KR20220087715A - Method for manufacturing hybrid type PVC stabilizer including liquid stabilizer and powder stabilizer - Google Patents

Abstract

The present invention manufactures a hybrid type PVC compound stabilizer that can produce PVC products with improved dispersibility and excellent appearance quality while minimizing the generation of volatile organic compounds (VOCs) by mixing and introducing a powder type and liquid type stabilizer it's about how to
The method for producing a hybrid-type composite stabilizer for PVC according to the present invention comprises the steps of: (a) mixing an emulsified adsorbent comprising a liquid stabilizer and a porous ceramic powder; (b) adsorbing the liquid stabilizer to the emulsion adsorbent to prepare an encapsulated stabilizer; and (c) mixing 10 to 40 parts by weight of the encapsulation stabilizer and 60 to 90 parts by weight of the powder stabilizer to prepare a composite stabilizer for PVC.

Description

Method for manufacturing hybrid type PVC stabilizer including liquid stabilizer and powder stabilizer

The present invention manufactures a hybrid-type PVC compound stabilizer that can produce PVC products with improved dispersibility and excellent appearance quality while minimizing the generation of volatile organic compounds (VOCs) by mixing and introducing powder-type and liquid-type stabilizers it's about how to

Polyvinyl chloride (PVC) has excellent processability and is eco-friendly because it generates less carbon dioxide compared to products using other plastic materials when manufacturing PVC and PVC molded products. In addition, as one of the representative thermoplastic resins used throughout the industry due to its economic feasibility, it is inexpensive compared to aluminum and has a good insulation effect as well as airtightness, sound insulation, chemical resistance, wind pressure resistance, watertightness, and electrical insulation. Therefore, it is used as a material for manufacturing various products such as building materials, automobile interior and exterior materials, food packaging materials, electrical and electronic products, and artificial leather.

PVC stabilizers mixed with various auxiliary materials such as antioxidants, heat stabilizers, UV stabilizers, flame retardants, lubricants, antistatic agents, foaming agents, impact modifiers, fillers, etc. is manufacturing

The PVC stabilizer as described above is an additive used to prevent discoloration of PVC by providing thermal stability during processing of PVC products.

The PVC heat stabilizer can be classified into various types depending on the chemical composition, action performance, handling form, etc., and is divided into powder and liquid according to the form. Although there are few, there are disadvantages that the dispersibility is low and the working environment is somewhat unfavorable, and the liquid phase has excellent usability and stability, but has a disadvantage that the content of VOC is high.

On the other hand, PVC stabilizer has evolved into a complex stabilizer form by the unique formulation of the stabilizer manufacturer for each use, through the process of supplying the stabilizer individually and mixing it with the customer. Composite stabilizer means that the components of various components are blended according to the purpose, and the liquid phase is in the form of a mixture of liquids and powders of powders. Consumers are divided into liquid composite stabilizer alone, powder composite stabilizer alone, and liquid composite and powder composite 2 pack in consideration of the performance of the stabilizer for each application. In the case of using a liquid composite and a powder composite 2 pack, if one composite stabilizer is used, the desired physical properties cannot be satisfied, so the use of the 2 pack form is inevitably detrimental to productivity and working environment.

However, in the past, studies on how to use powder and liquid stabilizers simultaneously to minimize the generation of volatile organic compounds while improving the dispersibility of the powder stabilizer, improving the working environment, and improving the appearance quality of PVC products were insufficient. Research is needed on how to do this.

Korean Patent Registration No. 10-2152066 (Announcement Date: 2020.09.04.) Korea Patent Publication No. 10-2009-0127199 (published date: 2009.12.10.) Korean Patent Registration No. 10-0974995 (Announcement Date: 2010.08.09.)

The present invention was devised to solve the problems of the prior art as described above, and while minimizing the generation of volatile organic compounds (VOCs) by mixing and introducing a powder-type and liquid-type stabilizer, the advantages of a liquid stabilizer and a powder stabilizer The purpose of this is to provide technical details on a method for manufacturing a hybrid-type PVC composite stabilizer that can produce PVC products with excellent appearance quality, including all of them.

The technical problems to be solved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned are clearly understood by those of ordinary skill in the art to which the present invention belongs from the description below. it could be

In order to achieve the technical problem as described above, the present invention comprises the steps of: (a) mixing an emulsified adsorbent comprising a liquid stabilizer and a porous ceramic powder; (b) adsorbing the liquid stabilizer to the emulsion adsorbent to prepare an encapsulated stabilizer; and (c) mixing 10 to 40 parts by weight of the encapsulation stabilizer and 60 to 90 parts by weight of the powder stabilizer to prepare a composite stabilizer for PVC.

According to a preferred embodiment of the present invention, in the step (a), the liquid stabilizer is supplied to a droplet ejection device that ejects droplets using compressed air, and the liquid stabilizer droplets are discharged to the emulsion adsorbent to thereby discharge the liquid stabilizer. and emulsified adsorbents.

According to a preferred embodiment of the present invention, in step (a), 15 to 35 parts by weight of the liquid stabilizer and 65 to 85 parts by weight of the emulsion adsorbent may be mixed.

According to a preferred embodiment of the present invention, the porous ceramic powder may include at least one selected from the group consisting of silica, aluminosilicate, zeolite, illite, diatomaceous earth, talcite, and talc.

According to a preferred embodiment of the present invention, the porous ceramic powder includes modified silica powder, and the modified silica powder is prepared by (1) mixing 30 to 70 parts by weight of silica powder with 100 parts by weight of water to prepare a suspension. ; (2) electrolyzing the suspension to pretreat silica powder; (3) preparing a reaction mixture by mixing a surface modifier with the suspension containing the silica powder pretreated in step (2); And (4) heat-treating the reaction mixture to prepare a modified silica powder; characterized in that it was prepared by a method for producing a modified ceramic powder comprising a, wherein the surface modifier is propyl gallate, butyl gallate It may include at least one selected from the group consisting of butyl gallate, octyl gallate, hexyl resorcinol, and pentadecylphenol.

According to a preferred embodiment of the present invention, the liquid stabilizer is a calcium/zinc-based liquid stabilizer, a barium/zinc-based liquid stabilizer, a phosphoric acid-based liquid stabilizer, an epoxy zinc-based liquid stabilizer, a mercaptide-based liquid stabilizer, and malate. It may include at least one selected from the group consisting of (Maleate)-based stabilizers and carboxylate-based stabilizers.

According to a preferred embodiment of the present invention, the powder stabilizer is a calcium/zinc-based powder stabilizer, a barium/zinc-based powder stabilizer, a magnesium/zinc-based powder stabilizer, hydrotalcite, a calcium/magnesium/zinc-based powder stabilizer, and aluminum magnesium. It may include at least one selected from the group consisting of a carbonate-based powder stabilizer and a zinc-based powder stabilizer.

According to a preferred embodiment of the present invention, the composite stabilizer for PVC is a plasticizer, processing aid, color improver, antioxidant, UV stabilizer, flame retardant, lubricant, antistatic agent, foaming agent, filler, antibacterial agent, colorant, anti-fouling agent, nucleating agent, blocking agent It may further include one or more additives selected from the group consisting of an inhibitor and a slip agent.

The manufacturing method of the composite stabilizer for hybrid type PVC according to the present invention uses an emulsion adsorbent to absorb a liquid stabilizer to prepare an encapsulated stabilizer with a liquid stabilizer, and then mixes the prepared encapsulated stabilizer with a powder stabilizer. And it is possible to prepare a hybrid type PVC composite stabilizer having uniform dispersibility and stability by minimizing the aggregation of the powder stabilizer generated when mixing the powder stabilizer.

The composite stabilizer for hybrid type PVC prepared in the above way can minimize the emission of harmful components to the human body, such as volatile organic compounds (VOCs), which is a disadvantage of liquid stabilizers, so that eco-friendly PVC products can be manufactured. It can contribute to the productivity improvement of PVC products by improving dispersibility and working environment, which are disadvantages, and can be easily used in the production of PVC products such as wallpaper, flooring, window frames, pipes, and artificial leather.

1 is a process diagram showing a method for manufacturing a composite stabilizer for hybrid type PVC according to the present invention.

Hereinafter, with reference to the accompanying drawings, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, since the description of the present invention is merely an embodiment for structural or functional description, the scope of the present invention should not be construed as being limited by the embodiment described in the text. That is, since the embodiment is capable of various changes and may have various forms, it should be understood that the scope of the present invention includes equivalents capable of realizing the technical idea. In addition, since the object or effect presented in the present invention does not mean that a specific embodiment should include all of them or only such effects, it should not be understood that the scope of the present invention is limited thereby.

The meaning of the terms described in the present invention should be understood as follows.

Terms such as “first” and “second” are for distinguishing one component from another, and the scope of rights should not be limited by these terms. For example, a first component may be termed a second component, and similarly, a second component may also be termed a first component. When a component is referred to as being “connected to” another component, it may be directly connected to the other component, but it should be understood that other components may exist in between. On the other hand, when it is mentioned that a certain element is "directly connected" to another element, it should be understood that the other element does not exist in the middle. Meanwhile, other expressions describing the relationship between elements, that is, "between" and "between" or "neighboring to" and "directly adjacent to", etc., should be interpreted similarly.

The singular expression is to be understood to include the plural expression unless the context clearly dictates otherwise, and terms such as "comprise" or "have" are not intended to refer to the specified feature, number, step, action, component, part or any of them. It is intended to indicate that a combination exists, and it should be understood that it does not preclude the possibility of the existence or addition of one or more other features or numbers, steps, operations, components, parts, or combinations thereof.

All terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs, unless otherwise defined. Terms defined in the dictionary should be interpreted as being consistent with the meaning of the context of the related art, and cannot be interpreted as having an ideal or excessively formal meaning unless explicitly defined in the present invention.

Hereinafter, the present invention will be described in detail.

1 is a process diagram showing a method for manufacturing a composite stabilizer for hybrid type PVC according to the present invention.

Referring to FIG. 1 , the method for manufacturing a composite stabilizer for hybrid type PVC according to the present invention comprises the steps of (a) mixing an emulsion adsorbent comprising a liquid stabilizer and a porous ceramic powder, (b) adding the liquid stabilizer to the emulsion adsorbent and (c) mixing 10 to 40 parts by weight of the encapsulation stabilizer and 60 to 90 parts by weight of the powder stabilizer to prepare a composite stabilizer for PVC.

The step (a) is a step of mixing the emulsified adsorbent containing the liquid stabilizer and the porous ceramic powder.

The liquid stabilizer is a calcium/zinc-based liquid stabilizer, a barium/zinc-based liquid stabilizer, a phosphoric acid-based liquid stabilizer, an epoxy zinc-based liquid stabilizer, a mercaptide-based stabilizer, a maleate-based stabilizer, A carboxylate-based stabilizer or a mixture thereof may be included.

In particular, the liquid stabilizer may be adjusted so that the average particle size of the particles included in the liquid stabilizer is 1 to 100 Å by adjusting the physical structure so that hybridization to the emulsion adsorbent can be smoothly induced.

Preferably, the liquid stabilizer may utilize a mixed liquid stabilizer including a calcium/zinc-based liquid stabilizer and a barium/zinc-based liquid stabilizer, and the mixed liquid stabilizer includes 60 to 90 parts by weight of a Ca/Zn liquid stabilizer, Ba/Zn A liquid stabilizer prepared by mixing 10 to 40 parts by weight may be used.

Specifically, the calcium/zinc liquid stabilizer is 3 to 20 parts by weight of calcium stearate, 3 to 20 parts by weight of zinc stearate, 20 to 80 parts by weight of cyclohexane dicarboxylic acid dialkyl ester , can be used prepared by mixing 3 to 8 parts by weight of stearyl benzoyl methane, but is not limited thereto.

In addition, the barium / zinc-based liquid stabilizer is barium stearate (Barium stearate) 3 to 20 parts by weight, zinc stearate (zinc stearate) 3 to 20 parts by weight, cyclohexane dicarboxylic acid dialkyl ester 20 to 80 parts by weight, What is prepared by mixing 3 to 8 parts by weight of stearyl benzoyl methane may be used, but is not limited thereto.

The emulsion adsorbent may include a porous ceramic powder having a plurality of pores formed on its surface to absorb and support the liquid stabilizer.

The porous ceramic powder is made of silica, alumino silicate, zeolite, illite, diatomite, talcite, talc, or a mixture thereof. The porous ceramic powder may have an average particle size of 0.01 to 1,000 μm, and a plurality of pores having a size of 50 to 10,000 Å formed on the surface may be used to adsorb the liquid stabilizer. Preferably, the porous ceramic powder may utilize silica powder.

On the other hand, in general, the liquid stabilizer is composed of fatty acid ester and an organic solvent capable of dissolving it and exhibits hydrophobicity. , there is a problem that the absorption time becomes long.

In the present invention, the surface-modified silica powder can be used as an emulsion adsorbent to compensate for the above disadvantages to promote absorption of the liquid stabilizer, and the modified silica powder can be prepared by the following method.

Specifically, the modified silica powder may be prepared by: (1) mixing 30 to 70 parts by weight of silica powder with 100 parts by weight of water to prepare a suspension; (2) electrolyzing the suspension to pretreat silica powder; (3) preparing a reaction mixture by mixing a surface modifier with the suspension containing the silica powder pretreated in step (2); and (4) heat-treating the reaction mixture to prepare a modified silica powder.

Looking at the manufacturing method of the modified silica powder in detail, in step (1), the silica powder is mixed with water to prepare a suspension, and the silica powder and water are mixed and then stirred so that the silica powder can sufficiently absorb water. and 30 to 100 parts by weight of silica powder to 100 parts by weight of water to prepare a suspension.

In step (2), the suspension is electrolyzed to pretreat the silica powder. After supplying the suspension to the electrolysis device, a voltage is applied to electrolyze the water contained in the suspension to form hydrogen gas and oxygen gas. Excessive bubbles can be generated, and excessive bubbles are formed even in the water absorbed by the silica powder, so that a large amount of pores can be formed on the surface of the silica powder by supplying the bubbles to the silica powder. The surface area of the particles is greatly increased, so that the surface modifier, which will be described later, can increase the reaction surface area that can contact the silica powder particles, and can be easily modified by using such pre-treated silica powder particles.

In step (3), a reaction mixture is prepared by mixing a surface modifier with the suspension containing the pretreated silica powder. The surface modifier is introduced into the suspension to prepare a reaction mixture, and then the reaction mixture is reacted for a certain period of time, followed by pretreatment. The amphipathic component can be introduced so that the surface modifier is introduced into the pores and surfaces of the silica powder particles, and the amphipathic component is introduced into the silica powder particles so that the liquid stabilizer can be easily absorbed into the pores of the silica particles.

To this end, the surface modifier may be used without limitation as long as it is an amphiphilic component, and the amphiphilic surface modifier is propyl gallate, butyl gallate, octyl gallate, hexyl resorsi Nol (hexyl resorcinol), pentadecylphenol (pentadecylphenol) or a mixture thereof may be used.

The surface modifier may be mixed in a ratio of 0.01 to 3 parts by weight relative to 100 parts by weight of the suspension. When the content of the surface modifier is less than 0.01 parts by weight, it is difficult to sufficiently modify the silica powder, and when it exceeds 3 parts by weight, additional physical property improvement is obtained. hard to expect

In addition, in this step, after preparing the reaction mixture, the prepared reaction mixture is heated to a temperature of 60 to 200° C. and reacted for 1 to 24 hours to introduce a surface modifier to the surface of the pre-treated silica powder particles.

The step (4) is a step of heat-treating the reaction mixture to prepare a modified silica powder, heat-treating the silica powder introduced to the surface of the surface modifier to fix the surface modifier on the surface of the silica powder to prepare a modified silica powder. .

To this end, in this step, a silica powder having a surface modifier introduced into the surface is obtained, dried, and then the dried modified silica powder is heated at a temperature of 200 to 1,000 ° C. for 0.5 to 12 hours to prepare a modified silica powder. can

The modified silica powder prepared by the above method has a large surface area due to the formation of a large number of pores by electrolysis, and the amphiphilic component is fixed on the surface to form a structure that can easily absorb the liquid stabilizer, and harmful components such as VOCs It has a structure that minimizes the emission of

In this step, 15 to 35 parts by weight of the liquid stabilizer and 65 to 85 parts by weight of the emulsified adsorbent can be mixed, and when the content of the liquid stabilizer is less than 15 parts by weight, the content of the liquid component is low, so the composite stabilizer for PVC is easily scattered, so that the working environment This worsens, there is a risk that thermal stability may be lowered, and when it exceeds 35 parts by weight, the amount of liquid stabilizer discharged from the encapsulated stabilizer is high during the manufacture of the composite stabilizer for PVC, which will be described later, so mixing with the powder stabilizer is difficult, and the dispersibility may be lowered. There are concerns.

In addition, in this step, in order to uniformly adsorb the liquid stabilizer to the emulsion adsorbent, a liquid stabilizer is supplied to a droplet ejection device that ejects droplets using compressed air, and the liquid stabilizer droplets are discharged to the emulsion adsorbent to discharge the liquid stabilizer. and a method of mixing an emulsified adsorbent may be used.

Through the above method, the liquid phase can be uniformly supplied to the emulsified adsorbent, and the liquid stabilizer can be uniformly supplied to the emulsified adsorbent in a short time by spraying fine droplets so as not to generate coarse liquid stabilizer particles.

The droplet discharging device includes a storage chamber for storing the liquid stabilizer so as to uniformly supply the liquid stabilizer to the emulsion adsorbent, and an air tank connected to the storage chamber and discharging the liquid stabilizer of the storage chamber to the outside by providing compressed air to the storage chamber and a nozzle connected to the storage chamber through a pipe and receiving a liquid stabilizer discharged from the storage chamber to discharge droplets.

On the other hand, the step (b) is a step of preparing the encapsulated stabilizer by adsorbing the liquid stabilizer to the emulsion adsorbent.

In this step, the encapsulated stabilizer can be prepared by reacting the liquid stabilizer and the emulsified adsorbent, and the reaction time can be shortened by using a means such as a stirring device.

As described above, when the liquid stabilizer is adsorbed to the emulsion adsorbent to prepare an encapsulation stabilizer, and the prepared encapsulation stabilizer is mixed with the powder stabilizer, the liquid stabilizer is encapsulated and agglomeration does not occur as it is mixed with the powder stabilizer. Acidity, viscosity increase, and dust generation can be minimized, and the discharge of harmful components to the human body such as volatile organic compounds, phenol, and formaldehyde can be minimized by making the liquid stabilizer aqueous.

In addition, when mixing the existing liquid and powder stabilizers, the dispersibility of the powder stabilizer is lowered due to the occurrence of agglomeration, and it is possible to prevent the deterioration of the surface smoothness of the PVC product, so that it is possible to manufacture a high-quality PVC product.

In addition, in this step, the mixture of the liquid stabilizer and the emulsion adsorbent is heated to a temperature of 50 to 120 °C to increase the diffusion rate as the temperature is increased to promote adsorption.

The step (c) is a step of preparing a composite stabilizer for PVC by mixing the encapsulation stabilizer and the powder stabilizer. Mixing the liquid stabilizer and the powder stabilizer through a method of mixing the encapsulation stabilizer and the powder stabilizer in which the liquid stabilizer is adsorbed. It is possible to minimize the occurrence of agglomeration that occurs when the

The composite stabilizer for PVC as described above serves as a heat stabilizer to increase the thermal stability of the composition during PVC processing, and as a lead-free heat stabilizer, it is environmentally friendly because it does not contain harmful heavy metal components such as lead and cadmium.

In addition, by allowing the liquid stabilizer to be absorbed into the emulsion adsorbent to prepare the encapsulation stabilizer, and then mixing the prepared encapsulation stabilizer with the powder stabilizer, the powder stabilizer and the liquid stabilizer are mixed by blocking exposure of the powder stabilizer to an excess of the liquid stabilizer. It is possible to solve the aggregation phenomenon of powder stabilizers that arise during mixing or kneading synthesis, overcome difficulties in insufficient dispersibility and fine particles, and synergistic effects are induced. shortcomings can be compensated for.

The powder stabilizer as described above is a calcium/zinc-based powder stabilizer, a barium/zinc-based powder stabilizer, a magnesium/zinc-based powder stabilizer, hydrotalcite, a calcium/magnesium/zinc-based powder stabilizer, a magnesium aluminum carbonate-based powder stabilizer, and a zinc-based powder. stabilizers or mixtures thereof.

More preferably, the powder stabilizer, 30 to 50 parts by weight of hydrotalcite, 10 to 20 parts by weight of zinc stearate, 15 to 30 parts by weight of calcium stearate, dibenzoylmethane (dibenzoyl methane) 3 to 8 parts by weight, stearyl benzoyl methane 3 to 8 parts by weight, antioxidant (anti-oxidant) 1 to 3 parts by weight, and filler (filler) 5 to 20 parts by weight of a mixture comprising A Ca/Zn mixed powder stabilizer prepared using

In this step, a composite stabilizer for PVC may be prepared by mixing the encapsulation stabilizer and the powder stabilizer, and the weight ratio of the encapsulation stabilizer and the powder stabilizer may be adjusted according to the use of the PVC product for manufacturing.

Encapsulation stabilizer improves the initial coloration, transparency, weather resistance, foamability, etc. of PVC resin products as it contains a liquid stabilizer, and while exhibiting the characteristic of not emitting harmful components to the human body, there is a problem of lowering activity and heat resistance, and powder stabilizer While improving activity, weather resistance, and foamability, there is a problem of lowering initial coloration and transparency, so in the present invention, the above encapsulation stabilizer and powder stabilizer are mixed and introduced to solve the problems of each stabilizer.

In addition, the composite stabilizer for PVC can overcome the difficulties of powder stabilizer agglomeration, insufficient dispersibility and fine particles, which arise when the powder stabilizer and the liquid stabilizer are mixed or kneaded.

To this end, the composite stabilizer for PVC can be prepared by mixing 10 to 40 parts by weight of the encapsulation stabilizer and 60 to 90 parts by weight of the powder stabilizer. If it exceeds 40 parts by weight, it is difficult to uniformly disperse the powder stabilizer, so that the appearance quality of the PVC resin product may be deteriorated.

In addition, in this step, an additive may be additionally mixed to improve the physical properties of PVC products to prepare a composite stabilizer for PVC.

Additives may include plasticizers, processing aids, color improvers, antioxidants, UV stabilizers, flame retardants, lubricants, antistatic agents, foaming agents, fillers, antibacterial agents, colorants, antifouling agents, nucleating agents, antiblocking agents, slip agents, or mixtures thereof. .

Plasticizers play a role in increasing the flexibility, workability, and expansibility of PVC resin, and can be mixed to produce soft PVC products, and the amount added can be adjusted to impart soft properties.

Plasticizers include phthalate-based plasticizers, fatty acid (aliphate)-based plasticizers, trimellitate-based plasticizers, polyester-based plasticizers, epoxy-based plasticizers, phosphate-based plasticizers, and glycols. )-based plasticizers or mixtures thereof may be used.

The processing aid is added to improve the processability of PVC resin, prevent melt fracture, reduce the occurrence of flow marks and fish eyes, and improve gloss. A processing aid, a styrene-based processing aid, or an organic phosphite-based composite processing aid may be used.

The auxiliary stabilizer serves to supplement the physical properties of the PVC resin together with the liquid stabilizer and powder stabilizer, and an organotin stabilizer including tin malate, tin laurate, powdered tin malate ester, or mixtures thereof can be mixed and used. .

Antioxidants inhibit or block the reaction between PVC resin and oxygen to prevent decomposition and help maintain physical properties, and phenolic antioxidants such as alkylthiomethylphenol or thiodipropionic acid ester for example.

A UV stabilizer serves to inhibit or block thermal decomposition of the PVC resin due to UV rays, and azodiphenylaniline and the like are representative examples.

The flame retardant serves to reduce the combustibility of PVC resin by flame, and the lubricant lubricates the metal surface in contact with the polyvinyl chloride resin during calendar processing, molding, and extrusion to increase fluidity. may include

The internal lubricant lowers the flow viscosity of the polyvinyl chloride-based resin composition dissolved during molding process to reduce frictional heat generation, and includes butyl stearate, stearyl stearate, glycerin monostearate, stearic acid, bis-amide, Lauryl alcohol, epoxidized soybean oil, or a mixture thereof may be used.

The external lubricant reduces the friction between the dissolved resin and the processing equipment during molding and serves to enhance the releasability of the polyvinyl chloride-based resin composition on the surface of the processing equipment, and contains montanic acid wax, paraffin wax, polyolefin wax, ester wax, or Mixtures thereof may be used.

The antistatic agent functions to suppress or remove static electricity generation in the PVC resin, and a blowing agent may be added to produce a porous product.

The reinforcing agent includes an impact modifier that improves impact resistance, an extender filler added in large quantities for the purpose of cost reduction, and a filler that improves processability.

It serves as a reinforcing filler added to improve the mechanical, thermal, electrical properties or processability of the PVC resin composition, and inorganic, organic, or mixtures thereof can be introduced. Powder, flat, needle, spherical, Those having various shapes such as fibers, fibrous fabrics, and the like can be used. As a filler, glass fiber, calcium carbonate, talc, mica, silica stone, wood powder, etc. are representative examples. Calcium carbonate can be used alone, or glass fiber, talc, mica, silica stone, wood powder, etc. can be mixed with calcium carbonate. and is not limited thereto.

The impact modifier is a material for reinforcing impact resistance by giving elasticity to the polyvinyl chloride-based resin composition. It can increase fracture, tensile, compression, bending, and impact strength, and enhance dimensional stability and resistance to thermal deformation. The reinforcing agent may be methyl methacrylate-butadiene-styrene, chlorinated polyethylene, acrylic, or a mixture thereof.

The antibacterial agent serves to improve the antibacterial properties of polyvinyl chloride resin, and includes antimicrobial metals such as silver (Ag), copper (Cu), manganese (Mn), zinc (Zn), titanium dioxide or mixtures thereof such as zeolite, silica, A porous composite antibacterial agent prepared by substituting an inorganic carrier such as alumina may be introduced.

The pigment (colorant) serves to impart color to PVC products, and pigments including titanium and nickel can be used, and the antifogging agent serves to suppress the generation of air bubbles generated inside the polyvinyl chloride resin composition. do

The composite stabilizer for hybrid type PVC according to a preferred embodiment of the present invention may be introduced into a high molecular weight PVC resin having a polymerization degree of 1700 to 2200 and a K value of 74 to 80.

The composite stabilizer for PVC according to the present invention can be used to prepare PVC products by mixing with polyvinyl chloride resin using conventional various types of equipment such as mixers, calendars, kneaders, extruders, mills, etc., calendaring, extrusion PVC products may be manufactured by processing using a variety of conventional methods such as injection molding, sintering or spinning, extrusion blow molding or plastisol processes.

The composite stabilizer for PVC according to the present invention is a semi-rigid PVC product, container, It can be used to manufacture rigid injection molded products or extruded products such as packaging films, thermoformable films, blown films, pipe bodies, foams, frames, and the like.

As described above, the manufacturing method of the composite stabilizer for hybrid type PVC according to the present invention is a method of absorbing a liquid stabilizer using an emulsifying adsorbent to prepare an encapsulated stabilizer in which the liquid stabilizer is encapsulated, and then mixing the prepared encapsulating stabilizer with a powder stabilizer. Through this, it is possible to minimize the aggregation of the powder stabilizer that occurs when mixing the liquid stabilizer and the powder stabilizer, and to manufacture a hybrid-type composite stabilizer for PVC with uniform dispersibility and stability.

The composite stabilizer for hybrid type PVC prepared in the above way can minimize the discharge of harmful components to the human body, which is a disadvantage of the liquid stabilizer, so it is possible to manufacture eco-friendly PVC products, and it improves the dispersibility and the working environment, which are the disadvantages of the powder stabilizer It can contribute to the improvement of the productivity of PVC products.

On the other hand, the present invention provides a composite stabilizer for hybrid type PVC prepared by the method as described above.

The hybrid-type composite stabilizer for PVC is a measure to minimize the disadvantages of powder stabilizer, such as low dispersibility, increase in viscosity, and generation of dust, and encapsulate the liquid stabilizer using an emulsifying adsorbent to mix the powder stabilizer and the liquid stabilizer. and finally, a stabilizer with a moist feeling can be prepared.

However, in the prior art, when a liquid and powder stabilizer are mixed, agglomeration occurs and dispersibility is greatly reduced, and there is a problem that the surface smoothness of PVC products is greatly reduced. ) to mix the powder stabilizer and the liquid stabilizer to solve the problem.

The composite stabilizer for hybrid type PVC according to the present invention as described above can dramatically reduce the content of volatile organic compounds contained in the stabilizer, and can be used as a phenol and formaldehyde-free stabilizer, and can be used as a wallpaper, flooring, window frame, It can be easily used in the production of PVC products such as wall materials, building materials, electric wire covering materials, automotive interior and exterior materials, artificial leather, agricultural materials, food packaging materials, pipes, paints, hoses, sheets, toys, daily necessities, and sanitary materials.

Hereinafter, the present invention will be described in more detail by way of examples.

The presented examples are only specific examples of the present invention, and are not intended to limit the scope of the present invention.

<Example>

(1) encapsulation evaluation

In order to evaluate the characteristics of each emulsified adsorbent material for encapsulating the liquid stabilizer, a ceramic material having a large specific surface area and a plurality of pores formed on the surface was searched. (silica), synthetic zeolite, natural zeolite, diatomite, talcite, talc and modified silica were selected as candidates.

Modified silica is prepared by mixing 100 parts by weight of water, 50 parts by weight of silica powder, and 0.5 parts by weight of sodium chloride to prepare a suspension, supplying the prepared suspension to an electrolysis device, and then using a voltage to electrolyze water and electrolyte, sodium chloride, in the suspension It was decomposed to form bubbles, and the silica powder was pretreated with the generated bubbles, and the surface modifier was mixed with the suspension containing the pretreated silica powder and heated at 90 ° C. for 2 hours to react the silica powder and the surface modifier. . A silica powder reacted with a surface modifier was obtained and dried, and the dried silica powder was supplied to a heating chamber and then heat-treated at a temperature of 350° C. for 3 hours to prepare a modified silica powder. The surface modifier was mixed in a ratio of 0.5 parts by weight based on 100 parts by weight of the suspension, and octyl gallate was supplied to the suspension as a surface modifier.

The adsorption characteristics of each material were evaluated by allowing the liquid stabilizer to be absorbed using the selected candidate material, and the results are shown in Table 1. The adsorption property evaluation was performed by mixing 30 parts by weight of a liquid stabilizer with respect to 70 parts by weight of the emulsified adsorbent powder. By spraying the liquid stabilizer into the emulsion adsorbent through a nozzle using compressed air, the liquid stabilizer and the emulsified adsorbent were mixed and emulsified. A facility was devised and carried out to adsorb the liquid stabilizer to the adsorbent to prepare the encapsulated stabilizer. As the liquid stabilizer, a mixed liquid stabilizer in which 80 parts by weight of a Ca/Zn liquid stabilizer and 20 parts by weight of a Ba/Zn liquid stabilizer were mixed was used.

As shown in Table 1, all of the candidate materials were judged to be capable of adsorbing the liquid phase or impossible to adsorb depending on the porous material or the size of the pores, and the liquid stabilizer was subjected to a mixing test at a ratio of 30 parts by weight higher than the actual expected ratio. However, this was performed to determine the stable adsorption capacity. Considering the product cost, high to low cost materials were reviewed, and silica was found to be the most suitable for the purpose, so silica and modified silica were selected as emulsified adsorbents for encapsulation.

(2) Evaluation of mixing ratio

In order to confirm the optimal mixing ratio of the emulsion adsorbent and the liquid stabilizer, the mixing ratio of the encapsulated stabilizer in which the liquid stabilizer is adsorbed to the emulsion adsorbent was evaluated, and the results are shown in Table 2 below.

Mixing ratio evaluation was performed by mixing in a simple method by ratio on lab scale to check the appearance, and silica powder and liquid stabilizer were mixed using on-site production equipment to prepare sealed stabilizer samples 1 to 5, and mixing ratio evaluation was performed. For the encapsulation stabilizer samples 1 to 5, the composition is as shown below. In addition, by using the modified silica powder as an emulsion adsorbent powder, encapsulation stabilizer samples 6 to 8 were prepared.

As shown in Table 3, as a result of checking the mixing ratio of the liquid stabilizer and the emulsified adsorbent powder, it was possible to confirm the optimal mixing ratio for the preparation of the encapsulated stabilizer sample, and 20 to 30 parts by weight of the liquid stabilizer and 70 to 80 parts by weight of the silica powder were mixed. Or a mixture of 20 to 35 parts by weight of a liquid stabilizer and 65 to 80 parts by weight of silica powder had the best appearance characteristics, so it was possible to grasp the suitable adsorption capacity of the emulsified adsorbent powder.

Through the above results, the modified silica powder has a large number of pores on the surface compared to the basic silica powder particles showing hydrophilicity, so that the surface area that can absorb the liquid stabilizer is increased, and the amphiphilic component is fixed on the surface to make hydrophobicity. It was confirmed that the absorption amount for the liquid stabilizer was significantly increased, and accordingly, it was confirmed that the appearance and encapsulation performance were improved.

(4) Evaluation of properties of composite stabilizers for hybrid type PVC

Composite stabilizer samples 1 to 4 for hybrid-type PVC were prepared by mixing the encapsulation stabilizer sample 4 and the powder stabilizer with the composition shown in Table 4 below, and the physical properties of the prepared hybrid-type PVC composite stabilizer were evaluated and the results are as follows. Table 5 shows. The encapsulation stabilizer was prepared by mixing 20 parts by weight of the liquid stabilizer and 80 parts by weight of the emulsified adsorbent powder.

In addition, by mixing the encapsulated stabilizer sample 7 and the powder stabilizer, composite stabilizer samples 5 to 7 for hybrid-type PVC were prepared, and the physical properties of the prepared composite stabilizer for hybrid-type PVC were evaluated.

1) Thermal stability

The physical properties of the prepared PVC composite stabilizer sample were evaluated, and the results are shown in Table 5 below. Thermal stability and appearance were evaluated in a test mill and oven using a specimen prepared by mixing the prepared PVC composite stabilizer with PVC resin (however, in Table 5 below, NA is not applied, ◎ is very good, ○ is excellent, △ indicates normal, X indicates inferior).

As shown in Table 5, the thermal stability of the PVC product prepared using the prepared composite stabilizer sample is the best in Sample 2 prepared by mixing 20 parts by weight of the encapsulation stabilizer and 80 parts by weight of the powder stabilizer, and in the case of Samples 1 and 3 was judged to be good.

As a result of evaluating the appearance of the composite stabilizer sample, it was confirmed that when using the sealed stabilizer sample 4, the mixing ratio was 20 to 30 parts by weight of the sealed stabilizer and 70 to 80 parts by weight of the powder stabilizer.

The thermal stability and appearance of the PVC product manufactured using the prepared composite stabilizer sample was confirmed to be the best when the composite stabilizer 6 prepared using the encapsulated stabilizer sample 8 was used.

<Experimental Example 3>

(1) Total volatile organic compound content evaluation

The amount of total volatile organic compounds (TVOCs) emitted from PVC products manufactured using complex stabilizer samples 1 to 7 was evaluated, and the results are shown in Table 6 below. TVOCs were performed according to the test method for eco-friendly building materials (SPS-KACA008-138), and PVC specimens (size: 165 × 165 mm) prepared by adding a composite stabilizer for PVC were left in an enclosed space at 25 °C for 7 days. The chamber method was used to collect the released TVOC and analyze it with GC analysis equipment, and the unit was expressed as the amount of mg TVOC released per hour at 1 m ² (mg/m ² h).

However, for PVC products, 10 parts by weight of a composite stabilizer sample prepared based on 100 parts by weight of PVC resin, 1.5 parts by weight of methyl methacrylate, 7 parts by weight of chlorosulfonated polyethylene, 2 parts by weight of stearyl stearate, butyl methacrylate And a PVC composition prepared by mixing 5 parts by weight of a methyl methacrylate mixture (weight ratio 1:2), 10 parts by weight of calcium carbonate, 2 parts by weight of a sunscreen, and 5 parts by weight of titanium dioxide was molded by injection molding.

As shown in Table 6, as a result of evaluating the release amount of total volatile organic compounds in the PVC specimen prepared by adding the composite stabilizer for PVC, it was confirmed that all but less than 0.01 mg/m ² h of the composite stabilizer sample 4 were As for the emission amount, the emission of total volatile organic compounds from the wallpaper meets the environmental mark certification standards (less than 20 mg/m ² h) and indoor flooring materials certification standards (less than 0.4 mg/m ² h), so it is possible to manufacture eco-friendly PVC products. I was able to confirm that it was possible.

In particular, in the case of PVC product specimens prepared with samples 5 to 7 in which the modified silica powder was introduced, the liquid stabilizer was included in excess compared to samples 1 to 4, but the emission amount of total volatile organic compounds was low compared to the content, so eco-friendliness could be improved. was judged to be

(2) Phenol content evaluation

The content (unit: ppm) of phenol contained in PVC products prepared using the composite stabilizer samples 1 to 7 was evaluated, and the results are shown in Table 6 above.

To evaluate the phenol content, based on the GC-MSD analysis method, a PVC specimen (size: 165 × 165 mm) prepared by adding a composite stabilizer for PVC was left in a closed space at 25°C for 7 days, and released phenol was collected. The chamber method was analyzed by GC analysis equipment, and the unit was expressed as the amount of mg TVOC released per hour at 1 m ² (mg/m ² h).

As shown in Table 6, as a result of evaluating the phenol content of the PVC specimens prepared by adding the composite stabilizer for PVC, it was confirmed that all phenol components were not detected.

(3) Formaldehyde content evaluation

The content (unit: ppm) of formaldehyde (HCHO) contained in PVC products prepared using the complex stabilizer samples 1 to 7 was evaluated, and the results are shown in Table 6 above.

To evaluate the formaldehyde content, the PVC specimen (size: 165 × 165 mm) prepared by adding a composite stabilizer for PVC was left in a closed space at 25 °C for 7 days according to the GC-MSD analysis method, and the formaldehyde released It was carried out by the chamber method for collecting and analyzing with GC analysis equipment, and the unit was expressed as the amount of mg TVOC released per hour at 1 m ² (mg/m ² h).

As shown in Table 6, as a result of evaluating the formaldehydenol content of the PVC specimens prepared by adding the composite stabilizer for PVC, it was confirmed that no formaldehyde component was detected.

The detailed description of the preferred embodiments of the present invention disclosed as described above is provided to enable any person skilled in the art to make and practice the present invention. Although the above has been described with reference to preferred embodiments of the present invention, it will be understood by those skilled in the art that various modifications and changes can be made to the present invention without departing from the scope of the present invention. For example, a person skilled in the art may use each configuration described in the above-described embodiments in a way that is combined with each other. Accordingly, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

The present invention may be embodied in other specific forms without departing from the spirit and essential characteristics of the present invention. Accordingly, the above detailed description should not be construed as restrictive in all respects but as exemplary. The scope of the present invention should be determined by a reasonable interpretation of the appended claims, and all modifications within the equivalent scope of the present invention are included in the scope of the present invention. The present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein. In addition, claims that are not explicitly cited in the claims may be combined to form an embodiment, or may be included as new claims by amendment after filing.

Claims (8)

(a) mixing an emulsified adsorbent comprising a liquid stabilizer and a porous ceramic powder;
(b) adsorbing the liquid stabilizer to the emulsion adsorbent to prepare an encapsulated stabilizer; and
(c) mixing 10 to 40 parts by weight of the encapsulation stabilizer and 60 to 90 parts by weight of the powder stabilizer to prepare a composite stabilizer for PVC. According to claim 1,
In the step (a), the liquid stabilizer is supplied to a droplet discharge device that discharges droplets using compressed air, and the liquid stabilizer droplets are discharged to the emulsion adsorbent to mix the liquid stabilizer and the emulsion adsorbent. A method for manufacturing a composite stabilizer for hybrid type PVC. According to claim 1,
In the step (a), 15 to 35 parts by weight of the liquid stabilizer and 65 to 85 parts by weight of the emulsion adsorbent are mixed. According to claim 1,
The porous ceramic powder, silica, aluminosilicate, zeolite, illite, diatomaceous earth, a method for producing a hybrid type PVC composite stabilizer, characterized in that it comprises at least one selected from the group consisting of talcite and talc. According to claim 1,
The porous ceramic powder comprises a modified silica powder,
The modified silica powder is
(1) mixing 30 to 70 parts by weight of silica powder with 100 parts by weight of water to prepare a suspension;
(2) electrolyzing the suspension to pretreat silica powder;
(3) preparing a reaction mixture by mixing a surface modifier with the suspension containing the silica powder pretreated in step (2); and
(4) preparing a modified silica powder by heat-treating the reaction mixture;
The surface modifier,
Contains at least one selected from the group consisting of propyl gallate, butyl gallate, octyl gallate, hexyl resorcinol and pentadecylphenol A method for producing a composite stabilizer for hybrid type PVC, characterized in that According to claim 1,
The liquid stabilizer is a calcium/zinc-based liquid stabilizer, a barium/zinc-based liquid stabilizer, a phosphoric acid-based liquid stabilizer, an epoxy zinc-based liquid stabilizer, a mercaptide-based stabilizer, a maleate-based stabilizer, and a carboxylate-based liquid stabilizer. ) A method for producing a composite stabilizer for hybrid type PVC, comprising at least one selected from the group consisting of stabilizers. According to claim 1,
The powder stabilizer is a calcium/zinc-based powder stabilizer, a barium/zinc-based powder stabilizer, a magnesium/zinc-based powder stabilizer, hydrotalcite, a calcium/magnesium/zinc-based powder stabilizer, a magnesium aluminum carbonate-based powder stabilizer, and a zinc-based powder stabilizer. A method for producing a composite stabilizer for hybrid type PVC, comprising at least one selected from the group consisting of. According to claim 1,
The composite stabilizer for PVC is one selected from the group consisting of plasticizers, processing aids, color improvers, antioxidants, UV stabilizers, flame retardants, lubricants, antistatic agents, foaming agents, fillers, antibacterial agents, colorants, anti-fouling agents, nucleating agents, anti-blocking agents and slip agents Method for producing a composite stabilizer for hybrid-type PVC, characterized in that it further comprises more than one kind of additive.

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