a particle size distribution as described above can be obtained.

The vinyl chloride-based monomer may refer to a vinyl chloride monomer alone, or may refer to a mixture of a vinyl chloride monomer and a vinyl-based monomer copolymerizable therewith. That is, the vinyl chloride-based polymer latex according to an embodiment of the present invention may be a vinyl chloride homopolymer latex or a copolymer latex of a vinyl chloride monomer and a vinyl-based monomer copolymerizable therewith. If the vinyl chloride-based polymer latex is the copolymer latex, it may contain 50% or more of vinyl chloride.

The vinyl-based monomer capable of copolymer latex with the vinyl chloride-based monomer is not particularly limited, but, for example, olefin compounds such as ethylene, propylene, butene, vinyl esters such as vinyl acetate, vinyl propionate, and vinyl stearate. And unsaturated nitriles such as acrylonitrile, vinyl alkyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl octyl ether, and vinyl lauryl ether, halogenated vinylidene such as vinylidene chloride, acrylic acid, meta Unsaturated fatty acids such as acrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride, and anhydrides of these fatty acids, methyl acrylate, ethyl acrylate, monomethyl maleate, dimethyl maleate, and unsaturated fatty acid esters such as butylbenzyl maleate ( ester), and a crosslinkable monomer such as diallyl phthalate, and the like, and the vinyl-based monomer may be a single or a combination of two or more.

In addition, the present invention provides a method for producing the above vinyl chloride-based polymer latex.

The manufacturing method of the vinyl chloride-based polymer latex according to an embodiment of the present invention includes a step (step A) of polymerizing a vinyl chloride-based monomer in the presence of at least three seed particles having different average particle diameters (D ₅₀ ). I can.

Specifically, the polymerization of step A is a step for preparing a vinyl chloride-based polymer latex, and is performed by adding a vinyl chloride-based monomer to a polymerization reactor filled with the first seed particles, the second seed particles and the third seed particles, and polymerizing them. It can be. In this case, the polymerization of step A may be performed by a seed emulsion polymerization method.

Here, the polymerization reactor filled with the first seed particles, the second seed particles, and the third seed particles represents a polymerization reactor containing a mixed solution including the first seed particles, the second seed particles and the third seed particles. Can be.

According to an embodiment of the present invention, at least one of the seed particles may be produced through polymerization of two or more times during manufacture, and hard and large seed particles that are difficult to implement by emulsion polymerization through two or more polymerizations are produced. Can be.

The first seed particles may have an average particle diameter (D ₅₀ ) of 0.10 µm to 0.29 µm, specifically 0.10 µm to 0.23 µm, more specifically 0.10 µm to 0.20 µm, and 100 parts by weight of a vinyl chloride monomer Based on 1.0 parts by weight to 6.0 parts by weight, preferably 1.5 parts by weight to 3.4 parts by weight, more preferably 2.0 parts by weight to 2.8 parts by weight may be used. When the first seed particles are used in the particle size range and content ratio, the particle size distribution of the finally prepared vinyl chloride-based polymer latex can exhibit the desired properties, and as a result, excellent foaming properties and viscosity properties are obtained when the plastisol is blended. While securing low gloss characteristics can be improved.

In addition, the second seed particles may have an average particle diameter (D ₅₀ ) of 0.30 µm to 1.19 µm, specifically 0.30 µm to 1.00 µm, and 2.0 parts by weight to 15.0 parts by weight based on 100 parts by weight of the vinyl chloride monomer , Preferably, 3.0 parts by weight to 10.0 parts by weight, more preferably 4.0 parts by weight to 8.0 parts by weight may be used.

In addition, the third seed particles may have an average particle diameter (D ₅₀ ) of 1.20 µm to 1.60 µm, preferably 1.30 µm to 1.60 µm, and 3.0 parts by weight to 9.0 parts by weight based on 100 parts by weight of the vinyl chloride monomer Parts, preferably 3.5 parts by weight to 8.0 parts by weight, more preferably 4.0 parts by weight to 7.5 parts by weight, may be used. When the third seed particles are used in the particle size range and content ratio, the particle size distribution of the finally prepared vinyl chloride-based polymer latex can exhibit the desired characteristics, and as a result, excellent foaming characteristics and viscosity characteristics when blending plastisols are obtained. While securing, low gloss characteristics can be improved.

In general, when polymer latex seed particles are produced through emulsion polymerization, particles having a particle size range of about 0.10 to 1.00 µm are produced, and when particles having a particle diameter of more than that are produced, the strength of the particles is weakened. It was difficult to manufacture a polymer latex having a desired particle diameter because most of it was broken during the transfer to the polymerization reactor or during the polymerization process, and it was not easy to control the particle diameter of the produced polymer latex. Accordingly, in the present invention, particles smaller than the particle diameter of the third seed particles were first prepared through primary seed polymerization, and then additional seed polymerization was performed to prepare particles having the average particle diameter of the third seed particles. Likewise, as it is manufactured through two or more polymerizations, even by emulsion polymerization, particles having a relatively large particle size and yet hard particles can be produced.

In the present invention, by controlling the particle diameter range and amount of the first seed particles, the second seed particles, and the third seed particles as described above, excellent foaming properties and viscosity characteristics are exhibited, and low gloss characteristics can be greatly improved.

In addition, in the present invention, the first seed particle, the second seed particle, and the third seed particle may be materials having different average particle diameters even if they have the same vinyl chloride-based polymer composition, and the expressions of the first, second and third Silver may be used to distinguish seed particles having different average particle diameters.

Meanwhile, the first seed particles, the second seed particles, and the third seed particles may be prepared by adding a vinyl chloride-based monomer to a polymerization reactor and emulsion polymerization. Specifically, the first seed particles, the second seed particles, and the third seed particles may each be independently prepared, and chlorinated in a polymerization reactor filled with 0.01 parts by weight to 5 parts by weight of polymerization water, polymerization initiator and primary emulsifier. It may be prepared by adding 100 parts by weight of a vinyl-based monomer and emulsion polymerization at a temperature of 30° C. to 70° C., and if necessary, a homogenization process before emulsion polymerization may be performed. In addition, if necessary, after the polymerization reaction is started, 1 part by weight to 10 parts by weight of a secondary emulsifier may be added continuously for 1 to 10 hours, and the polymerization reaction may be performed.

Here, the polymerization initiator may be any one or more of the polymerization initiators described later.

In addition, parts by weight of the first and second emulsifiers may be parts by weight based on 100 parts by weight of the vinyl chloride-based monomer.

In the present invention, the first emulsifier and the second emulsifier may be different materials or the same material. When the first and second emulsifiers are the same material, the expressions of the first and second emulsifiers indicate the order in which the emulsifier is added. It may be to distinguish.

The polymerization reactor filled with the polymerization water, polymerization initiator, and primary emulsifier may represent a polymerization reactor containing a mixed solution containing polymerization water, a polymerization initiator, and a primary emulsifier, and the mixed solution is polymerization water, a polymerization initiator And an electrolyte, a reaction inhibitor, and a dispersant in addition to the primary emulsifier, but are not limited thereto.

The polymerization initiator may be used in an amount of 0.01 parts by weight to 2.0 parts by weight based on 100 parts by weight of the vinyl chloride-based monomer. The polymerization initiator is not particularly limited, but may be one or more selected from the group consisting of peroxy carbonates, peroxy esters, and azo compounds. Specifically, the polymerization initiator is lauryl peroxide (LPO), di-2-ethylhexyl peroxycarbonate (OPP), diisopropyl peroxy dicarbonate, t-butyl peroxypivalate, t-butyl peroxy Neodecanoate, 2,2-azobisisobutyronitrile, and the like may be used alone, or two or more may be used in combination.

In addition, the polymerization initiator may be a water-soluble initiator. When the polymerization initiator is a water-soluble initiator, it is not particularly limited, but may be one or more selected from the group consisting of potassium persulfate, ammonium persulfate, and hydrogen peroxide.

The reaction inhibitor is not particularly limited, for example, paraquinone, hydroquinone, butylated hydroxy toluene, monomethyl ether hydroquinone, quaternary butyl catechol, diphenyl amine, triisopropanol amine, triethanol Amines and the like can be used. In addition, the dispersant is not particularly limited, for example, higher alcohols such as lauryl alcohol, myristic alcohol, stearyl alcohol, or higher fatty acids such as lauryl acid, myristic acid, palmitic acid, and stearic acid. have.

The electrolyte is, for example, potassium chloride, sodium chloride, potassium bicarbonate, sodium carbonate, potassium carbonate, potassium hydrogen sulfite, sodium hydrogen sulfite, tetrapotassium pyrophosphate, tetrasodium pyrophosphate, tripotassium phosphate, trisodium phosphate, dipotassium hydrogen phosphate, and disodium hydrogen phosphate. It may be one or more selected from the group consisting of, and the electrolyte is not particularly limited, for example, potassium chloride, sodium chloride, potassium bicarbonate, sodium carbonate, potassium carbonate, potassium hydrogen sulfite, sodium hydrogen sulfite, tetrapotassium pyrophosphate, tetrasodium pyrophosphate , Tripotassium phosphate, trisodium phosphate, dipotassium hydrogen phosphate, and disodium hydrogen phosphate may be one or more selected from the group consisting of.

The first and second emulsifiers are each independently alkyl sulfate, alkyl ether sulfate, sulfated alkanolamide, glycerite sulfate, alkyl benzene sulfonate, alpha-olefin sulfonate, lignosulfonate, and alkyl sulfo acetate. It may include one or more selected from the group consisting of. In addition, the first emulsifier and the second emulsifier may each independently exist in a state in which the above-described salt has an ionic bond with an alkali metal such as sodium ions (Na ⁺ ). For example, the primary emulsifier and secondary emulsifier is one of sodium lauryl sulfate, lauryl benzene sulfonate, sodium dodecyl benzene sulfonate, sodium lauryl ethoxylated sulfate, sodium octadecyl sulfate, and sodium lauryl ether sulfate. It may be more than that. The primary emulsifier and secondary emulsifier used in the present invention may mean substances of different types, the same type and may mean only the order of addition. Therefore, the first emulsifier and the second emulsifier may be the same material or different materials.

The homogenization may be performed by homogenizing for 1 to 3 hours using a homogenizer at a temperature of 30 °C or less, specifically 5 °C to 25 °C. At this time, the homogenizer is not particularly limited, and a conventional one known in the art may be used, for example, a rotor-stator type homogenizer may be used.

The vinyl chloride-based monomer used in the emulsion polymerization of step A, the first seed particle, the second seed particle, and the vinyl chloride-based monomer used to prepare the third seed particle may be of the same material, and the vinyl chloride-based monomer is As described above, it may be a vinyl chloride monomer, or a combination of a vinyl chloride monomer and a vinyl-based monomer copolymerizable therewith. The specific type of the vinyl-based monomer may be as described above.

In addition, in the polymerization of step A, the polymerization reactor filled with the first seed particles, the second seed particles, and the third seed particles may contain a polymerization initiator, for example, a water-soluble polymerization initiator, if necessary, and the first emulsifier, 2 It may further contain any one or more of an emulsifier and polymerized water. In this case, the first emulsifier may be added before the vinyl chloride-based monomer is introduced into a reactor in which the seed particles and polymerized water are mixed, and the secondary emulsifier may be continuously added after polymerization is initiated.

Here, the first emulsifier, the second emulsifier, the water-soluble polymerization initiator, and the polymerization water are the first emulsifier, the second emulsifier, the polymerization initiator and the polymerization water used in the step of preparing the first seed particles or the second seed particles, respectively. It can be the same.

The polymerized water may be used in an amount of 70 to 120 parts by weight based on 100 parts by weight of the vinyl chloride-based monomer, and the polymerized water may be deionized water.

In the polymerization of step A, the water-soluble polymerization initiator may be used in an amount of 0.01 parts by weight to 2.0 parts by weight based on 100 parts by weight of the vinyl chloride-based monomer, but is not limited thereto. The water-soluble polymerization initiator is not particularly limited as described above, but may be one or more selected from the group consisting of potassium persulfate, ammonium persulfate, and hydrogen peroxide.

When the first emulsifier is added in the emulsion polymerization of step A, the first emulsifier may be used in an amount of 0.01 parts by weight to 0.4 parts by weight based on 100 parts by weight of the vinyl chloride-based monomer. Also, as an example, the present invention may not include the first emulsifier in step A.

In the emulsion polymerization of step A, the second emulsifier is continuously added after polymerization is started, as described above, and may be used in an amount of 1 to 10 parts by weight based on 100 parts by weight of the vinyl chloride-based monomer.

In the present invention, in the emulsion polymerization of step A, the first emulsifier and the second emulsifier may be different materials or the same material, and the first and second expressions when the first and second emulsifiers are the same material May be for distinguishing the order of addition of the emulsifier.

Meanwhile, in the emulsion polymerization of step A according to an embodiment of the present invention, additives such as a dispersant, a reaction inhibitor, and an electrolyte may be further used as needed, and each of the dispersant, reaction inhibitor, and electrolyte is the aforementioned first seed particle. , It may be the same as a dispersant, a reaction inhibitor, and an electrolyte used to prepare the second and third seed particles.

The manufacturing method according to an embodiment of the present invention may further include at least one or more of washing, coagulation, and drying after the polymerization of step A. The drying is not particularly limited and may be performed by a method commonly known in the art. For example, the vinyl chloride-based polymer latex may be dried through a spray drying method.

In addition, according to an embodiment of the present invention, it is possible to obtain a vinyl chloride polymer powder by drying the vinyl chloride polymer latex.

In addition, the present invention provides a plastisol containing the vinyl chloride-based polymer powder.

The plastisol according to an embodiment of the present invention may further contain 40 parts by weight to 180 parts by weight, preferably 50 parts by weight to 160 parts by weight of a plasticizer, based on 100 parts by weight of the vinyl chloride-based polymer powder. Depending on, it may further include additives such as a dispersion diluent, a heat stabilizer, a viscosity modifier, and a foaming agent.

The term “plastisol” used in the present invention refers to a mixture of a resin and a plasticizer so that it can be molded, molded or processed into a continuous film by heating. For example, a vinyl chloride-based polymer and a plasticizer are mixed. It may have a paste form.

The term “plasticizer” used in the present invention may refer to an organic additive material that serves to improve the molding processability of the resin at a high temperature by adding to a thermoplastic resin to increase thermoplasticity.

The plasticizers and additives may be those commonly known in the art.

The plastisol according to an embodiment of the present invention may exhibit viscosity characteristics, foam properties, and low gloss characteristics as described above by including the vinyl chloride-based polymer having a specific particle size distribution characteristic.

Hereinafter, the present invention will be described in more detail by examples and experimental examples. However, the following examples and experimental examples are for illustrative purposes only, and the scope of the present invention is not limited thereto.

Example

Manufacturing Example 1

After adding 230 kg of deionized water, 184 g of sodium lauryl sulfate (SLS) and 110 g of potassium persulfate (KPS) to a 500 L high-pressure reactor, a vacuum was applied to the reactor while stirring. After 185 kg of vinyl chloride monomer was added to a reactor in a vacuum state, the temperature of the reactor was raised to 56° C. to perform polymerization. When the polymerization reaction started, 11.1 kg of sodium lauryl sulfate (SLS) was continuously added to the reactor for 5 hours. And when the pressure in the reactor reached 3.5 kgf/cm ² , the reaction was terminated, the unreacted vinyl chloride monomer was recovered and removed, and then vinyl chloride-based first seed particles having an average particle diameter of 0.15 μm were obtained.

Manufacturing Example 2

70 kg of deionized water, 1.3 kg of lauryl peroxide (LPO), and 0.3 g of paraquinone were added to a 200 L high-pressure reactor, and then vacuum was applied to the reactor at -730 mmHg. 62 kg of vinyl chloride monomer and 6.8 kg of sodium dodecyl benzene sulfonate were added to a reactor in a vacuum state, followed by stirring for 30 minutes. The temperature in the reactor was lowered to 20° C. or less, and homogenization was performed for 3 hours using a rotor-stator type homogenizer. Upon completion of homogenization, polymerization was carried out by raising the temperature in the reactor to 45°C. When the pressure in the reactor reached 3.5 kgf/cm ² , the reaction was terminated, unreacted monomers were recovered and removed, and second seed particles having an average particle diameter of 0.60 μm were obtained.

Manufacturing Example 3

In a 500 L high-pressure reactor, 230 kg of deionized water, 81 g of potassium persulfate (KPS), and 1.8 kg of the second seed particles prepared in Preparation Example 2 were added, and a vacuum was applied to the reactor while stirring. After adding 180 kg of vinyl chloride monomer to a reactor in a vacuum state, the temperature of the reactor was raised to 56° C. to carry out polymerization. When the polymerization reaction started, 9.0 kg of sodium lauryl sulfate (SLS) was continuously added to the reactor for 5 hours. And when the pressure in the reactor reached 3.5 kgf/cm ² , the reaction was terminated, the unreacted vinyl chloride monomer was recovered and removed, and then a third vinyl chloride seed particle having an average particle diameter of 1.35 μm was obtained.

Example 1

In a 500 L high-pressure reactor, 143 kg of polymerization water, 24 g of potassium perate (KPS) as a water-soluble initiator, 3.9 kg of the first seed particle of Preparation Example 1, 9.9 kg of the second seed particle of Preparation Example 2, and Preparation Example 3 3 After adding 9.7 kg of seed particles, a vacuum was applied to the reactor while stirring. After adding 150 kg of vinyl chloride monomer to a reactor in a vacuum state, the temperature of the reactor was raised to 58° C. to carry out polymerization. When the polymerization reaction started, 1.6 kg of sodium lauryl sulfate was continuously added to the reactor for 6 hours. Thereafter, when the pressure in the reactor reached 3.5 kgf/cm ² , the reaction was terminated, and unreacted vinyl chloride monomer was recovered and removed to prepare a vinyl chloride polymer latex.

Example 2

In Example 1, a vinyl chloride polymer latex was prepared in the same manner as in Example 1, except that 4.7 kg of the first seed particles and 8.4 kg of the second seed particles were added.

Example 3

In Example 1, a vinyl chloride polymer latex was prepared in the same manner as in Example 1, except that 4.3 kg of the first seed particles and 7.5 kg of the third seed particles were added.

Example 4

In Example 1, a vinyl chloride polymer latex was prepared in the same manner as in Example 1, except that 10.2 kg of the second seed particles and 7.5 kg of the third seed particles were added.

Example 5

In Example 1, a vinyl chloride polymer latex was prepared in the same manner as in Example 1, except that 4.3 kg of the first seed particles and 9.3 kg of the second seed particles were added.

Comparative Example 1

After adding 143 kg of polymerization water, 24 g of potassium perate (KPS) as a water-soluble initiator, 5.1 kg of first seed particles having an average particle diameter of 0.25 μm, and 9.9 kg of the second seed particles of Preparation Example 2 to a 500 L high-pressure reactor Vacuum was applied to the reactor while stirring. After adding 150 kg of vinyl chloride monomer to a reactor in a vacuum state, the temperature of the reactor was raised to 58° C. to carry out polymerization. When the polymerization reaction started, 1.6 kg of sodium lauryl sulfate was continuously added to the reactor for 6 hours. Thereafter, when the pressure in the reactor reached 3.5 kgf/cm ² , the reaction was terminated, and unreacted vinyl chloride monomer was recovered and removed to prepare a vinyl chloride polymer latex.

Comparative Example 2

In Comparative Example 1, a vinyl chloride polymer latex in the same manner as in Comparative Example 1, except that 8.4 kg of the second seed particles of Preparation Example 2 were added, and 9.7 kg of the third seed particles of Preparation Example 3 were further added. Was prepared.

Comparative Example 3

In Comparative Example 1, a vinyl chloride polymer in the same manner as in Comparative Example 1, except that 4.5 kg of first seed particles having an average particle diameter of 0.25 µm were added, and 9.7 kg of the third seed particles of Preparation Example 3 were further added. The latex was prepared.

Comparative Example 4

In Example 1, a vinyl chloride polymer latex was prepared in the same manner as in Example 1, except that 3.2 kg of the first seed particles of Preparation Example 1 and 17 kg of the third seed particles of Preparation Example 3 were added. I did.

Comparative Example 5

In Example 1, a vinyl chloride polymer latex was prepared in the same manner as in Example 1, except that 11.6 kg of the third seed particles having an average particle diameter of 1.80 µm were not added, and the third seed particles of Preparation Example 3 were not added. Was prepared.

Comparative Example 6

In Example 1, a vinyl chloride polymer latex was prepared in the same manner as in Example 1, except that 3.0 kg of first seed particles having an average particle diameter of 0.07 µm were added instead of the first seed particles of Preparation Example 1.

Comparative Example 7

In Example 1, except that 4.35 kg of the first seed particles of Preparation Example 1 were added, 10.2 kg of the second seed particles of Preparation Example 2 were added, and 3.3 kg of the third seed particles of Preparation Example 3 were added. A vinyl chloride polymer latex was prepared in the same manner as in Example 1.

Comparative Example 8

In Example 1, a vinyl chloride polymer latex was prepared in the same manner as in Example 1, except that 7.5 kg of the third seed particles having an average particle diameter of 1.0 µm were not added without adding the third seed particles of Preparation Example 3. Was prepared.

Comparative Example 9

In Example 1, a vinyl chloride polymer latex was prepared in the same manner as in Example 1, except that 5.3 kg of the first seed particle, 8.1 kg of the second seed particle, and 7.5 kg of the third seed particle were added. .

Experimental Example 1: Analysis of particle size distribution of vinyl chloride polymer latex

A sample was prepared by diluting the vinyl chloride-based polymer latex of each Example and Comparative Example in deionized water to 1% by weight, and then the particle size distribution and each peak top particle size were measured using a particle size meter (DC24000 UHR, CPS Instrument).

division 1st peak top particle diameter (㎛) 2nd peak top particle diameter (㎛) 3rd peak top particle diameter (㎛) Particle distribution in the first peak top particle diameter range
(weight%) 2nd peak top particle diameter range particle distribution
(weight%) 3rd peak top particle diameter range particle distribution
(weight%) Example 1 0.25 1.2 1.8 50 35 15 Example 2 0.25 1.2 1.8 65 20 15 Example 3 0.25 1.2 1.8 55 35 10 Example 4 0.25 1.2 1.8 50 40 10 Example 5 0.25 1.2 1.8 55 30 15 Comparative Example 1 0.4 1.2 - 65 35 - Comparative Example 2 0.4 1.2 1.8 65 20 15 Comparative Example 3 0.4 1.2 1.8 50 35 15 Comparative Example 4 0.25 1.2 1.8 35 35 30 Comparative Example 5 0.25 1.2 2.2 50 35 15 Comparative Example 6 0.15 1.2 1.8 50 35 15 Comparative Example 7 0.25 1.2 1.8 55 40 5 Comparative Example 8 0.25 1.2 1.3 50 35 15 Comparative Example 9 0.25 1.2 1.8 75 15 10 Particle distribution in the first peak top particle diameter range: the content ratio of particles having a particle diameter less than or equal to the first minimum particle diameter
Particle distribution in the second peak top particle diameter range: The content ratio of particles having a particle diameter exceeding the first minimum particle diameter and less than the second minimum particle diameter
Particle distribution in the third peak top particle diameter range: Content ratio of particles having a particle diameter exceeding the second minimum particle diameter

Experimental Example 2: Compounding properties of plastisol

100 g of vinyl chloride polymer powder obtained by spray drying each vinyl chloride polymer latex prepared in the above Examples and Comparative Examples, diisononylphthalate (DINP) 60 g, TiO ₂ (KA100, Cosmo Chemical) 10 g, CaCO ₃ (S500H, REXM) 50g, azodicarbonamide (ADCA) as a blowing agent (AC7000, Keumyang Chemical) 4g, K/Zn metal complex stabilizer (KK42, BAERLOCHER) 3g, viscosity regulator (BYK1148, BYK CHEMI) 1g 5 g of a hydrocarbon solvent (Dsol200, Isu Chemical) was mixed with an overhead stirrer (EUROSTAR Digital, EURO-ST D, IKA) and stirred at 800 rpm for 10 minutes to prepare each plastisol. The viscosity, gloss, and foam cell properties of the plastisol were evaluated in the following manner.

1) viscosity

Each plastisol was stored for 1 hour in a thermo-hygrostat at 25° C., and the viscosity was measured under the conditions of 64 spindles and 12 rpm with a digital viscometer (DV1M LV, AMETEK-BROOKFIELD).

2) Glossiness

Each plastisol was prepared as a semi-finished product or a finished product, and then glossiness was measured using a gloss meter (micro-TRI-gloss, BYK gardner) 60°. At this time, the semi-finished product is a pregelling sheet manufactured under conditions of 150°C for 45 seconds using a matis oven after coating a plastisol on a 0.5 mm rod. It is a foamed sheet foamed by gelling at 200°C for 90 seconds. In addition, the smaller the value of the measured glossiness is, the better the matte property is.

3) Foam cell properties

The cell density of the cross-section of the finished product manufactured in 2) was measured and classified according to the following criteria.

(Circle): The cells of the foamed cross section are very uniform and dense. The foam sheet surface is very uniform.

X: Foamed cross-section cells form open cells. The cell size is very large and the surface of the foam sheet is uneven.

division Semi-finished product gloss Finished product gloss Viscosity (Pa·s) Foam cell characteristics Example 1 10.6 3.1 16.5 ○ Example 2 17.5 4.0 17.5 ○ Example 3 14.5 3.2 17.0 ○ Example 4 13.5 3.1 16.4 ○ Example 5 13.2 3.2 16.8 ○ Comparative Example 1 26.5 6.4 16.8 ○ Comparative Example 2 18.5 4.8 15.5 X Comparative Example 3 17.7 4.7 13.0 X Comparative Example 4 13.0 3.6 11.9 X Comparative Example 5 13.9 3.9 14.8 X Comparative Example 6 21.4 6.1 24.3 ○ Comparative Example 7 26.3 6.4 16.7 ○ Comparative Example 8 23.8 6.2 18.9 ○ Comparative Example 9 20.5 5.8 24.0 ○

As shown in Table 2, the vinyl chloride polymer latex of Examples 1 to 5 in which the content ratio of particles for each particle size range was adjusted to a specific range in the present invention while having a trimodal particle size distribution had a specific particle size distribution in the present invention. Compared to the unsatisfied vinyl chloride polymer latex of Comparative Examples 1 to 9, excellent matte properties and foaming properties may be exhibited without a significant increase in viscosity.

Specifically, it can be seen that Examples 1 to 5 show significantly lower glossiness of semi-finished products and finished products compared to the vinyl chloride polymer latex of Comparative Example 1 having a bimodal particle size distribution. In addition, Examples 1 to 5 confirmed that the glossiness of the semi-finished and finished products was low and the foaming properties were excellent compared to Comparative Examples 2 and 3 in which the first peak-top particle diameter, which is the smallest peak-top particle diameter, exceeds a specific range in the present invention. I can. In Comparative Examples 2 and 3, it can be seen that the foamed cells of the foamed cross-section are very large, and accordingly, collapse of the foamed cells occurs, and an open cell is observed.

In addition, Examples 1 to 5 are Comparative Example 4 in which a very large number of particles having a particle diameter exceeding the second minimum particle diameter are included, and Comparative Examples in which the third peak-top particle diameter, which is the largest peak top particle diameter, exceeds a specific range in the present invention. Compared to 5, foaming properties are remarkably superior

In addition, it can be seen that Examples 1 to 5 have lower glossiness and particularly low viscosity of semi-finished products and finished products compared to Comparative Example 6 in which the first peak top particle diameter is less than a specific range in the present invention. When the viscosity is significantly increased as in Comparative Example 6, it is not easy to mix it with a plastisol, and even when it is compounded with a sol, there may be a problem that the processability and moldability of the compounded sol are deteriorated.

In addition, Examples 1 to 5 are compared to Comparative Example 7 in which particles having a particle diameter exceeding the second minimum particle diameter are less than a specific range in the present invention and Comparative Example 8 in which the third peak top particle diameter does not fall within the scope of the present invention. It can be seen that the glossiness of semi-finished and finished products has a remarkably low value.

In addition, in Examples 1 to 5, it can be seen that particles having a particle diameter less than the first minimum particle diameter have lower gloss and particularly low viscosity than Comparative Example 9 exceeding a specific range in the present invention. Comparative Example 9 may have the same problem as Comparative Example 6.

Through this, when a specific particle size distribution pattern in the present invention, for example, a trimodal particle size distribution curve, and the peak top particle size range and the distribution ratio of the particles satisfy a specific range in the present invention, the matte property and the foaming property are excellent, It can be seen that the low viscosity characteristic appears.

Claims (14)

A particle size distribution curve of a trimodal having a first peak with a peak top particle diameter of 0.20 µm to 0.32 µm, a second peak with a peak top particle diameter of 0.33 µm to 1.39 µm, and a third peak with a peak top particle diameter of 1.40 µm to 2.00 µm have,
40% to 70% by weight of particles having a particle diameter less than or equal to the first minimum particle diameter present between the first peak and the second peak based on the weight of the vinyl chloride-based polymer latex in the particle size distribution curve,
5% to 52% by weight of particles having a particle diameter that exceeds the first minimum particle diameter and is less than or equal to the second minimum particle diameter present between the second peak and the third peak, and
A vinyl chloride-based polymer latex comprising 8% to 25% by weight of particles having a particle diameter exceeding the second minimum particle size.
The method of claim 1,
The vinyl chloride-based polymer latex,
45% to 55% by weight of particles having a particle diameter less than or equal to the first minimum particle diameter present between the first peak and the second peak,
30% to 40% by weight of particles having a particle diameter that exceeds the first minimum particle diameter and is less than or equal to the second minimum particle diameter present between the second peak and the third peak, and
The vinyl chloride-based polymer latex comprising 10% to 20% by weight of particles having a particle diameter exceeding the second minimum particle diameter.
The method of claim 1,
The peak top particle diameter of the first peak is 0.23 ㎛ to 0.28 ㎛ of vinyl chloride-based polymer latex.
The method of claim 1,
The peak top particle diameter of the third peak is 1.55 μm to 1.90 μm, which is a vinyl chloride-based polymer latex.
The method of claim 1,
The first minimum particle diameter is 0.30 ㎛ to 0.80 ㎛,
The second minimum particle diameter is 1.40 μm to 1.75 μm of vinyl chloride-based polymer latex.
To prepare a vinyl chloride-based polymer latex according to any one of claims 1 to 5,
A method for producing a vinyl chloride-based polymer latex comprising the step of polymerizing a vinyl chloride-based monomer in the presence of at least three seed particles having different average particle diameters (D ₅₀ ).
The method of claim 6,
At least one of the seed particles is a method for producing a vinyl chloride-based polymer latex that is produced through polymerization of two or more times.
The method of claim 6,
The seed particle is a method of producing a vinyl chloride-based polymer latex containing third seed particles having an average particle diameter (D ₅₀ ) of 1.20 μm to 1.60 μm.
The method of claim 8,
The third seed particle is a method of producing a vinyl chloride-based polymer latex that is included in an amount of 3.0 parts by weight to 9.0 parts by weight based on 100 parts by weight of the vinyl chloride-based monomer.
The method of claim 6,
The seed particle is a method for producing a vinyl chloride-based polymer latex comprising first seed particles having an average particle diameter (D ₅₀ ) of 0.10 µm to 0.20 µm.
The method of claim 6,
The polymerization is a method for producing a vinyl chloride-based polymer latex that is carried out by a seed emulsion polymerization method.
A vinyl chloride-based polymer powder prepared by drying the vinyl chloride-based polymer latex according to any one of claims 1 to 5.
Plastisol containing the vinyl chloride-based polymer powder of claim 12.
The method of claim 13,
The plastisol is a plastisol containing 40 to 180 parts by weight of a plasticizer based on 100 parts by weight of the vinyl chloride-based polymer powder.