KR102152066B1 - Hybrid type PVC stabilizer comprising liquid and powder - Google Patents

Abstract

The present invention relates to a composite stabilizer for PVC, including 50-150 parts by weight of a Ca/Zn liquid stabilizer, 50-150 parts by weight of a Ca/Zn powder stabilizer and 2-30 parts by weight of a silicon compound, and mixed with a polyvinyl chloride resin at a ratio of 0.5-90 parts by weight based on the PVC resin. The composite stabilizer for PVC includes both the Ca/Zn liquid stabilizer and the Ca/Zn powder stabilizer, and thus each of the liquid stabilizer and the powder stabilizer complements each other′s shortcomings, and can produce a PVC product having improved heat stability and weather resistance as compared to a product using either of the Ca/Zn liquid stabilizer and the Ca/Zn powder stabilizer.

Description

Hybrid type PVC stabilizer comprising liquid and powder, and a PVC resin composition comprising the same {Hybrid type PVC stabilizer comprising liquid and powder}

The present invention relates to a hybrid-type composite stabilizer for PVC containing both liquid and powder and a PVC resin composition comprising the same.

Polyvinyl chloride (PVC) has excellent processability and is eco-friendly because it generates less carbon dioxide than 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 cheaper than aluminum and has good thermal insulation effects, as well as excellent properties such as airtightness, sound insulation, chemical resistance, wind pressure resistance, water tightness, and electrical insulation. Therefore, it is used as a material for manufacturing various products such as various household products such as construction materials, interior and exterior materials for automobiles, and food packaging materials, electrical and electronic products, and artificial leather.

PVC is a variety of PVC products by adding a PVC stabilizer mixed with various subsidiary materials such as antioxidants, heat stabilizers, UV stabilizers, flame retardants, lubricants, antistatic agents, foaming agents, impact modifiers, and fillers in order to exhibit the properties required in the product's use. Are manufacturing.

PVC stabilizers as described above are added in a small amount at the stage of molding a product in a PVC processing company to help maintain the physical and chemical properties of the resin during the use period of the finished product, and have a great effect on the quality of the product during or after processing. As an essential additive, PVC resin has developed into a representative thermoplastic resin due to the development of PVC stabilizers.

In particular, PVC contains a large amount of chlorine and has a disadvantage that it is weak to heat compared to other polymers, so protection against thermal degradation caused by heating, light irradiation, and mechanical stress is particularly important.To improve the thermal stability of PVC, PVC PVC products are manufactured by introducing heat stabilizers.

The PVC heat stabilizer can be classified into various types according to chemical composition, functioning performance, handling type, etc., and is classified into powder and liquid according to its shape, and lead-based/ Ca-Zn-based/ Ba-Zn-based /Cd- It can be classified into Ba-Zn type/organic TIN type.

Conventionally, stabilizers containing cadmium (Cd) or lead (Pb) are not only heat resistant but also transparent. It is recognized as a stabilizer with the best performance because it can manufacture products with excellent properties in colorability and processability, but recently, environmental pollution and harmful heavy metal poisoning have been problems, so Ca-Zn-based, K-Zn-based, Na-Zn-based Attempts to use environmentally friendly lead-free thermal stabilizers such as stabilizers are increasing.

However, although the lead-free thermal stabilizer as described above has the advantage of being eco-friendly, the effect of improving thermal stability and weathering resistance is insignificant, and thus a study on a method to supplement it is needed.

The inventors of the present invention are that when a composite stabilizer including both a Ca/Zn liquid stabilizer and a Ca/Zn powder stabilizer is added during PVC processing, the disadvantages of each of the Ca/Zn liquid stabilizer or the Ca/Zn powder stabilizer are compensated and It was confirmed that PVC products with improved thermal stability and weather resistance could be manufactured compared to the case of using a Zn liquid stabilizer or a Ca/Zn powder stabilizer, respectively.

Accordingly, the present invention is to provide a composite stabilizer for PVC including a Ca/Zn liquid stabilizer and a Ca/Zn powder stabilizer and a technical content of a PVC product manufactured using the same.

In order to achieve the above-described technical problem, the present invention includes 50 to 150 parts by weight of a Ca/Zn liquid stabilizer, 50 to 150 parts by weight of a Ca/Zn powder stabilizer, and 2 to 30 parts by weight of a silicon compound, but the polyvinyl chloride resin It provides a composite stabilizer for PVC, characterized in that it is mixed in a ratio of 0.5 to 90 parts by weight based on 100 parts by weight.

The composite stabilizer for PVC is one or more additives selected from the group consisting of plasticizers, processing aids, antioxidants, ultraviolet stabilizers, flame retardants, lubricants, antistatic agents, foaming agents, fillers, antibacterial agents, coloring agents, anti-drop agents, nucleating agents, anti-blocking agents, and slip agents. It may further include.

In addition, the composite stabilizer for PVC may be mixed with a polyvinyl chloride resin having a K value of 50 to 85 and a polymerization degree of 500 to 2500.

According to a preferred embodiment of the present invention, the composite stabilizer for PVC comprises: (a) preparing a mixture by mixing 50 to 150 parts by weight of the Ca/Zn liquid stabilizer and 2 to 30 parts by weight of a silicon compound; And (b) mixing 50 to 150 parts by weight of the Ca/Zn powder stabilizer in the mixture.

In addition, the present invention provides a PVC composition comprising the above-described PVC composite stabilizer and polyvinyl chloride resin, wherein the polyvinyl chloride resin 100 parts by weight and 0.5 to 90 parts by weight of the PVC composite stabilizer do.

The composite stabilizer for PVC according to the present invention includes both a Ca/Zn liquid stabilizer and a Ca/Zn powder stabilizer to complement each other's disadvantages of a liquid stabilizer or a powder stabilizer, and use a Ca/Zn liquid stabilizer or a Ca/Zn powder stabilizer. Compared to the case of each use, it is possible to manufacture PVC products with improved thermal stability and weather resistance.

1 is a table showing the physical property analysis results of PVC specimens prepared by the method according to Examples 1, 2, and Comparative Examples 1 to 4.

In the present specification, the'composite stabilizer for PVC' is a thermal stabilizer, Ca/Zn liquid stabilizer, Ca/Zn powder stabilizer, silicon compound and plasticizer, antioxidant, ultraviolet stabilizer, flame retardant, lubricant, antistatic agent, foaming agent, impact modifier, filler, It means a mixture of the composition type comprising an additive including an antibacterial agent, a colorant, an anti-drop agent, a nucleating agent, an antiblocking agent, a slip agent, or a mixture thereof.

In the present specification,'Ca/Zn liquid stabilizer'and'Ca/Zn powder stabilizer' refer to a liquid stabilizer and a powder stabilizer containing calcium (Ca) and zinc (Zn), respectively, and'Ca/Zn liquid stabilizer' is Typical examples are those prepared using a mixture containing calcium hydroxide (Ca(OH) ₂ ), zinc oxide (ZnO), benzoic acid, oleic acid, citric acid, and distilled water.'Ca/Zn powder stabilizer' is calcium hydroxide (Ca (OH) ₂ ), zinc nitrate (Zn (NO ₃ ) ₂ ) powder, urea (urea), and a representative example of a mixture containing distilled water.

Hereinafter, the present invention will be described in detail.

The composite stabilizer for PVC according to the present invention includes a Ca/Zn liquid stabilizer and a Ca/Zn powder stabilizer to manufacture a PVC molded article having improved physical properties.

Specifically, the Ca/Zn liquid stabilizer and the Ca/Zn powder stabilizer serve as a heat stabilizer that increases the thermal stability of the composition during PVC processing, and as a lead-free heat stabilizer, it is eco-friendly because it does not contain harmful components of heavy metals such as lead and cadmium. .

In particular, the composite stabilizer for PVC, which includes both a Ca/Zn liquid stabilizer and a Ca/Zn powder stabilizer, enables the manufacture of PVC products with more improved properties such as heat resistance and weather resistance, which is a Ca/Zn liquid stabilizer and Ca/ This is because synergistic effects are induced when all of the Zn powder stabilizers are included, so that the disadvantages of the thermal stabilizer in which a Ca/Zn liquid stabilizer or a Ca/Zn powder stabilizer is added alone can be compensated.

According to a preferred embodiment of the present invention, the composite stabilizer for PVC may include a Ca/Zn liquid stabilizer and a Ca/Zn powder stabilizer in a weight ratio of 10:1 to 1:10, respectively, and use of a PVC molded article for manufacturing It can be used by adjusting the weight ratio according to.

In addition, the Ca/Zn liquid stabilizer and the Ca/Zn powder stabilizer may be mixed in a ratio of 0.5 to 90 parts by weight based on 100 parts by weight of the polyvinyl chloride resin, and the Ca/Zn liquid stabilizer and the Ca/Zn powder stabilizer are 0.5 If it is mixed in less than parts by weight, there is a problem that the thermal stability of the polyvinyl chloride resin is deteriorated, and if it exceeds 90 parts by weight, there is a problem that a blooming phenomenon occurs during molding.

Preferably, the composite stabilizer for PVC may include a Ca/Zn liquid stabilizer and a Ca/Zn powder stabilizer in a weight ratio of 2:3 to 3:2, respectively, and 3 to 15 parts by weight based on 100 parts by weight of a polyvinyl chloride resin It can be added by mixing in a negative ratio.

More specifically, the Ca/Zn liquid stabilizer improves the initial coloration, transparency, weather resistance, and foamability of the polyvinyl chloride resin, and while exhibiting characteristics that do not emit harmful components to the human body, there is a problem of lowering the activity and heat resistance. While the Ca/Zn powder stabilizer improves activity, weather resistance, and foamability, there is a problem of lowering initial coloration and transparency.

As the PVC composition according to the present invention contains the Ca/Zn liquid stabilizer and the Ca/Zn powder stabilizer at the same time, it compensates for the disadvantages of each of the Ca/Zn liquid stabilizer and the Ca/Zn powder stabilizer, thereby greatly improving weather resistance, colorability, and heat resistance. Improved PVC moldings can be produced.

In addition, the composite stabilizer for PVC is prepared by the following method so that the powder stabilizer and the liquid stabilizer can overcome the difficulties of the agglomeration of the powder stabilizer, insufficient dispersibility and microparticles, which arise during mixing or kneading synthesis. It can be hybridized by mixing a stabilizer and a powder stabilizer.

To this end, the composite stabilizer for PVC may be configured to further include a silicon compound such as porous silica or alumino silicate.

Specifically, the composite stabilizer for PVC is a Ca/Zn liquid stabilizer and a silicon compound, respectively, so that the Ca/Zn liquid stabilizer is absorbed by the porous silicon compound, and then Ca/Zn powder is added to a mixture of a Ca/Zn liquid stabilizer and a silicon compound. Stabilizer is mixed, and the liquid stabilizer is absorbed into the silicon compound to block exposure of the powder stabilizer to an excessive amount of liquid stabilizer, so that the agglomeration of Ca/Zn powder stabilizer that arises when the powder stabilizer and liquid stabilizer are mixed or kneaded. It can solve the problem and overcome the difficulty of insufficient dispersibility and atomization.

To this end, a silicon compound such as porous silica or alumino silicate may be used by introducing a porous silica or porous alumino silicate having a large number of pores having an average size of 1 to 500 Å, and the silicon compound has an average particle size of 0.01 to 1,000. It is possible to use ㎛.

In addition, the silicon compound may be a porous silica, alumino silicate, or a mixture thereof, and it is preferable to add in a ratio of 2 to 10 parts by weight based on 100 parts by weight of a Ca/Zn liquid stabilizer and a Ca/Zn powder stabilizer, If the added amount of the silicon compound is less than 2 parts by weight, a problem may occur in which the anti-aggregation effect and the atomization effect are insignificant, and if it exceeds 10 parts by weight, the thermal stability may be impaired.

More specifically, the composite stabilizer for PVC is a Ca/Zn liquid stabilizer 50 to 150 parts by weight and a silicon compound 2 to 30 parts by weight so that the Ca/Zn liquid stabilizer is absorbed by the silicon compound, and then the Ca/Zn powder stabilizer 50 to 150 parts by weight may be mixed to prepare a stabilizer composition, and a composite stabilizer for PVC may be prepared by mixing an additive with the prepared stabilizer composition.

In particular, the preparation of a mixture of Ca/Zn liquid stabilizer and silicon compound, and mixing of the mixture and Ca/Zn powder stabilizer are performed by rotating the stirring blade to apply a disturbing flow motion to the mixture and the Ca/Zn powder stabilizer to obtain the mixture and the Ca/Zn powder stabilizer. It is preferable to carry out using a kneading device such as a rotor kneader to ensure uniform kneading.

As an example, the kneading device can form a structure in which the upper and lower parts are intersected during kneading by using a twin-axial kneading device equipped with a low-speed stirring blade and a high-speed stirring blade (7,000 to 12,000 rpm) so that the upper and lower parts can be crossed during mixing. It has a double structure that allows the Ca/Zn liquid stabilizer, silicon compound, Ca/Zn powder stabilizer, and additives to be suspended and rolled to be mixed, and to maintain a temperature of 35 to 40 ℃ in consideration of frictional heat. What is equipped with a water cooling jacket can be introduced and used.

In addition, the Ca/Zn liquid stabilizer used is a mixture containing 10 parts by weight of calcium hydroxide, 3 parts by weight of zinc oxide, 2 parts by weight of benzoic acid, 3 parts by weight of oleic acid, 2 parts by weight of citric acid, and 80 parts by weight of distilled water. After reacting at temperature for 10 to 60 minutes, water is removed by vacuum, and then, in order to control saturation and molecular weight, 2 to 3 parts by weight of PVA and emulsifier mixture are mixed based on 100 parts by weight of the mixture from which distilled water is removed, and then atomized by high speed rotation. By controlling the physical structure of the Ca/Zn liquid stabilizer so that the hybridization of the Ca/Zn liquid stabilizer and the Ca/Zn powder stabilizer can be smoothly induced, the average particle size of the Ca/Zn particles contained in the Ca/Zn liquid stabilizer is 1 It can be used to adjust to 100 Å.

In addition, the Ca/Zn powder stabilizer is mixed by applying 100 to 2000 W of ultrasonic waves to a mixture containing 10 parts by weight of calcium hydroxide powder, 5 parts by weight of Zn Nitrate powder, 30 parts by weight of urea, and 55 parts by weight of distilled water. Then, put in a hydrothermal synthesis container with a built-in Teflon tube, sealed, and hydrothermal treatment at 120 to 220°C for 5 to 12 hours to prepare a synthetic powder, and then to obtain a synthetic powder using a centrifuge (FLETA5, Hanil), A flake Ca/Zn powder stabilizer having an average particle size of 50 to 500 nm prepared by heat-treating the obtained powder at 150 to 300° C. for 12 hours may be used.

Polyvinyl chloride (PVC) resin for introducing the composite stabilizer for PVC according to the present invention is a kind of thermoplastic plastic, which is easy to color, is relatively hard, and has excellent moldability, and polyvinyl chloride resin is suitable for molding processing. During fermentation, it is easy to decompose or deteriorate by heat, or because crystallinity is remarkably low, it is decomposed by light or heat during storage, colored yellow or brown, is brittle, and is weak against heat.

As the polyvinyl chloride resin, a polyvinyl chloride resin obtained by polymerizing a vinyl chloride monomer alone may be used, and a copolymer of a vinyl chloride monomer and a vinyl chloride monomer copolymerizable with a monomer or a polymer may be used.

The monomer copolymerizable with the vinyl chloride monomer is an olefin monomer including ethylene, propylene, butylene or a mixture thereof, a vinyl ester monomer including vinyl propionate, an ethyl vinyl ether, a vinyl including butyl vinyl ether, or a mixture thereof. (Meth)acrylate monomers including ether monomers, methyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate or mixtures thereof, styrene, alpha-methyl styrene, or their Aromatic vinyl monomer including a mixture, vinyl fluoride, vinylidene fluoride, vinylidene chloride, or halogen-based monomers including mixtures thereof, and N-phenylmaleimide, N-cyclohexylmaleimide, or mixtures thereof Representative examples include N-substituted maleimide-based monomers or mixtures thereof. In addition, as a polymer copolymerizable with a vinyl chloride monomer, a polymer obtained by polymerizing the above-described monomers may be used.

Preferably, the polyvinyl chloride resin has a degree of polymerization of 500 to 2,500, and a K value of 50 to 85. When the degree of polymerization is less than 500 or the K value is less than 50, such as tensile strength and hardness There is a problem with low mechanical properties, and when the degree of polymerization exceeds 2,500 or the K value exceeds 85, the moldability is low at a normal processing temperature, and when the processing temperature is increased, a problem of lowering the thermal stability may occur. More preferably, the polyvinyl chloride resin has a polymerization degree of 1700 to 2200, and a high molecular weight polyvinyl chloride resin having a K value of 74 to 80 may be used, and the composite stabilizer for PVC according to the present invention is a liquid type and a powder type. Including all of the stabilizers of the high molecular weight polyvinyl chloride resin can contribute to the improvement of physical properties such as weather resistance and thermal stability.

Specifically, when only a Ca/Zn liquid stabilizer is introduced into a polyvinyl chloride resin having a degree of polymerization of 1700 to 2200, the Ca/Zn liquid stabilizer is a stability problem in the polyvinyl chloride resin, so thixotropy and pinhole ( pinhole), but the PVC composition according to the present invention complements the disadvantages of the Ca/Zn liquid stabilizer by simultaneously including a Ca/Zn liquid stabilizer and a Ca/Zn powder stabilizer to increase the activity of the polyvinyl chloride resin. Compared to the case of using /Zn powder stabilizer alone, it can be increased significantly.

This means that the high molecular weight polyvinyl chloride resin increases mechanical properties as the degree of polymerization of the resin increases, but the problems of lowering the extrusion processability due to lower resin meltability and melt flow properties, increased extrusion load, and heat generation in the extruder are further improved. This is because the activity of the polyvinyl chloride resin can be significantly increased compared to the case of using only the Ca/Zn powder stabilizer.

In addition, the polyvinyl chloride resin as described above may further include a chlorinated olefin polymer in order to improve impact resistance.

Chlorinated olefin polymer is chlorosulfonated polyethylene, chlorinated ethylene vinyl acetate copolymer, chlorosulfonated ethylene vinyl acetate copolymer, chlorinated ethylene acrylic acid copolymer, chlorosulfonated ethylene acrylic acid copolymer, chlorinated ethylene methacrylic acid copolymer, chlorosulfonated Ethylene methacrylic acid copolymer, chlorinated ethylene methyl acrylate copolymer, chlorinated ethylene methyl methacrylate copolymer, chlorinated ethylene n-butyl methacrylate copolymer, chlorinated ethylene glycidyl methacrylate copolymer, maleic anhydride and Representative examples include a chlorinated graft copolymer of ethylene, a chlorosulfonated copolymer of ethylene and propylene, butene, 3-methyl-1-pentene, or octene, or a copolymer including one or more thereof.

Composite stabilizers for PVC according to the present invention are plasticizers, processing aids, auxiliary stabilizers, antioxidants, UV stabilizers, flame retardants, lubricants, antistatic agents, foaming agents, fillers, antibacterial agents, coloring agents, anti-drop agents, nucleating agents, anti-blocking agents, slip agents, or their It may further include an additive including a mixture.

Plasticizers play a role in increasing the flexibility, workability and expandability of the polyvinyl chloride resin, and can be mixed to manufacture soft PVC products, and the amount of addition can be adjusted to impart soft properties.

Plasticizers are phthalate plasticizers, aliphate plasticizers, trimellitate plasticizers, polyester plasticizers, epoxy plasticizers, phosphate plasticizers, glycols )-Based plasticizers or mixtures thereof may be used, and may be included in an amount of 20 to 40 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.

If the content of the plasticizer is less than 20 parts by weight, the plasticizer is not good, so the defect rate increases during the manufacturing process of PVC products, and it is difficult to manufacture a soft product.If the content of the plasticizer exceeds 40 parts by weight, the polyvinyl chloride The increase in plasticity may cause problems that do not satisfy the strength required by the product, and the amount of addition can be adjusted according to the hardness of a PVC molded product made of polyvinyl chloride resin.

The processing aid is added to improve the workability of the polyvinyl chloride resin, prevent melt fracture, reduce the occurrence of flow marks and fish eyes, and improve gloss. , Acrylic processing aids, styrene processing aids, or organic arric acid ester complex processing aids can be used.

Preferably, the processing aid may be mixed in a ratio of 0.5 to 2 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin, and when the content of the processing aid is less than 1 part by weight, the surface property and processability of the polyvinyl chloride resin are low. And, if it exceeds 2 parts by weight, there is a problem that the extrusion load is increased.

The auxiliary stabilizer plays a role of supplementing the physical properties of the polyvinyl chloride resin together with the Ca/Zn liquid stabilizer and the Ca/Zn powder stabilizer, and is an organic alcohol containing tin maleate, tin laurate, powdered tin maleate ester, or a mixture thereof. Stone-based stabilizers can be mixed and used. The auxiliary stabilizer may be included in a ratio of 1 to 15 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.

Antioxidants help to maintain physical properties by inhibiting or blocking the reaction between polyvinyl chloride resin and oxygen, preventing decomposition, and phenolic antioxidants such as alkylthiomethylphenol or thiodipropionic acid esters. Is a representative example.

Antioxidants can be mixed in a ratio of 0.1 to 5 parts by weight based on 100 parts by weight of the polyvinyl chloride resin, and when the content of the antioxidant is less than 0.1 parts by weight, the antioxidant effect is insignificant, and when it exceeds 5 parts by weight, PVC Problems of deteriorating the physical properties of the composition may occur.

The UV stabilizer plays a role of inhibiting or blocking the thermal decomposition of the polyvinyl chloride resin due to ultraviolet rays, and azodiphenylaniline, etc., is a typical example, and from 0.5 to 100 parts by weight of the polyvinyl chloride resin. It can be mixed in a proportion of 6 parts by weight.

When the sunscreen is mixed in an amount of less than 0.5 parts by weight, the ultraviolet blocking effect is not great, and when it exceeds 6 parts by weight, mechanical properties are deteriorated and manufacturing cost may increase.

The flame retardant serves to reduce the flammability of the polyvinyl chloride resin by flame, and may be mixed in a ratio of 0.5 to 5 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.

The lubricant serves to increase fluidity by lubricating the metal surface in contact with the polyvinyl chloride resin during calendar processing, molding, and extrusion, and may include an internal lubricant and an external lubricant.

The internal lubricant reduces the flow viscosity of the polyvinyl chloride-based resin composition dissolved during molding and reduces the occurrence of frictional heat generation.Butyl stearate, stearyl stearate, glycerin monostearate, stearic acid, bis-amide, Lauryl alcohol, epoxidized soybean oil, or mixtures thereof may be used.

The external lubricant reduces the friction between the dissolved resin and the processing device during molding and improves the releasability of the polyvinyl chloride resin composition on the surface of the processing device. Montanic acid wax, paraffin wax, polyolefin wax, ester wax, or Mixtures of these can be used.

Preferably, the lubricant may be mixed in a ratio of 1 to 2 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.

The antistatic agent functions to suppress or eliminate the generation of static electricity in the polyvinyl chloride resin, and the antistatic agent may be mixed in a ratio of 1 to 2 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.

The blowing agent is added to produce a porous product, and the blowing agent may be mixed in a ratio of 1 to 2 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.

Reinforcing agents include an impact modifier that improves impact resistance and a filler that acts as an extender filler added in large quantities for the purpose of cost reduction and improves processability.

It serves as a reinforcing filler added to improve the mechanical, thermal, electrical properties or processability of the polyvinyl chloride-based resin composition, and can introduce inorganic, organic, or mixtures thereof, and powder, flat, needle , Spherical, fiber, fibrous fabric, etc. can be used having a variety of shapes.

Typical examples of fillers are glass fiber, calcium carbonate, talc, mica, silica, wood powder, etc., and calcium carbonate can be used singly, or glass fiber, talc, mica, silica, wood powder, etc. can be mixed with calcium carbonate. However, it is not limited thereto.

For example, the filler may be a mixture of glass fiber and calcium carbonate in a weight ratio of 6:4, and the glass fiber serves to improve heat resistance, corrosion resistance and tensile strength of a molded product made of a polyvinyl chloride-based resin composition. Do it.

Calcium carbonate improves the moldability of the polyvinyl chloride resin composition, reduces the wear of the mixing and processing equipment, is easy to use due to a wide range of particle size adjustment, and is inexpensive. In particular, calcium carbonate having an average particle size of less than 0.1 µm may be used, and calcium carbonate of this size serves to enhance the impact resistance of the molded product by dispersing the impact applied to the outside.

Preferably, the filler may be mixed in a ratio of 1 to 30 parts by weight based on 100 parts by weight of the polyvinyl chloride resin, and if it is mixed less than 1 part by weight, the extrusion load may increase and the production cost may increase. If it exceeds 30 parts by weight, a problem of lowering the strength may occur.

The impact modifier is a material that reinforces impact resistance by imparting elasticity to the polyvinyl chloride resin composition, and can increase fracture, tensile, compression, warpage, and impact strength, and improve dimensional stability and resistance to thermal deformation.

The impact modifier may be methyl methacrylate-butadiene-styrene, chlorinated polyethylene, acrylic, or a mixture thereof, and may be mixed in a ratio of 3 to 5 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.

Specifically, methyl methacrylate-butadiene styrene (MBS)-based impact modifiers include methyl methacrylate (MMA) and styrene monomer (SM) in diene rubber. As a graft-polymerized copolymer, it serves to improve the low-temperature impact and processability of a polyvinyl chloride-based resin molded product.

Chlorinated polyethylene-based impact modifiers have excellent affinity with polyvinyl chloride-based resins and play a role in reducing extrusion resistance, and prevent breakage of the cutting part during the process of cutting molded products and improve light stability.

Acrylic impact modifier is a weather resistant impact modifier used in outdoor products and plays a role in improving the weather resistance, impact resistance and processability of polyvinyl chloride resin.

The antimicrobial agent serves to improve the antimicrobial properties of the polyvinyl chloride resin, and antimicrobial metals such as silver (Ag), copper (Cu), manganese (Mn), zinc (Zn), titanium dioxide, or mixtures thereof are used in zeolite, silica, A porous composite antimicrobial agent prepared by substitution with an inorganic carrier such as alumina may be introduced, and preferably, the antimicrobial agent may be mixed in a ratio of 0.1 to 6 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.

The colorant plays a role of imparting color to PVC products, and pigments containing titanium and nickel can be used.

It can be mixed in a ratio of 0.2 to 2 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.If the content of the pigment is less than 0.2 parts by weight, a problem of reducing the weather resistance of the product may occur, and if it exceeds 2 parts by weight, the physical properties It may be degraded, and a problem of increasing cost may arise.

The antifogging agent serves to suppress the generation of air bubbles generated inside the polyvinyl chloride resin composition, and may be mixed in a ratio of 0.5 to 5 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.

The composite stabilizer for PVC according to a preferred embodiment of the present invention is introduced into a high molecular weight polyvinyl chloride resin having a polymerization degree of 1700 to 2200 and a K value of 74 to 80, and a Ca/Zn liquid stabilizer and a Ca/Zn powder stabilizer Each is included in a weight ratio of 2:3 to 3:2, and may be mixed in a ratio of 5 to 15 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.

In particular, the composite stabilizer for PVC is 1 to 2 parts by weight of methacrylic acid methyl ester, 5 to 10 parts by weight of chlorosulfonated polyethylene, 1 to 3 parts by weight of stearyl stearate, and butyl methacrylic based on 100 parts by weight of polyvinyl chloride resin. Rate and methyl methacrylate mixture (weight ratio 1:2) 3 to 7 parts by weight, calcium carbonate 5 to 15 parts by weight, 0.5 to 5 parts by weight of a sunscreen agent, and 0.1 to 3 parts by weight of titanium dioxide may be included.

On the other hand, the present invention includes the PVC composite stabilizer and the polyvinyl chloride resin described above, characterized in that it comprises the PVC composite stabilizer in a ratio of 0.5 to 90 parts by weight based on 100 parts by weight of the polyvinyl chloride resin The composition is provided.

The composite stabilizer for PVC according to the present invention can be used to manufacture PVC products by mixing with polyvinyl chloride resin using various types of conventional devices such as mixers, calenders, kneaders, extruders, mills, etc. PVC products can be manufactured by processing using a variety of conventional methods such as extrusion, 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 for the manufacture of decorative films, foams, sheets, tubes, office films, extrusion profiles or plates, flooring films or panel coatings, artificial leather, interior materials for automobiles, etc. It can be used to manufacture rigid injection molded products or extrusion molded products such as packaging films, thermoforming films, blown films, pipe bodies, foams, frames, and the like.

The composite stabilizer for PVC according to the present invention as described above complements the disadvantages of each of a liquid stabilizer or a powder stabilizer, including both a Ca/Zn liquid stabilizer and a Ca/Zn powder stabilizer, and complements the disadvantages of each of the Ca/Zn liquid stabilizer or Ca/ Compared to the case of using each of the Zn powder stabilizers, it is possible to manufacture a PVC product with improved thermal stability and weather resistance, and for this purpose, the present invention includes a composite stabilizer for PVC and a polyvinyl chloride resin, the polyvinyl chloride resin 100 It provides a PVC composition comprising 0.5 to 90 parts by weight of the PVC composite stabilizer and parts by weight.

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

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

<Example 1>

PVC resin 100 parts by weight, complex heat stabilizer composition 10 parts by weight, methacrylic acid methyl ester 1.5 parts by weight, chlorosulfonated polyethylene 7 parts by weight, stearyl stearate 2 parts by weight, butyl methacrylate and methyl methacrylate mixture ( Weight ratio 1:2) 5 parts by weight, 10 parts by weight of calcium carbonate, 2 parts by weight of sunscreen, and 5 parts by weight of titanium dioxide were mixed, and a PVC composition was prepared by high-speed stirring at a temperature of 100° C. for 10 minutes using a mixer. In this case, a polyvinyl chloride resin having a polymerization degree of 1,300 to 1,600 and a K value of 70 to 74 was used for the PVC resin.

The prepared PVC composition was supplied to a two-sided two-way extruder (BT-50, Plastic Engineering Research Institute) having a screw diameter of 50 mm, and extruded, to prepare a pipe specimen having a diameter of 30 mm.

At this time, the composite thermal stabilizer composition was mixed with 40 parts by weight of a Ca/Zn liquid stabilizer and 5 parts by weight of aluminosilicate to hybridize the Ca/Zn liquid stabilizer and the Ca/Zn powder stabilizer, and the Ca/Zn liquid stabilizer was mixed with the silicon compound. Then, it was prepared by mixing 60 parts by weight of a Ca/Zn powder stabilizer.

10 parts by weight of a composite heat stabilizer prepared based on 100 parts by weight of PVC resin, 1.5 parts by weight of methacrylic acid methyl ester, 7 parts by weight of chlorosulfonated polyethylene, 2 parts by weight of stearyl stearate, butyl methacrylate and methyl methacrylate 5 parts by weight of a mixture (weight ratio 1:2), 10 parts by weight of calcium carbonate, 2 parts by weight of sunscreen and 5 parts by weight of titanium dioxide were mixed to prepare a composite stabilizer for PVC, and 100 parts by weight of PVC resin was mixed with a composite stabilizer for PVC. A PVC composition was prepared.

In addition, the Ca/Zn liquid stabilizer used is a mixture containing 10% by weight of calcium hydroxide, 3% by weight of zinc oxide, 2% by weight of benzoic acid, 3% by weight of oleic acid, 3% by weight of citric acid, and the remaining distilled water at a temperature of 100 to 150°C. In order to react for 10 to 60 minutes, water was removed by vacuum, and then, in order to adjust the saturation degree and molecular weight size, 2 to 3 parts by weight of the PVA and emulsifier mixture were mixed based on 100 parts by weight of the mixture from which distilled water was removed, and then atomized by high speed rotation. By adjusting the physical structure of the Ca/Zn liquid stabilizer so that the hybridization of the Ca/Zn liquid stabilizer and the Ca/Zn powder stabilizer can be smoothly induced, the average particle size of the Ca/Zn particles contained in the Ca/Zn liquid stabilizer is 1 to The one adjusted to be 10 Å was used.

In addition, the Ca/Zn powder stabilizer is a mixture of 10% by weight of calcium hydroxide powder, 5 parts by weight of Zn Nitrate powder, 30% by weight of urea, and the remaining distilled water by adding 100 to 2000 W of ultrasonic waves to the mixture. Next, put in a hydrothermal synthesis container with a built-in Teflon tube, sealed, and hydrothermal treatment at 120 to 220°C for 5 to 12 hours to prepare a synthetic powder, and then obtain a synthetic powder using a centrifuge (FLETA5, Hanil). One powder was heat-treated at 150 to 300° C. for 12 hours, and a flake Ca/Zn powder stabilizer having an average particle size of 50 to 500 nm was used.

In addition, the composite stabilizer was prepared by mixing 2 to 10 parts by weight of porous silica to 100 parts by weight of a Ca/Zn-based stabilizer including a Ca/Zn liquid stabilizer and a Ca/Zn powder stabilizer in a weight ratio of 2:3, respectively.

<Example 2>

A pipe specimen was prepared in the same manner as in Example 1, except that the PVC resin had a polymerization degree of 1700 to 2200 and a high molecular weight polyvinyl chloride resin having a K value of 74 to 80 was used.

<Comparative Example 1>

A pipe specimen was prepared in the same manner as in Example 1, except that a PVC composition was prepared using 10 parts by weight of a Ca/Zn liquid stabilizer.

<Comparative Example 2>

A pipe specimen was prepared in the same manner as in Example 1, except that a PVC composition was prepared using 10 parts by weight of a Ca/Zn powder stabilizer.

<Comparative Example 3>

A pipe specimen was prepared in the same manner as in Example 2, except that a PVC composition was prepared using 10 parts by weight of a Ca/Zn liquid stabilizer.

<Comparative Example 4>

A pipe specimen was prepared in the same manner as in Example 2, except that a PVC composition was prepared using 10 parts by weight of a Ca/Zn powder stabilizer.

<Test Example> Evaluation of the physical properties of the specimen

(1) impact strength

Impact strength was evaluated using specimens prepared by the methods according to Examples and Comparative Examples, and the impact strength test was 24 at standard temperature (23 ± 2 ℃) and low temperature (-10 ± 1 ℃) according to KS M 3056. It was carried out by adjusting the condition for a period of time, and the measurement results are shown in Table 1 below. For reference, according to KS F 5602 standard, it must be 12.7 kJ/m2 or more at standard temperature and 4.9 kJ/m ² or more at low temperature to pass.

(2) Weatherability evaluation

Weather resistance was evaluated in accordance with KS F 2274, and the spray cycle was adjusted to 20 minutes with a XENON-ARC type device, and the specimens prepared by the method according to the Examples and Comparative Examples at a temperature of 63 ± 3 °C were exposed for 1,000 hours. , Color difference change (unit: L*a*b*) of the specimen was measured using a color difference meter, and the results are shown in Table 1 below. For reference, according to KS F 5602, it is passed only when there is no significant discoloration.

(3) Initial coloring evaluation

The color difference value (unit: L*a*b*) was checked through a color difference meter CR-400 to determine whether the specimens prepared by the methods according to the examples and comparative examples were initially colored.

(4) Heat resistance evaluation

In order to check the heat resistance of the specimens prepared by the methods according to the examples and comparative examples, two specimens were prepared, and then heated at 200 °C, and the specimens were recovered at the time of 10 and 30 minutes of heating time. The color difference (unit: L*a*b*) between the specimen heated for 10 minutes and the specimen heated for 30 minutes was evaluated, and the results are shown in FIG. 1.

As shown in Figure 1, as a result of evaluating the physical properties of the specimens prepared by the methods according to Examples 1 and 2 and Comparative Examples 1 to 4, the impact strength of the specimens prepared by the method according to Examples 1 and 2 As a result of the evaluation of weather resistance, initial coloration, and heat resistance, the color difference was not large. Therefore, the physical properties of the specimen using the liquid stabilizer and the powder stabilizer were significantly improved compared to the specimens using the liquid stabilizer and the powder stabilizer. I was able to confirm the fact.

In particular, it was confirmed that the composite stabilizer further greatly improved the physical properties of the high molecular weight PVC resin with a high degree of polymerization.

Claims (5)

50 to 150 parts by weight of a Ca/Zn liquid stabilizer, 50 to 150 parts by weight of a Ca/Zn powder stabilizer, and 2 to 30 parts by weight of a silicon compound,
(a) preparing a mixture by mixing 50 to 150 parts by weight of the Ca/Zn liquid stabilizer and 2 to 30 parts by weight of a silicon compound and absorbing the Ca/Zn liquid stabilizer into the silicon compound to prepare a mixture, and (b) the mixture Prepared by a method comprising the step of mixing 50 to 150 parts by weight of a Ca/Zn powder stabilizer,
The Ca/Zn liquid stabilizer,
A mixture comprising 10 parts by weight of calcium hydroxide, 3 parts by weight of zinc oxide, 2 parts by weight of benzoic acid, 3 parts by weight of oleic acid, 2 parts by weight of citric acid, and 80 parts by weight of water was reacted at a temperature of 100 to 150° C. for 10 to 60 minutes. After water is removed, 2 to 3 parts by weight of a PVA and emulsifier mixture are mixed based on 100 parts by weight of the water-removed mixture, prepared through rotational stirring, and the average particle size of Ca/Zn particles contained in the Ca/Zn liquid stabilizer It is characterized in that it is atomized to be 1 to 100 Å,
The silicon compound has an average particle size of 0.01 to 1,000 µm, and includes porous silica or porous alumino silicate having pores of 1 to 500 Å,
Composite stabilizer for PVC, characterized in that it is mixed in a ratio of 3 to 15 parts by weight based on 100 parts by weight of the polyvinyl chloride resin. The method of claim 1,
Plasticizers, processing aids, antioxidants, UV stabilizers, flame retardants, lubricants, antistatic agents, foaming agents, fillers, antibacterial agents, colorants, anti-drop agents, nucleating agents, anti-blocking agents and slip agents that further include at least one additive selected from the group consisting of Composite stabilizer for PVC, characterized by. The method of claim 1,
The polyvinyl chloride resin has a K value of 50 to 85 and a polymerization degree of 500 to 2500. Composite stabilizer for PVC. delete Including the composite stabilizer for PVC and polyvinyl chloride resin according to any one of claims 1 to 3,
PVC composition comprising 100 parts by weight of the polyvinyl chloride resin and 0.5 to 90 parts by weight of the composite stabilizer for PVC.

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