KR20060064210A - Pvc processing-aids and process for manufacturing thereof - Google Patents

Abstract

The present invention relates to a processing aid for vinyl chloride resin and a method for producing the same, comprising a plasticizer for vinyl chloride resin in a methyl methacrylate-based polymer, the process containing the plasticizer according to the present invention The preparation aids the melting of the vinyl chloride resin faster than the conventional methyl methacrylate polymer alone, and ultimately improves the processability and physical properties of the vinyl chloride resin.

Processing aids, processing aids, thermoplastics, plasticizers, vinyl chloride resins, miniemulsions

Description

Processing aid for vinyl chloride resin and its manufacturing method {PVC Processing-Aids and Process for Manufacturing example}

1 is a TEM photograph of a processing aid containing a plasticizer prepared according to an embodiment of the present invention.

2 is a functional diagram of a vinyl chloride resin and a processing aid.

3 is a graph of a vinyl chloride resin gelation curve showing the relationship between time and torque during the progress of gelation of vinyl chloride resin.

The present invention relates to a processing aid used in a vinyl chloride resin and a method for preparing the same, and more particularly, to form a latex particle containing a plasticizer by polymerizing a monomer, a plasticizer, an emulsifier, an initiator, and deionized water by mixing and miniemulsion polymerization. The present invention relates to a processing aid for preparing a processing aid and improving the processability and physical properties of the vinyl chloride resin by providing it to a processing step of the vinyl chloride resin.

In general, vinyl chloride resin has the advantages of excellent physical, chemical and electrical properties compared to low price, and it can satisfy various physical properties from rigid to flexible products by adjusting the prescription properly. Wide range of products, pipes, window frames, containers, decorative materials, etc., and a variety of products. However, hard vinyl chloride resins have disadvantages that are difficult to process. Vinyl chloride resin is molded by two kinds of energy: mechanical shear force transmitted from the processing machine to the resin and external heat energy. The vinyl chloride resin must be carried out under conditions so that the internal temperature of the resin is maintained within a limited range during molding. The reason is that the pyrolysis temperature of PVC resin is very close to the upper limit of the processing temperature, so if it is processed incorrectly under the conditions outside of this processing range, the resin itself will undergo pyrolysis, which will lead to rapid deterioration of physical properties and environmental pollution. This happens because.

On the other hand, the vinyl chloride resin can fully exhibit the advantages of the resin itself should be processed to reach the molten state in which the molecules are uniformly mixed while the boundaries between the primary particles constituting the basic grains are released. However, due to the characteristics of the resin, vinyl chloride resin has a very long time to be completely melted, and when molding is completed before complete melting, the impact resistance, formability, mechanical properties, etc. of the final product are reduced, and the surface of the product is also rough. Commodity value is halved. This problem, namely, to improve the intrinsic melt retardation characteristics of vinyl chloride resins to fully exhibit their mechanical and chemical properties is called a processing aid, and the use of these is essential for the processing of vinyl chloride resins. This processing aid is added to about 1 to 5 parts by weight based on 100 parts by weight of the vinyl chloride resin to improve the processability so that the excellent physical properties of the vinyl chloride resin can be maximized.

For example, processing aids added to vinyl chloride resins improve the bank rolling properties, flow marks, air streak and surface projections of vinyl chloride resins when they are processed into calendars. It serves to reduce. In addition, when producing foamed products, the melting of the vinyl chloride resin, which forms the walls of the gas cell, helps to proceed sufficiently to increase the high temperature melt strength and to withstand the pressure of the gas that decomposes and expands at a high temperature. Burst to prevent the formation of open cells that are connected to each other. And when vacuum or blow molding also serves to improve the breaking strength and elongation at high temperatures.

The effect is that the processing aid breaks down the boundaries of the primary particles, the basic structural unit, during the molding of vinyl chloride, thereby promoting a uniform melt state at the molecular level, so that the molded product exhibits uniform mechanical and chemical properties. Because it is possible to obtain.

Most commercially available vinyl chloride processing aids are commercially available as high molecular weight polymers or methyl methacrylate monomers using methyl methacrylate having excellent compatibility with vinyl chloride resin as the main monomer. Made by using high molecular weight (molecular weight 500,000 ~ 5,000,000g / mole) polymer copolymerized with methacrylate type, compound having nitrile unsaturated double bond or monomer having aromatic unsaturated double bond by emulsion polymerization method Methyl methacrylate polymer.                         

On the other hand, the plasticizer is added to the resin to increase the fluidity, elasticity and adhesiveness to facilitate processing, give flexibility to the product, and lower the melting temperature to change the rigid glassy solid into a flexible and tough material, relatively A highly volatile solvent that is added to high molecular materials to improve processability and change physical properties. When the plasticizer is added to the polymer resin, the plasticizer penetrates between the molecules of the resin, and the strong bonds acting between the resin molecules and the molecules are changed into bonds between the resin molecules and the molecules of the plasticizer. Thus, the strong bonds are released and the plasticizer is released between the resin molecules. Will act as a lubricant. In particular, amorphous polymers have resistance to deformation mainly due to three-dimensional cross-linking between polymers, and plasticizers can easily deform by easily relieving stresses between polymers.

However, when a small amount of plasticizer is added, the free space inherent in the polymer becomes a space filled with the plasticizer, thereby decreasing the glass transition temperature of the polymer, increasing the tensile strength and tensile modulus, and decreasing the elongation and impact strength. In the case of general plasticizers, the degree of semi-plasticization is about 5 to 10% depending on the type. Therefore, when the plasticizer is used at this semi-plasticization concentration, the glass transition temperature of the vinyl chloride resin is lowered, so that low temperature processing is possible, but it does not help melting, so deterioration of the physical properties of the resin product cannot be avoided, so care must be taken in using it.

In order to solve the above problems, the present invention is used by mixing the processing aid and the plasticizer in order to maximize the effect of the methyl methacrylate-based polymer processing aid in the plasticizer in a special way in the polymer used as a processing aid at present It is an object of the present invention to provide a novel concept of a processing aid and a method for producing the same, which can exhibit the melting assistance characteristics of vinyl chloride resin superior to the processing aid used.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention provides a processing aid comprising a plasticizer for vinyl chloride resin in the methyl methacrylate-based polymer microparticles.

The processing aid for the vinyl chloride resin may be polymethyl methacrylate.

The processing aid for the vinyl chloride resin may further include a polymer material formed by copolymerizing a monomer having an unsaturated double bond copolymerizable with methyl methacrylate and a methyl methacrylate monomer.

The plasticizer may be used in 5 to 900 parts by weight based on 100 parts by weight of the processing aid.

The particle size of the processing aid may be 100 to 1500 nm.

The molecular weight of the processing aid may be 100,000 to 10,000,000.

In addition, the present invention comprises the steps of mixing and homogenizing a monomer having a unsaturated double bond, which can be polymerized by free radicals, a hydrophobic agent, a plasticizer, an emulsifier, an initiator and deionized water to obtain a minimal emulsion; And a mini emulsion polymerization step of heating and polymerizing the mini emulsion.

In addition, the present invention comprises the steps of mixing and homogenizing a monomer, a plasticizer, an emulsifier, an initiator and deionized water having an unsaturated double bond and polymerizable by free radicals to obtain a minimization; And a mini emulsion polymerization step of heating and polymerizing the mini emulsion, wherein the plasticizer has a solubility in water of 5 × 10 ⁻⁶ g / g or less at 25 ° C. do.

In the step of obtaining the mini-emulsion may further comprise a copolymerizable monomer copolymerizable with the monomer.

The homogenization method may use a microfluidizer, an ultrasonifier, a Molton-Gaulin homogenizer or an omni-mixer.

The size of the mini-emulsion particles may be 100 to 1600 nm.

The plasticizer is 5 to 900 parts by weight, the emulsifier is 0.05 to 3 parts by weight, the initiator is 0.01 to 0.3 parts by weight, the deionized water may be 100 to 500 parts by weight based on 100 parts by weight of the monomer. It may be up to 10 parts by weight.

The monomer is a compound having an unsaturated double bond in which the polymerization reaction proceeds by free radicals, methacrylate derivative, acrylate derivative, acrylic acid derivative, methacrylonitrile derivative, styrene, styrene derivative, acrylonitrile derivative, vinyl ester It may be selected from the group consisting of derivatives, vinyl halide derivatives butadiene, isoprene, maleic anhydride and fumaric acid.

The emulsifier may be at least one selected from the group consisting of anionic emulsifiers, cationic emulsifiers and nonionic emulsifiers.

The initiator may be at least one selected from the group consisting of persulfate-based, peroxide, peroxide-based initiators, azo-based initiators and redox-based initiators.

Jiangsu the hand that is soluble in water at not more than ^{25 ℃ 5 × 10 -6 g /} g, a carbon number of C ₁₂ -C ₂₀ aliphatic hydrocarbons, C ₁₂ -C ₂₀ aliphatic alcohols, C ₁₂ -C ₂₀ of the An acrylate composed of an alkyl group having a C ₁₂ -C ₂₀ alkyl mercaptan, an organic dye, a fluorinated alkane, a silicone oil, a natural oil, a synthetic oil, an oligomer having a molecular weight of 1,000 to 500,000, and a polymer having a molecular weight of 1,000 to 500,000 One or more may be selected from the group.

The plasticizer consisting of C ₃ -C ₂₀ of phthalate derivatives, C ₃ -C ₂₀ fatty acid ester derivatives, trimellitate derivatives, phosphate derivatives, epoxy derivatives, soybean oil, and polyethylene derivatives of C ₁ -C ₂₀ in C ₃ -C ₃₀ It can be selected from the group.

The C ₃ -C ₂₀ phthalate derivative is di 2-ethylhexyl phthalate, di n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, di Heptyl phthalate, dinonyl phthalate, ditridecyl phthalate, butylbenzyl phthalate and butyl phthalyl butyl glycolate, wherein the C ₃ -C ₂₀ fatty acid ester derivatives are dioctyl adipate, diisononyl adipate , Diisodecyl adipate, dioctyl azelate, dioctyl sebacate, methyl acetyl ricinolate, dibutyl glycol adipate, di2-ethylhexyl maleate, dibutyl maleate, dibutyl acetyl fumalate, citric acid acetyl Triethyl, acetyl citrate 2-ethylhexyl, triethyl citrate, acetyl tributyl citrate and citric acid Acid is selected from the group consisting of acetyltriethyl, the C ₃ -C ₃₀ meritate derivatives are trioctylmelitate or triisodecylmeliate, and the C ₁ -C ₂₀ phosphate derivatives are triceresyl phosphate, tri It is selected from the group consisting of phenyl phosphate, trioctyl phosphate, triisopropyl phosphate, tri betachloroethyl phosphate, octyl diphenyl phosphate and tri dichloropropyl phosphate, wherein the epoxy derivative may be an epoxy fatty acid ester or an epoxidized fat or oil derivative.

In addition, the present invention may further comprise the step of forming a dry particle by spray drying after the step of heating and polymerizing the mini-emulsion in the manufacturing method of the processing aid, or drying after aggregation to remove moisture.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention is to improve the processability of polyvinyl chloride by incorporating a plasticizer into the interior cavity of the processing aid by the mini-emulsion method with respect to the addition of a processing aid and a plasticizer in the processing of conventional vinyl chloride resin, respectively. A processing aid in the form of a latex.

The processing aid according to the present invention contains a plasticizer in a methyl methacrylate polymer that provides shear force to the vinyl chloride resin through adhesion, thereby lowering the glass transition temperature of the processing aid polymer and making the plasticizer and the processing aid polymer into one particle. To present. The plasticizer lowers the glass transition temperature of the acrylate polymer to promote adhesion of the vinyl chloride resin around the methyl methacrylate polymer.

Processing aids containing the above plasticizer may be prepared by the following method.

(a) 100 parts by weight of monomer

(b) 5 to 900 parts by weight of plasticizer

(c) 0 to 10 parts by weight of a strong additive

(d) 0.05 to 3 parts by weight of an emulsifier

(e) 0.01 to 0.3 parts by weight of initiator and

(f) 100 to 500 parts by weight of deionized water

After mixing the weighted components as described above using a microfluidizer, ultrasonifier (Ultrasonifier), Morton-Gaulin homogenizer (Omni-Mixer) After homogenizing to 100-2000 nm in size, it is put into a polymerization reactor, heated to a temperature of 50 to 100 ° C. for polymerization, and latex obtained by polymerization to obtain a powder through a powdering process such as coagulation or spray drying.                     

The monomer is methyl methacrylate as a main component (50 to 100% by weight), and as an auxiliary component, ethyl acrylate, hydroxyethyl methacrylate, n-butyl methacrylate, which can be copolymerized with the main component and free radicals, Isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, decyl acryl Laterate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, stearyl acrylate, stearyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl methacrylate Benzyl acrylate, benzyl methacrylate, phenylethyl acrylate, phenylethyl methacrylate, phenyl Propyl acrylate, phenylpropyl methacrylate, phenylnonyl acrylate, phenylnonyl methacrylate, 3-methoxybutyl acrylate, 3-methoxybutyl methacrylate, butoxyethyl acrylate, butoxyethyl methacrylate , Diethylene glycol monoacrylate, diethylene glycol monomethacrylate, triethylene glycol monoacrylate, triethylene glycol monomethacrylate, tetraethylene glycol monoacrylate, tetraethylene glycol monomethacrylate, furfuryl acrylate Methacryl or acrylic monomers, such as furfuryl methacrylate, a nitrile monomer such as acrylonitrile or methacrylonitrile, and a monomer having an aromatic unsaturated double bond such as styrene, alphamethyl styrene or vinyl toluene; Copolymerization with Other Methyl Methacrylates It can be used any monomer, and the like, can be used by one or more selected from these groups, but is not limited to these monomers.                     

The plasticizer may be di 2-ethylhexyl phthalate, di n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, diheptyl phthalate, dinonyl phthalate C ₃ -C ₂₀ phthalate-based, dioctyl adipate, diisononyl adipate, diisodecyl adipate, dioctyl, including isomers such as ditridecyl phthalate, butylbenzyl phthalate and butyl phthalyl butyl glycolate Azelate, dioctyl sebacate, methyl acetyl ricinolate, dibutyl glycol adipate, di 2-ethylhexyl maleate dibutyl methacrylate, dibutyl acetyl fumalate, acetyl triethyl citrate, acetyl 2-ethylhexyl citrate, triethyl citrate, citric acid, acetyl tributyl citrate acetylation of the C ₃ -C ₂₀ fatty acid esters such as triethyl C ₃ -C ₃₀ methalates, such as trioctylmelitate or triisodecylmelitate, triceresyl phosphate, triphenyl phosphate, trioctyl phosphate, triisopropyl phosphate, tri betachloroethyl phosphate, octyl diphosphate One or more of epoxy, soybean oil, polyethylene, such as C ₁ -C ₂₀ phosphate system such as phenyl phosphate and tridichloropropyl phosphate, epoxy fatty acid ester, epoxidized fat and oil system, etc. can be used in combination, and limited to these plasticizers. It doesn't happen.

The amount of the plasticizer is preferably 5 to 900 parts by weight relative to 100 parts by weight of the monomer. When the amount is 5 parts by weight or less, the effect is insignificant as a processing aid including the plasticizer.                     

The hydrophobic agent (强 疏 水劑, ultrahydrophobe) is dissolved in water at 25 ℃ of 5 × 10 ^-6 g / g or less, C ₁₂ -C ₂₀ aliphatic alcohols, C ₁₂ -C ₂₀ Alkyl group having a carbon number At least one selected from the group consisting of acrylates, C ₁₂ -C ₂₀ alkyl mercaptans alone or mixtures, organic dyes, fluorinated alkanes, silicone oil compounds, natural oils and synthetic oils. If the solubility of the plasticizer in water is 5 × 10 ⁻⁶ g / g or less, the plasticizer may take the role of the hydrophobic agent necessary for the formation of the miniemulsion, and thus, it may be omitted if necessary. As a strong water agent, for example, hexadecane, heptadecane, octadecane, cetyl alcohol, isopropyl laurate, isopropyl palmitate, hexyl laurate, isopropyl myristate, myristyl myristate, cetyl myristate, 2-octyl Decyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, butyl stearate, decyl oleate and 2-octyldodecyloleate, glycol ester oils such as polypropylene glycol monooleate and neopentyl glycol 2-ethylhexanoate and polyhydric alcohol ester oils, isostearate, triglycerides and coco fatty acid triglycerides, almond oil, apricot oil, avocado oil, theobroma oil, carrot seed oil, castor oil, citrus seed oil, coconut oil , Corn oil, cottonseed oil, cucumber oil, egg oil, jojoba oil, lanolin o Sun, flaxseed oil, mineral oil, mink oil, olive oil, palm oil, phosphorus oil, peach oil, peanut oil, rape seed oil, safflower oil, sesame oil, shark liver oil, soybean oil, sunflower seed oil, sweet almond oil, tallow, sheep oil, At least one of turtle oil, vegetable oil, whale oil and wheat germ oil, organosilicon, siloxane, alkyl mercaptan such as n-dodecyl mercaptan, t-dodecyl mercaptan, fluorinated alkanes such as hexafluorobenzene It may be used in combination, but is not limited to these.

The said emulsifier can select 1 or more types from the group which consists of an anionic emulsifier, a cationic emulsifier, and a nonionic emulsifier. In other words, the emulsifiers include sulfonates, carboxylates, succinates, sulfosuccinates and metal salts thereof, such as alkylbenzenesulfonic acid, sodium alkylbenzenesulfonate, alkylsulfonic acid, sodium alkylsulfonate, sodium poly Anionic emulsifiers widely used in emulsion polymerization, such as oxyethylene nonylphenylether sulfonate, sodium stearate, sodium dodecyl sulfate, sodium lauryl sulfate, sodium dodecyl sulfosuccinate, abienic acid salts and the like; Cationic emulsifiers in which amine halides, alkyl quaternary ammonium salts, alkylpyridinium salts, and the like are bonded as functional groups of higher aliphatic hydrocarbons; One or more types can be selected from the group which consists of nonionic emulsifiers, such as polyvinyl alcohol and polyoxyethylene nonylphenyl, It is not limited to these emulsifiers.

As the initiator, an initiator that generates free radicals is suitable, and typical ones may be used in the group consisting of a redox initiator composed of a peroxide compound initiator, an azo compound initiator, and a combination of various redox compounds. It is not limited to these.

The gelation time of the vinyl chloride resin mixed with the appropriate processing formulation is measured as a measure of the performance as a processing aid of the thus obtained polymerization composition.

Here, gelation time refers to the time taken until the primary particles of the vinyl chloride resin are lost due to the shear force and thermal energy of the vinyl chloride resin and melted into a homogeneous mixture at the molecular level. The melting curve of a typical vinyl chloride resin is shown in FIG. 3. 3 shows that initially, the vinyl chloride resin particles are present in the form of particles, but the processing load is increased by the resistance acting on the processing machine while the particles are partially dissolved-friction-welded by energy generated by heat and shear force. do. Under constant shearing and thermal energy, the vinyl chloride resin particles are released into polymer chains and ultimately gelate as they transition from the particles to the molten state. This time until gelation is called gelation time.

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

Manufacture of processing aids containing plasticizers

After polymerizing the composition in a combination as shown in Table 1 to obtain a polymer latex, it was spray-dried or flocculated to dry to prepare a processing aid (PEP) containing a plasticizer. The formulation for obtaining processing aid particles containing a plasticizer is shown in Table 1 below.

Composition (part by weight) PEP1 PEP2 PEP3 PEP4 PEP5 PEP6 PEP7 PEP8 Monomer Methyl methacrylate 100 100 100 100 100 100 100 100 Plasticizer Dioctyl phthalate 100 100 100 - - - 10 100 Trioctyl Melitate - - - 100 50 - - - Diisononyl phthalate - - - - - 100 - - Jiangsu Handmade Hexadecane - 3 5 - 3 - - - Emulsifier Sodium lauryl sulfate 0.3 0.2 0.1 0.2 0.2 0.2 0.2 0.2 Initiator Lauryl peroxide 0.1 0.1 0.1 0.2 0.1 0.1 0.05 0.05 Deionized water 500 500 500 500 500 500 500 500 Polymerization temperature (℃) 70 70 90 90 80 90 70 70 Number average molecular weight (× 10 ^ 4) 120 125 70 68 90 89 121 123 Particle size (nm) 250 365 500 380 370 366 340 338

[Examples 1 to 9]

As shown in Table 2 below, the processing aid containing the plasticizer prepared above (PEP), a vinyl chloride resin and other additives necessary for processing of the vinyl chloride resin, the processing aid containing a plasticizer in 100 parts by weight of polyvinyl chloride resin 1 The gelling time was measured by recording a mechanical load appearing by adding a certain amount of the dry powder mixture obtained by adding and mixing 1 part by weight and a stabilizer to a Hakke Torque Rheomixer and melting at 30 RPM at a temperature of 180 ° C. .

Comparative Example 1

Example 1 except for using a polymethyl methacrylate (PMMA) processing aid made by the method disclosed in the Republic of Korea Patent Publication No. 1996-0022602 instead of the processing aid in Example 1 to compare with the existing processing aids The same procedure was followed. The value measured by gelation time is shown in Table 2 below.

Comparative Example 2

The same process as in Example 1 was carried out except that the processing aid was not used in Example 1.                     

Comparative Example 3

Except for using the plasticizer dioctylphthalate (DOP) alone in place of the processing aid in Example 1 and was carried out in the same manner as in Example 1.

[Comparative Example 4]

Example 1 was carried out in the same manner as in Example 1 except that the plasticizer dioctylphthalate and polymethyl methacrylate were mixed and used instead of the processing aid.

Example Comparative example One 2 3 4 5 6 7 8 9 One 2 3 4 Processing aid PEP1 PEP2 PEP2 PEP3 PEP4 PEP5 PEP6 PEP7 PEP8 PMMA Not input DOP DOP / PMMA Drying method Spray drying Cohesion Spray drying Spray drying Cohesion Cohesion Cohesion Cohesion Cohesion Spray drying - - Spray drying Gel time (seconds) 121 123 124 125 125 124 126 110 108 150 180 181 148

As shown in Table 2 above, in the case of using the processing aid containing the plasticizer of the embodiment than the polymethyl methacrylate polymer of Comparative Example 1, which was used as a conventional processing aid, the gelling time was advanced about 30 seconds, which is very useful as the processing aid It was confirmed to have excellent physical properties.

In Comparative Examples 3 and 4, it was examined whether there was no effect when using the plasticizer alone or whether the plasticizer was shortened when the plasticizer was mixed with the processing aid made by the conventional method. The plasticizer alone was not effective in improving the processability, and the mixing of the plasticizer and the processing aid by post injection did not significantly deviate from the processability of the existing processing aid. Therefore, it can be seen that the processing aid and the plasticizer only help the improvement of processability with the composition made in the polymerization step.

Expecting the same effect, even when the plasticizer is added with the processing aid or mixed with the methyl methacrylate-based polymer and then mixed with the vinyl chloride resin, the effect as provided by the present invention does not appear. This is because the amount of plasticizer acts is reduced, mixed with the entire vinyl chloride resin, or the amount is small so that it acts only on the local part and cannot be delivered to the rest, slowing the effect.

Comparing Examples 1 and 2, the powders prepared using the spray drying method or the agglomeration method to produce the dry particles showed the same gelation time within the experimental error range, whereby the difference in the powdering process was effective as a processing aid. It can be seen that it does not affect.

It was confirmed that the gelation time was shortened in the same manner as in Examples 1 to 4 and 7 using the melitate-based plasticizer and also the examples 1 to 4 and 7 using the phthalate-based plasticizer. Examples 8 and 9 in which the number average molecular weight of the polymer in the processing aid was 2,000,000 showed that the gelation time was further shortened by about 15 seconds compared to Examples 1 to 7 in which the number average molecular weight of the polymer in the processing aid was about 1,000,000.

As described above, the processing aid comprising the plasticizer according to the present invention has an excellent effect in shortening the processing time of the vinyl chloride resin, and is a useful invention that has excellent workability.

Although the present invention has been described in detail with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the present invention, and such modifications and modifications belong to the appended claims. It is also natural.

Claims (22)

A processing aid for vinyl chloride resin, characterized by containing a plasticizer for vinyl chloride resin in the methyl methacrylate-based polymer microparticles. The processing aid according to claim 1, wherein the processing aid for the vinyl chloride resin is polymethyl methacrylate. The processing aid according to claim 1, wherein the processing aid for vinyl chloride resin further comprises a polymer material formed by copolymerizing a monomer having an unsaturated double bond copolymerizable with methyl methacrylate and a methyl methacrylate monomer. pharmacy. The processing aid of claim 1, wherein the plasticizer is used in an amount of 5 to 900 parts by weight based on 100 parts by weight of the processing aid. The method according to claim 1, wherein the plasticizer is a C ₃ -C ₂₀ phthalate derivative, C ₃ -C ₂₀ fatty acid ester derivative, C ₃ -C ₃₀ meritate derivative, C ₁ -C ₂₀ phosphate derivative, epoxy derivative, Processing aid, characterized in that selected from the group consisting of soybean oil and polyethylene derivatives. The phthalate derivative of C ₃ -C ₂₀ is di-ethylhexyl phthalate, di n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, dimethyl phthalate, diethyl phthalate, diisobutyl phthalate. , Dibutyl phthalate, diheptyl phthalate, dinonyl phthalate, ditridecyl phthalate, butylbenzyl phthalate and butylphthalyl butylglycolate; The C ₃ -C ₂₀ fatty acid ester derivatives include dioctyl adipate, diisononyl adipate, diisodecyl adipate, dioctyl azelate, dioctyl sebacate, methyl acetyl ricinolate, dibutyl glycol adipate, Di 2-ethylhexyl maleate, dibutyl maleate, dibutylacetyl fumarate, acetyl triethyl citrate, acetyl 2-ethylhexyl citrate, triethyl citrate, acetyl tributyl citrate and acetyl triethyl citrate; The C ₁ -C ₂₀ phosphate derivative is at least one selected from the group consisting of triceresyl phosphate, triphenyl phosphate, trioctyl phosphate, triisopropyl phosphate, tri betachloroethyl phosphate, octyl diphenyl phosphate and tri dichloropropyl phosphate And wherein the C ₃ -C ₃₀ meritate derivative is trioctyl melitate or triisodecyl melate, and the epoxy derivative is an epoxy fatty acid ester or an epoxidized fat or oil derivative. The method of claim 3, wherein the monomer is methacrylate derivative, acrylate derivative, acrylic acid derivative, methacrylonitrile derivative, styrene, styrene derivative, acrylonitrile derivative, vinyl ester derivative, halogenated vinyl derivative butadiene, isoprene, maleic anhydride And at least one selected from the group consisting of fumaric acid. The processing aid according to claim 1, wherein the processing aid has a particle size of 100 to 1500 nm. The processing aid according to claim 1, wherein the processing aid has a molecular weight of 100,000 to 10,000,000. Mixing and homogenizing a monomer having a unsaturated double bond and polymerizable by free radicals, a hydrophobic agent, a plasticizer, an emulsifier, an initiator, and deionized water to obtain a minimal emulsion; And A mini emulsion polymerization step of heating and polymerizing the mini emulsion; Process for producing a processing aid comprising a. Mixing and homogenizing a monomer, a plasticizer, an emulsifier, an initiator, and deionized water having an unsaturated double bond and polymerizable by free radicals to obtain a miniemulsion; And A mini emulsion polymerization step of heating and polymerizing the mini emulsion; It comprises, wherein the plasticizer is a method for producing a processing aid, characterized in that the solubility in water is 5 × 10 ^-6 g / g or less at 25 ℃. 12. The method of claim 10 or 11, further comprising a copolymerization monomer copolymerizable with the monomer in the step of obtaining the mini-emulsion. 12. The process for producing a processing aid according to claim 10 or 11, wherein the homogenization method uses a microfluidizer, an ultrasonicifier, a molton-gaulin homogenizer or an omnimixer. 12. The method of claim 10 or 11, wherein the size of the mini-emulsion particles is 100 to 1600 nm. The method according to claim 10 or 11, wherein the plasticizer is 5 to 900 parts by weight, the emulsifier is 0.05 to 3 parts by weight, the initiator is 0.01 to 0.3 parts by weight and the deionized water is 100 to about 100 parts by weight of the monomer Method for producing a processing aid, characterized in that 500 parts by weight. The method according to claim 10, wherein the water reducing agent is 10 parts by weight or less based on 100 parts by weight of the monomer. The method according to claim 10 or 11, wherein the emulsifier is selected from the group consisting of anionic emulsifiers, cationic emulsifiers and nonionic emulsifiers. 12. The method of claim 10 or 11, wherein the initiator is selected from the group consisting of persulfate, peroxide, peroxide initiator, azo initiator and redox initiator. . The method of claim 10, wherein the hydrophobic agent has a solubility in water of 5 x 10 ^-6 g / g or less at 25 ℃, C ₁₂ -C ₂₀ aliphatic hydrocarbons, C ₁₂ -C ₂₀ aliphatic alcohols, C Acrylates composed of alkyl groups having _12- C ₂₀ carbon atoms, alkyl mercaptans of C ₁₂ -C ₂₀ , organic dyes, fluorinated alkanes, silicone oils, natural oils, synthetic oils, oligomers having molecular weights of 1,000 to 500,000 and molecular weights of 1,000 Method for producing a processing aid, characterized in that at least one selected from the group consisting of 50 to 500,000 polymers. The method of claim 11, wherein the plasticizer is a C ₃ -C ₂₀ phthalate derivative, C ₃ -C ₂₀ fatty acid ester derivative, C ₃ -C ₃₀ meritate derivative, C ₁ -C ₂₀ phosphate derivative, epoxy derivative , Soybean oil and a process for producing a processing aid, characterized in that selected from the group consisting of polyethylene derivatives. 21. The method of claim 20, wherein the C ₃ -C ₂₀ phthalate derivative is di 2-ethylhexyl phthalate, di n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, dimethyl phthalate, diethyl phthalate, diisobutyl phthalate , Dibutyl phthalate, diheptyl phthalate, dinonyl phthalate, ditridecyl phthalate, butylbenzyl phthalate and butylphthalyl butylglycolate; The C ₃ -C ₂₀ fatty acid ester derivatives include dioctyl adipate, diisononyl adipate, diisodecyl adipate, dioctyl azelate, dioctyl sebacate, methyl acetyl ricinolate, dibutyl glycol adipate, Di 2-ethylhexyl maleate, dibutyl maleate, dibutylacetyl fumarate, acetyl triethyl citrate, acetyl 2-ethylhexyl citrate, triethyl citrate, acetyl tributyl citrate and acetyl triethyl citrate; The C ₁ -C ₂₀ phosphate derivative is at least one selected from the group consisting of triceresyl phosphate, triphenyl phosphate, trioctyl phosphate, triisopropyl phosphate, tri betachloroethyl phosphate, octyl diphenyl phosphate and tri dichloropropyl phosphate And wherein the C ₃ -C ₃₀ meritate derivative is trioctyl melitate or triisodecyl melate, and the epoxy derivative is an epoxy fatty acid ester or an epoxidized fat or oil derivative. The processing aid according to claim 10 or 11, further comprising forming dry particles by spray drying after the step of heating and polymerizing the mini-emulsion, or drying to remove moisture by flocculation. Manufacturing method.

Images