KR102006716B1 - Acrylic processing aid and vinyl chloride resin composition containing thereof - Google Patents
Acrylic processing aid and vinyl chloride resin composition containing thereof Download PDFInfo
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- KR102006716B1 KR102006716B1 KR1020150130885A KR20150130885A KR102006716B1 KR 102006716 B1 KR102006716 B1 KR 102006716B1 KR 1020150130885 A KR1020150130885 A KR 1020150130885A KR 20150130885 A KR20150130885 A KR 20150130885A KR 102006716 B1 KR102006716 B1 KR 102006716B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
Abstract
The present invention relates to an acrylic processing aid and a vinyl chloride-based resin composition comprising the same, more specifically methyl methacrylate, C2 to C8 alkyl acrylate, aromatic vinyl monomer, wherein the water-soluble comonomer is specified It relates to a processing aid comprising an acrylic copolymer copolymerized using a content and to a vinyl chloride resin composition comprising the same.
The processing aid not only effectively prevents the occurrence of fish-eye phenomenon occurring when the conventional acrylic processing aid is used in the foam molding process of the vinyl chloride-based resin, but also improves the foam moldability, thus enabling the production of high-quality vinyl chloride-based resin molded articles. .
Description
The present invention relates to an acrylic processing aid capable of improving foaming moldability of vinyl chloride resins and at the same time effectively suppressing the occurrence of fish eye phenomena and a vinyl chloride resin composition comprising the same.
Vinyl chloride-based resins are homopolymers of vinyl chloride or hybrid polymers comprising at least 50% vinyl chloride. The vinyl chloride resin is used for various types of processing methods such as foam molding, extrusion molding, injection molding, calendering, and the like to wires, electric machine products, toys, films, sheets, artificial leather, tarpaulins, tapes, food packaging materials, and medical supplies. Widely used as a material for various products.
A processing aid is used to improve the processing properties of the vinyl chloride resin. The processing aid means to improve the melt delay characteristics inherent to the vinyl chloride resin to fully exhibit the mechanical and chemical properties, and is essential for processing the vinyl chloride resin.
In particular, the processing aid during the foam molding of the vinyl chloride-based resin helps the melting of the vinyl chloride resin forming the wall of the gas cell to proceed sufficiently to increase the high-temperature melt strength and to withstand the pressure of the gas that decomposes and expands at a high temperature. This prevents the gas chambers from bursting to form open cells that are connected to each other.
The effect is that the processing aid breaks down the boundaries of the primary particles, the basic structural unit, during the molding of vinyl chloride, thereby promoting a uniform melt state at the molecular level, so that the molded product exhibits uniform mechanical and chemical properties. Because it is possible to obtain.
Most commercially available vinyl chloride processing aids are commercially available as high molecular weight polymers or methyl methacrylate monomers using methyl methacrylate having excellent compatibility with vinyl chloride resin as the main monomer. Made by using high molecular weight (molecular weight 500,000 ~ 5,000,000g / mole) polymer copolymerized with methacrylate type, compound having nitrile unsaturated double bond or monomer having aromatic unsaturated double bond by emulsion polymerization method Methyl methacrylate polymer.
Republic of Korea Patent Publication No. 2008-0026971 discloses that it is possible to improve the foam moldability by using an acrylic copolymer for processing aid of vinyl chloride resin composition, US Patent No. 6,391,976 is methyl methacrylate (MMA) It is disclosed that butyl methacrylate (BMA) or polyethyl methacrylate (PEMA) can be used in the monomer to improve foaming properties.
The acrylic processing aids proposed in these patents have improved to some extent the foam formability, but a fish eye phenomenon has occurred which was not generated when foaming the vinyl chloride resin alone.
Fish eye phenomenon is a projection in the form of fish-eye appearing on the surface of the molded article produced after the foam molding, it is caused by the gelling or undissolved dispersion. There are many reasons for this, but there are differences in the meltability of vinyl chloride resins, processing aids, and various additives. That is, each composition must be sufficiently melted and mixed uniformly for foam molding, but this occurs due to the presence of unmelted powder.
Thus, US Patent No. 5,306,763 discloses a method of reducing the amount of monomers by increasing the amount of monomer having a low glass transition temperature (Tg) such as butyl acrylate, but for this purpose, an excessive amount of butyl acrylate is used. As a result, the overall melt viscosity is reduced, the processing is not performed well, and problems such as bubbles are generated.
U.S. Patent No. 6,140,417 discloses a monomer mixture of methyl methacrylate and acrylate in a copolymer made from a large amount of butyl acrylate and a small amount of methyl methacrylate to reduce the formation of microglides, improve processability, and improve foamability. Although a method of preparing a processing aid for polymerization and polymerizing butyl acrylate and methyl methacrylate is disclosed herein, the above method has a problem in that the uniformity of the foaming cell is somewhat insufficient so that gelling may occur.
In addition, US Pat. No. 6,391,976 discloses a process for combining a two-stage polymer into processing aids with large amounts of methyl methacrylate and small amounts of alkyl methacrylate. However, when the processing aid is added to the polyvinyl chloride resin, it shows excellent characteristics in the stability of the foaming cell and the appearance of the foamed molded article, but there is a problem that the gelling may occur due to the insufficient dispersibility.
Therefore, it is possible to reduce the fisheye phenomenon occurring on the surface of the vinyl chloride-based molded article when using the processing aid, and further studies on processing aids having excellent foaming properties and stability in the foam molding process are required.
Accordingly, the present inventors have conducted various studies to solve the above problems, and when using a water-soluble comonomer with a monomer of a specific composition when preparing a processing aid, the gel chloride or unmelted dispersion is induced by inducing rapid gelation of the vinyl chloride-based resin. By preventing the occurrence of the sieve, it was confirmed that the fisheye phenomenon can be effectively suppressed, the melt pressure and extrusion amount can be increased, the foaming specific gravity can be reduced, and the cell uniformity can be improved.
Accordingly, an object of the present invention is to provide an acrylic processing aid that can improve the foam moldability of a vinyl chloride-based resin and effectively suppress the occurrence of fish-eye phenomenon.
Another object of the present invention is to provide a vinyl chloride resin composition comprising the acrylic processing aid.
In order to achieve the above object, the present invention is such that the total of the monomers satisfy 100% by weight,
Methyl methacrylate 70-85 wt%,
10-25 wt% of alkyl acrylate of C2 to C8,
0.5 to 10 weight percent of an aromatic vinyl monomer, and
It provides an acrylic processing aid comprising an acrylic copolymer copolymerized 0.5 to 5.0% by weight of the water-soluble comonomer.
The present invention also provides a vinyl chloride resin composition comprising the acrylic processing aid.
The acrylic processing aid according to the present invention not only effectively prevents the occurrence of fisheye phenomenon occurring when the conventional acrylic processing aid is used in the foam molding process of the vinyl chloride resin, but also shortens the melting time, increases the melt pressure and extrusion amount, and foams. By reducing the specific gravity and improving the cell uniformity to improve the foam formability, it is possible to produce a high-quality vinyl chloride-based resin molded article.
Hereinafter, the present invention will be described in more detail.
Processing aid
When an acrylic processing aid is added to improve the foaming characteristics that occur during the foam molding of the vinyl chloride resin, fisheye phenomenon that does not occur in the vinyl chloride resin foaming occurs. Accordingly, the present invention proposes an acrylic copolymer having a specific composition as a processing aid to minimize the generation of the gelled or undispersed melt causing the fisheye phenomenon.
Specifically, the acrylic processing aid according to the present invention is an acrylic copolymer including methyl methacrylate, C2 to C8 alkyl acrylate, aromatic vinyl monomer, and copolymerized using a water-soluble comonomer in a specific content.
The water-soluble comonomer minimizes the generation of microgelides or undispersed melts by increasing the dispersibility of the processing aid during the foam molding of the vinyl chloride resin and shortening the melting time of the vinyl chloride resin. This is due to the structural properties of the water-soluble comonomers. For example, sulfonate-based comonomers, one of the anionic comonomers, increase the dispersibility and melt viscosity at the time of melting the vinyl chloride resin and use a certain amount thereof. This allows the shell portion of the processing aid to be produced to be more efficiently dispersed.
The water soluble comonomer according to the present invention may be an anionic comonomer or a cationic comonomer.
The anionic comonomer is not particularly limited in the present invention, but acrylic acid, methacrylic acid, sodium p-styrene sulfonate, sodium metalallyl sulfonate, 2-sulfoethylmethacryl One kind selected from the group consisting of sodium salt of 2-sulfoethyl methacrylate, sodium undecylenic isethionate, and combinations thereof is preferable, and sodium metaallyl sulfonate is preferably used. use.
In addition, cationic comonomers are not limited in the present invention, but acrylamide, 1,2-dimethyl 5-vinyl-pyridinium methylsulfate and 1-methyl 2-ethyl 5-vinyl pyridinium bromide (1-methyl 2-ethyl-5-vinyl pyridinium bromide) and combinations thereof may be selected from the group consisting of 1-methyl 2-ethyl 5-vinylpyridinium bromide. use.
Such water-soluble comonomers are used in an amount of 0.5 to 5.0% by weight, preferably 1.0 to 3.0% by weight within 100% by weight of the total monomers. If the content is less than the above range, the gelled or undispersed melt is generated to cause the fisheye phenomenon. On the contrary, the same phenomenon occurs even when the content exceeds the above range, so that the content is appropriately controlled within the above range. In addition, when viewed from the foam molding, as shown in the experimental example of the present invention, when the water-soluble comonomer was used in a low content, the melt pressure was reduced, the foaming specific gravity was increased, and the cell uniformity was greatly reduced (see Comparative Example 1). In addition, when used in excess, the extrusion pressure and extrusion amount was appropriate, but it was confirmed that the foam specific gravity and the cell uniformity characteristics are greatly reduced.
Acrylic copolymers according to the present invention comprising the above water-soluble monomers include methyl methacrylate, C2 to C8 alkyl acrylates, aromatic vinyl monomers.
Methyl methacrylate plays a major role as a processing aid as a monomer which is a basic composition of an acrylic processing aid. The methyl methacrylate is used in 70 to 85% by weight, preferably 75 to 80% by weight within 100% by weight of the total monomers. If the content is less than the above range can not play a role as a processing aid to improve the molding processability, on the contrary, if it exceeds the above range, the content of other monomers is relatively reduced to achieve the desired level of physical properties in the present invention.
Alkyl acrylate of C2 to C8 increases the compatibility with the vinyl chloride-based resin due to the presence of a hydrophobic group serves to improve the foam moldability. Specific examples thereof use one selected from the group consisting of ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, and combinations thereof. Preferably, one or more alkyl acrylate monomers may be used. More preferably, two or more alkyl acrylate monomers may be used. In the embodiment of the present invention, butyl acrylate and 2-ethylhexyl acrylate are used.
The alkyl acrylate of C2 to C8 is used in 10 to 25% by weight, preferably 15 to 20% by weight within 100% by weight of the total monomers. If the content is less than the above range, in the foam molding process, the amount of extrusion decreases, the foam specific gravity increases, and the cell uniformity decreases. Use it appropriately.
Since the aromatic vinyl monomer has a high refractive index, it is possible to improve the transparency of the produced vinyl chloride resin.
Specific examples thereof may be one selected from the group consisting of styrene, α-methylstyrene, o-ethylstyrene, p-ethylstyrene, vinyltoluene, and combinations thereof. The aromatic vinyl monomers may be used alone or in combination of two or more, styrene was used in the embodiment of the present invention.
The aromatic vinyl monomer is used in 0.5 to 10% by weight, preferably 1 to 5% by weight within 100% by weight of the total monomers. If the content is less than the above range, the improvement of the physical properties cannot be expected. On the contrary, if the content exceeds the above range, the Tg rises, the melting time increases, the melt pressure increases, and the like is appropriately adjusted within the above range. .
Manufacturing method of processing aid
The preparation of the processing aid copolymerized with the monomers described above is not particularly limited in the present invention, and various methods for preparing the copolymer are possible.
For example, it may be polymerized by applying a variety of methods, such as emulsion polymerization, block polymerization, suspension polymerization, solution polymerization, preferably by emulsion polymerization.
The processing aid according to the present invention polymerizes methyl methacrylate, C2 to C8 alkyl acrylate, aromatic vinyl monomer, and water-soluble comonomer in the presence of a water-soluble initiator and an emulsifier to prepare a copolymer latex, and the copolymer latex It is a step of solidification.
As an initiator, a water-soluble initiator is possible, For example, inorganic peroxides, such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-mentanehydro peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide Organic peroxides such as oxides, 3,5,5-trimethylhexanol peroxide and t-butyl peroxy isobutylate; Nitrogen compounds such as azobis isobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, azobisisobutyric acid (butyl acid) methyl and the like. These initiators are used in 0.03-0.2 weight part with respect to 100 weight part of total monomers.
The emulsifier may be selected from one or more selected from the group consisting of anionic emulsifiers, cationic emulsifiers and nonionic emulsifiers, and is not particularly limited in the present invention. For example, the emulsifiers include sulfonates, carboxylates, succinates, sulfosuccinates and metal salts thereof, such as alkylbenzenesulfonic acid, sodium alkylbenzenesulfonate, alkylsulfonic acid, sodium alkylsulfonate, sodium poly Anionic emulsifiers widely used in emulsion polymerization, such as oxyethylene nonylphenylether sulfonate, sodium stearate, sodium dodecyl sulfate, sodium lauryl sulfate, sodium dodecyl sulfosuccinate, abienic acid salts and the like; Cationic emulsifiers in which amine halides, alkyl quaternary ammonium salts, alkylpyridinium salts, and the like are bonded as functional groups of higher aliphatic hydrocarbons; One or more types can be selected from the group which consists of nonionic emulsifiers, such as polyvinyl alcohol and polyoxyethylene nonylphenyl, It is not limited to these emulsifiers. Such emulsifiers may be used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the monomer mixture.
According to an embodiment of the present invention, the emulsion polymerization may further include additives such as molecular weight regulators, activators, redox catalysts, ionized water and the like commonly known in the art.
Although a molecular weight modifier does not specifically limit, For example, mercaptans, such as a-methylstyrene dimer, t-nodecyl mercaptan, n-dodecyl mercaptan, an octyl mercaptan; Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride and methylene bromide; Sulfur-containing compounds such as tetraethyl diuram disulfide, dipentamethylene diuram disulfide, diisopropylquixanthogen disulfide and the like, and the like, and may be used in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the monomer mixture.
Activators include, but are not limited to, at least one selected from sodium hydrosulfite, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, lactose, dextrose, sodium rirolate, and sodium sulfate The total amount of monomers may be added in the range of 0.01 to 0.15 parts by weight, respectively.
The redox catalyst is not particularly limited, but may be, for example, sodium formaldehyde sulfoxylate, ferrous sulfate, disodium ethylenediaminetetraacetate, copper disulphate, and the like, based on 100 parts by weight of 0.01 to 0.1 parts by weight of the monomer mixture. It can be used in parts by weight.
The polymerization may be capable of polymerization for 2 to 12 hours at 40 ~ 80 ℃.
In the present invention, the monomer mixture may be added at one time to polymerize, or the monomer mixture may be divided and added to polymerize step by step. When the monomer mixture is divided and polymerized step by step, 60 to 90% by weight of the total monomer mixture in the first step, 10 to 40% by weight in the second step.
According to a preferred embodiment of the present invention, the polymerization is carried out in the presence of a water-soluble initiator and an emulsifier in 60 to 90% by weight of the monomer mixture comprising methyl methacrylate, C2 to C8 alkyl acrylate, aromatic vinyl monomer, and water-soluble comonomer Primary polymerization under; And 10 to 40% by weight of the residual monomer mixture in the second polymerization in the presence of a water-soluble initiator and an emulsifier. The reason for the polymerization in two steps is that the processing aid properties, the surface properties, etc. can be improved, and the best physical properties are exhibited. In addition, since the melting of the tomb is smooth, there is an effect that the unmelting phenomenon is significantly reduced.
In the coagulation step, an antioxidant may be added to the polymer latex before coagulation. Methods of solidifying the polymer latex are well known by those of ordinary skill in the art. For example, the prepared methyl methacrylate-alkylacrylate-epoxide copolymer resin may be aggregated with calcium chloride. The coagulated copolymer may be dehydrated and dried in a conventional manner to obtain a powder processing aid.
The acrylic latex obtained by the emulsion polymerization may have a weight average molecular weight (MW) of 2,000,000 to 5,000,000. If the weight average molecular weight of the acrylic copolymer is less than 2,000,000, the foam specific gravity may increase and foam formability may be poor. On the other hand, if the weight average molecular weight of the acrylic copolymer exceeds 5,000,000, undispersed melt may be generated and workability may be poor. Can be.
Vinyl chloride resin composition
The acrylic processing aid according to the present invention may be obtained in a powder state and used in foam molding processing of vinyl chloride resin.
Such acrylic processing aids are used as processing aids in the foam molding of vinyl chloride resins, and the dispersibility of the processing aids in the foam molding of vinyl chloride resins and shortening of the melting time of vinyl chloride resins to reduce the Minimize occurrences. In addition, due to the high compatibility with the vinyl chloride-based resin to increase the friction (friction) to promote processing, as well as to increase the melt pressure (melt pressure) of the vinyl chloride-based resin composition can be improved workability. In addition, it may serve to lower the foaming specific gravity and to make the cell size small and uniform.
Specifically, the acrylic processing aid according to the present invention is mixed with 95.0 to 99.5% by weight of vinyl chloride-based resin in an amount of 0.5 to 5.0% by weight to produce a variety of molded articles through foam molding.
When the content of the acrylic processing aid is less than the above range, the processability, formability and thermal stability due to the use of the processing aid are low, and thus the quality of the manufactured molded article is lowered. And as the chemical properties are rather reduced, it is suitably used within the above range.
In this case, if necessary, it may further include various additives commonly used in the art. The additives include heat stabilizers, lubricants, impact modifiers, plasticizers, UV stabilizers, flame retardants, colorants, fillers, flame retardants, antibacterial agents, mold release agents, heat stabilizers, antioxidants, light stabilizers, compatibilizers, dyes, inorganic additives, surfactants, nucleating agents Conventional additives such as coupling agents, fillers, plasticizers, impact modifiers, admixtures, colorants, stabilizers, lubricants, antistatic agents, pigments, flame retardants and the like may be added, and these may be applied alone or in combination of two or more thereof.
Foam molding using the vinyl chloride-based resin composition is not particularly limited in the present invention and follows a known method.
The molded article through foam molding improves the foaming ratio and the stability of the foaming cell during foaming to obtain a low specific gravity foam of 0.4 to 0.5 g / cm 3, and has a uniform foaming cell.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.
Examples 1-5 and Comparative Examples 1-3: Preparation of Acrylic Processing Aid
(1) Manufacture of Acrylic Copolymer
A reactor of a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a circulation condenser was prepared, 70 parts by weight of deionized water, 0.002 parts by weight of ferrous sulfate, and disodium ethylenediaminetetraacetate ( disodium ethylenediaminetetraacetate) 0.04 parts by weight was added and the reactor internal temperature was maintained at 40 ° C. under a nitrogen atmosphere.
Separated from the reactor, to prepare a monomer preemulsion 60 parts by weight of ionized water, 0.60 parts by weight of sodium lauryl sulfonate (SLS), 100 parts by weight of the monomer shown in Table 1 was prepared to prepare a monomer preemulsion It was.
When the internal temperature of the reactor reached 40 ° C., 50 parts by weight of the monomer preemulsion, 0.002 parts by weight of t-butylhydroperoxide (TBHP), and 0.03 parts by weight of sodium formaldehyde sulfoxylate (SFS) were simultaneously added to perform polymerization for 3 hours. It was.
50% of the monomer preemulsion remaining after the completion of the first reaction was temporarily added with 0.001 parts by weight of TBHP and 0.002 parts by weight of SFS, and then subjected to secondary polymerization.
120 minutes after the completion of the monomer preemulsion, 0.002 parts by weight of initiator TBHP and 0.004 parts by weight of SFS were further added and aged for 1 hour.
The prepared acrylic copolymer latex TSC about 40%, the latex particle diameter was measured to 120 nm.
(2) Weight average molecular weight measurement
After drying the acrylic copolymer latex at room temperature, 0.03 g of solid content was dissolved in 10 ml of tetrahydrofuran (THF) for 24 hours, and then the weight average molecular weight was measured by gel permeation chromatography (Gel Permeation Cheromatography, GPC). The weight average molecular weight of the prepared acrylic copolymer was 3.8 million.
(3) Production of acrylic processing aid powder
4 parts by weight of a calcium chloride solution was added to 100 parts by weight of each of the acrylic latexes prepared in Examples and Comparative Examples to agglomerate to obtain a slurry, and the slurry was washed three times with deionized water to remove by-products. Thereafter, the ionized water was removed by filtration and dried at 80 ° C. for 3 hours using a small fluidized bed dryer to obtain an acrylic processing aid powder.
MMA: Methyl Methacrylate
BA: butyl acrylate
2EHA: 2-ethylhexyl acrylate
SM: Styrene
SMAS: Sodium Metaallyl Sulfonate
DVPM: 1,2-dimethyl 5-vinyl-pyridium methylsulfate
Experimental Example: Preparation of vinyl chloride resin and measurement of physical properties
(1) Manufacture of vinyl chloride resin
After adding 6.0 g of composite stabilizer KD-105 (composite heat stabilizer mixed uniformly with heat stabilizer and lubricant) and 15 g of filler (CaCO3) to 100 g of vinyl chloride resin (LS080, manufactured by LG Chemical), 5 g of the acrylic processing aid composition prepared in step 1 and 0.8 g of the azodicarbonamide blowing agent were added, and the mixture was heated and mixed up to 115 ° C. using a Henschel mixer to obtain a vinyl chloride-based resin composition comprising an acrylic copolymer. Prepared.
(2) property measurement
Melting time: 55 g of the vinyl chloride resin composition prepared above was processed using a Brabender under conditions of 175 ° C and 40 rpm, and the time taken from the minimum load to the maximum load was measured.
-Fish eye phenomenon: After preparing a vinyl chloride resin composition without adding a filler when preparing a vinyl chloride resin composition, a 20 mm single screw extruder equipped with a T-die was used. After extracting a 0.2 mm thick film at a cylinder temperature of 180 ° C and a screw speed of 30 rpm, the number of fisheyes in the defined area of the film surface was visually observed. 3 points were generated slightly, and 1 point was generated when a lot of fish eyes were generated.
Foam processing properties: Slit die size 2 mm (thickness) X 30 mm (width) of the vinyl chloride-based resin composition prepared above using a Haake twin extruder at a cylinder temperature of 180 ° C. and a screw speed of 30 rpm. After extracting for 1 minute, the amount of extrusion and the melt pressure were measured. Subsequently, it was cut into a length of 30mm and the foam density was measured using a plastic specific gravity meter. At this time, the higher the foaming density, the lower the foaming magnification, and the lower the foaming characteristics. In addition, the cross section of the foamed molded article obtained above was observed by an optical microscope, and the cell uniformity was set to 5 points when the foamed cell was uniform, 3 points when the foamed cell was slightly uneven, and 1 point when most of the foamed cells were not uniform. Sex was evaluated.
(s)
(point)
(bar)
(g / min)
(g / cm3)
(5pt)
Melting time: 70 ~ 100 seconds
Undispersed Melt: 4 ~ 5 points
Melting Pressure: 130 ~ 150 bar
Extrusion amount: 180 ~ 200 g / min
Foam specific gravity: 0.40 ~ 0.50 g / cm3
Referring to Table 1, it was confirmed that the vinyl chloride-based resin using the processing aid of the embodiment having a monomer system presented in the present invention, the melting time and foam processing properties belong to the appropriate range. In addition, it was confirmed that there was almost no undispersed melt.
In comparison, when the water-soluble comonomer of Comparative Example 1 was not used, the microdispersed melt was seriously generated, the melt pressure, the amount of compression and the cell uniformity were decreased, and the foam specific gravity was increased.
In addition, in Comparative Examples 2 and 3, even when used outside the content range of the water-soluble comonomer, this tendency was similar, and from these results, the physical properties of the vinyl chloride-based resin may be largely changed by the content of the water-soluble comonomer. It can be seen that.
As the results of the above experimental example, the acrylic processing aid according to the present invention by using the water-soluble comonomer in a specific range effectively suppress the generation of undispersed melt after foam molding of the vinyl chloride-based resin, melting time, melting pressure In order to increase the foamability by increasing the appropriate range, it is possible to increase the foam formability by reducing the specific gravity of foam and increasing the cell uniformity.
The acrylic processing aid of the present invention can be used as a processing aid in the production of various molded products using vinyl chloride-based resins to enable the production of molded articles having excellent physical properties.
Claims (8)
Methyl methacrylate 70-85 wt%,
10-25 wt% of alkyl acrylate of C2 to C8,
0.5 to 10 weight percent of an aromatic vinyl monomer, and
A water-soluble comonomer 0.5-5.0 wt% comprises an copolymer of acrylic copolymer,
The water-soluble comonomer is acrylamide, 1,2-dimethyl 5-vinyl-pyridinium methylsulfate, 1-methyl 2-ethyl 5-vinyl pyridinium bromide Methyl 2-ethyl-5-vinyl pyridinium bromide), and an acrylic processing aid comprising a cationic comonomer selected from the group consisting of these.
The alkyl acrylate of C2 to C8 is one kind selected from the group consisting of ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, and combinations thereof. .
The aromatic vinyl monomer is an acrylic processing aid, characterized in that one selected from the group consisting of styrene, α-methylstyrene, o-ethylstyrene, p-ethylstyrene, vinyl toluene and combinations thereof.
The water-soluble comonomer acrylic processing aid further comprises an anionic comonomer.
The anionic comonomer is acrylic acid, methacrylic acid, sodium para-styrene sulfonate, sodium methalyl sulfonate, 2-sulfoethyl methacrylate sodium salt of 2-sulfoethyl methacrylate), sodium undecylenic isethionate, and an acrylic processing aid comprising one selected from the group consisting of a combination thereof.
The acrylic copolymer is an acrylic processing aid, characterized in that the weight average molecular weight (MW) is 2,000,000 to 5,000,000.
A vinyl chloride resin composition comprising 0.5 to 5.0% by weight of the acrylic processing aid according to any one of claims 1 to 5 and 7.
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| KR1020150130885A KR102006716B1 (en) | 2015-09-16 | 2015-09-16 | Acrylic processing aid and vinyl chloride resin composition containing thereof |
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