KR20170033056A - 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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- KR20170033056A KR20170033056A KR1020150130885A KR20150130885A KR20170033056A KR 20170033056 A KR20170033056 A KR 20170033056A KR 1020150130885 A KR1020150130885 A KR 1020150130885A KR 20150130885 A KR20150130885 A KR 20150130885A KR 20170033056 A KR20170033056 A KR 20170033056A
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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 resin composition containing the same, and more particularly to a vinyl chloride resin composition containing methyl methacrylate, C2 to C8 alkyl acrylate and aromatic vinyl monomer, And a vinyl chloride resin composition containing the copolymer. The present invention also relates to a vinyl chloride resin composition containing the acrylic copolymer.
The processing aid not only effectively prevents occurrence of fish eye phenomenon occurring when the acrylic processing aid is used in the foam molding process of a vinyl chloride resin, but also improves foam moldability and enables production of a high-quality vinyl chloride resin molded article .
Description
TECHNICAL FIELD The present invention relates to an acrylic-based processing aid and a vinyl chloride resin composition containing the acrylic-based processing aid capable of effectively suppressing the occurrence of fish eye phenomenon while improving the foaming moldability of a vinyl chloride resin.
The vinyl chloride resin is a homopolymer of vinyl chloride or an interpolymer containing 50% or more of vinyl chloride. The vinyl chloride resin can be applied to a variety of processing methods such as electric wire, electromechanical products, toys, films, sheets, artificial leather, tarpaulins, tapes, food packaging materials and medical supplies by various processing methods such as foam molding, extrusion molding, injection molding, It is widely used as a material for various products.
A processing aid is used to improve the processing characteristics of the vinyl chloride resin. The processing aid improves the inherent melt retardation characteristics of vinyl chloride resin and thus helps to fully exhibit mechanical and chemical properties, and is essential for the processing of vinyl chloride resin.
Particularly, the processing aid during the foaming molding of the vinyl chloride resin assists in sufficiently progressing the melting of the vinyl chloride resin forming the wall of the gas chamber, thereby increasing the high-temperature melt strength and enduring the pressure of the gas decomposing and expanding at high temperature Thereby preventing the formation of an open cell in which the gas is blown and connected to each other.
This effect is achieved by the fact that the processing aid prematurely breaks the boundaries of the primary particles, which are basic constituent units, during vinyl chloride molding, thereby promoting the uniform melting state at the molecular level, so that the molded product exhibits uniform mechanical and chemical properties And the like.
Most vinyl chloride processing aids currently commercialized are mainly composed of high molecular weight polymers or methyl methacrylate monomers using methyl methacrylate alone, which is excellent in compatibility with vinyl chloride resin as the main monomer, and a small amount of various acrylates, (Molecular weight: 500,000 to 5,000,000 g / mole) polymer prepared by copolymerizing a methacrylate-based, nitrile-based unsaturated double bond-containing compound or an aromatic unsaturated double bond-containing monomer with an emulsion polymerization method as an auxiliary component Methyl methacrylate based polymer.
Korean Patent Laid-Open Publication No. 2008-0026971 discloses that foam formability can be improved by using an acrylic copolymer for processing a vinyl chloride resin composition. U.S. Patent No. 6,391,976 discloses that methyl methacrylate (MMA) Butyl methacrylate (BMA) or polyethyl methacrylate (PEMA) may be used for the monomer to improve the foaming property.
The acrylic processing aids disclosed in these patents have improved foam formability to some extent, but fish eye (silver point) phenomenon has not occurred in the foaming molding of vinyl chloride resin alone.
The fish eye phenomenon occurs in the form of fish eyes on the surface of a molded article produced after the foaming molding, and is generated by a migrating or unmelted dispersion. There are many reasons for this, but the difference in the meltability of the vinyl chloride resin, the processing aid, and various additives may be mentioned. That is, each composition must be sufficiently melted and uniformly mixed for foaming, but it is caused by the presence of unmelted powder.
Accordingly, US Patent No. 5,306,763 discloses a method for increasing the amount of monomers having a low glass transition temperature (Tg) such as butyl acrylate to reduce the generation of miglygel. For this purpose, an excess amount of butyl acrylate is used And thus, the overall melt viscosity is lowered, resulting in poor processability and generation of bubbles.
U.S. Patent No. 6,140,417 discloses a monomer mixture of methyl methacrylate and acrylate in a copolymer made of a large amount of butyl acrylate and a small amount of methyl methacrylate in order to lower the generation of migellite, And then polymerizing butyl acrylate and methyl methacrylate thereon. However, this method has a problem in that the uniformity of the foamed cells is somewhat insufficient and that the migrated materials may be generated.
In addition, U.S. Patent No. 6,391,976 discloses a method of blending a two-stage polymer with a large amount of methyl methacrylate and a small amount of alkyl methacrylate in a processing aid. However, when added to a polyvinyl chloride resin, the processing aid exhibits excellent properties in terms of the stability of the foamed cell and the appearance of the foamed molded article, but has a problem that the dispersibility is somewhat insufficient and the migrated material may be generated.
Therefore, it is necessary to further study a processing aid having excellent foam characteristics and stability in a foam molding process, which can reduce the fish eye phenomenon occurring on the surface of a vinyl chloride-based molded article when using a processing aid.
The present inventors have conducted various studies to solve the above problems. As a result, they have found that when a water-soluble comonomer is used together with a monomer of a specific composition in the preparation of a processing aid, quick gelation of a vinyl chloride resin leads to migration, It is possible to effectively prevent fish eye phenomenon, increase the melt pressure and extrusion amount, lower the specific gravity of foam, and improve the cell uniformity.
Accordingly, an object of the present invention is to provide an acrylic-based processing aid capable of improving foaming moldability of a vinyl chloride resin and effectively inhibiting the occurrence of a 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 attain the above object, the present invention provides a method for producing a thermoplastic resin composition,
70 to 85% by weight of methyl methacrylate,
From 10 to 25% by weight of C2 to C8 alkyl acrylates,
0.5 to 10% by weight of an aromatic vinyl monomer, and
And an acrylic copolymer copolymerized with 0.5 to 5.0% by weight of a water-soluble comonomer.
Further, the present invention provides a vinyl chloride resin composition comprising the acrylic processing aid.
The acrylic processing aid according to the present invention effectively prevents occurrence of fish eye phenomenon occurring in the conventional acrylic processing aid in the foam molding process of a vinyl chloride resin, as well as shortening the melting time, increasing the melt pressure and the extrusion amount, The specific gravity is lowered, the cell uniformity is improved, the foam formability is improved, and a high-quality vinyl chloride resin molded article can be produced.
Hereinafter, the present invention will be described in more detail.
Processing aid
In the case of adding an acrylic processing aid to improve the foaming property which occurs in the foaming molding of the vinyl chloride resin, a fish eye phenomenon which is not caused by the foaming of the vinyl chloride resin alone occurs. Accordingly, in the present invention, an acrylic copolymer having a specific composition is proposed as a processing aid so as to minimize the occurrence of migrating or undispersed melts causing a fish eye phenomenon.
Specifically, the acrylic processing aid according to the present invention is an acrylic copolymer copolymerized with methyl methacrylate, C2 to C8 alkyl acrylate, aromatic vinyl monomer, and water-soluble comonomer in a specific amount.
The water-soluble comonomer enhances the dispersibility of the processing aid during the foaming molding of the vinyl chloride resin and shortens the melting time of the vinyl chloride resin to minimize the occurrence of migrated or undispersed melts. This is due to the structural characteristics of the water-soluble comonomer. For example, in the case of a sulfonate-based comonomer, which is one of the anionic comonomers, the dispersibility and melt viscosity of the vinyl chloride resin are increased, Thereby making it possible to distribute the shell portion of the processing aid more efficiently.
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 may be selected from acrylic acid, methacrylic acid, sodium p-styrene sulfonate, sodium metallyl sulfonate, 2-sulfoethyl methacrylate One kind selected from the group consisting of sodium salt of 2-sulfoethyl methacrylate, sodium undecylenic isethionate, and combinations thereof, preferably sodium methallylsulfonate use.
In addition, the cationic comonomer is not limited to the present invention, but may be selected from the group consisting of acrylamide, 1,2-dimethyl 5-vinyl-pyridinium methylsulfate and 1-methyl 2- 1-methyl-2-ethyl-5-vinyl pyridinium bromide, and combinations thereof, preferably 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 amount of the monomers. If the content is less than the above range, a migrating material or a microdistribution molten material is generated to cause a fish eye phenomenon. On the other hand, when the content exceeds the above range, the same phenomenon occurs. In addition, as shown in the experimental examples of the present invention, when the water-soluble comonomer is used in a low content, the melt pressure is reduced, the specific gravity of the foam is increased, and the cell uniformity is greatly reduced (see Comparative Example 1). In addition, when used in an excessive amount, the extrusion pressure and the extrusion amount were appropriate, but it was confirmed that the specific gravity of foam and the cell uniformity property were significantly lowered.
The acrylic copolymer according to the present invention containing the water-soluble monomer includes methyl methacrylate, C2-C8 alkyl acrylate, and aromatic vinyl monomer.
Methyl methacrylate is a monomer which is a basic composition of an acrylic processing aid and plays a major role as a processing aid. The methyl methacrylate is used in an amount of 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, it can not serve as a processing aid for improving the molding processability. On the other hand, if the content exceeds the above range, the content of the other monomers may be decreased, and the desired level of physical properties can not be achieved in the present invention.
The alkyl acrylates of C2 to C8 have the role of improving compatibility with the vinyl chloride resin due to the presence of the hydrophobic group and improving the foam formability. Specific examples thereof include one selected from the group consisting of ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, and combinations thereof. Preferably, the alkyl acrylate monomers may be used singly or in combination of two or more. More preferably, two or more kinds of the alkyl acrylate monomers may be used in combination. In the examples of the present invention, butyl acrylate and 2-ethylhexyl acrylate are used.
The C2 to C8 alkyl acrylates are used in an amount of 10 to 25% by weight, preferably 15 to 20% by weight within a total amount of 100% by weight of the monomers. If the content is less than the above range, the extrusion amount is decreased, the specific gravity of foam is increased, and the cell uniformity is lowered in the foam molding process. On the contrary, even if the content exceeds the above range, the same phenomenon occurs, As appropriate.
Since the aromatic vinyl monomer has a high refractive index, the transparency of the produced vinyl chloride resin can be improved.
Specific examples thereof include at least one member selected from the group consisting of styrene,? -Methylstyrene, o-ethylstyrene, p-ethylstyrene, vinyltoluene, and combinations thereof. One or more of the aromatic vinyl monomers may be used, and styrene is used in the examples of the present invention.
The aromatic vinyl monomer is used in an amount of 0.5 to 10% by weight, preferably 1 to 5% by weight, within 100% by weight of the total amount of the monomers. If the content is less than the above range, improvement of properties can not be expected. On the other hand, when the content is in excess of the above range, the Tg increases and the melting time becomes longer and the melting pressure increases. .
Process for the preparation of a processing aid
The production of the above-mentioned copolymerized monomers is not particularly limited in the present invention, and various methods for producing the copolymer are possible.
For example, the polymerization may be carried out by various methods such as emulsion polymerization, bulk polymerization, suspension polymerization and solution polymerization. Preferably, emulsion polymerization is used.
The processing aid according to the present invention can be prepared by polymerizing methyl methacrylate, C2-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 solidifying.
As the initiator, a water-soluble initiator can be used, and inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, hydrogen peroxide and the like; t-butyl peroxide, cumene hydroperoxide, p-menthol hydroperoxide, di-t-butyl peroxide, t-butyl cumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide Organic peroxides such as oxides, 3,5,5-trimethylhexanol peroxide, t-butyl peroxyisobutyrate; Nitrogen compounds such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyric acid (butyl acid) methyl. These initiators are used in an amount of 0.03 to 0.2 part by weight based on 100 parts by weight of the total monomers.
The emulsifier may be selected from the group consisting of an anionic emulsifier, a cationic emulsifier and a nonionic emulsifier, and is not particularly limited in the present invention. Examples of the emulsifier include sulfonate, carboxylate, succinate, sulfosuccinate and metal salts thereof, such as alkylbenzenesulfonic acid, sodium alkylbenzenesulfonate, alkylsulfonic acid, sodium alkylsulfonate, sodium poly Anionic emulsifiers widely used in emulsion polymerization generally such as oxyethylene nonylphenyl ether sulfonate, sodium stearate, sodium dodecyl sulfate, sodium lauryl sulfate, sodium dodecyl sulfosuccinate, and abietic acid salt; A cationic emulsifier to which an amine halide, an alkylammonium salt, an alkylpyridinium salt or the like is bonded as a functional group of a higher aliphatic hydrocarbon; And nonionic emulsifiers such as polyvinyl alcohol and polyoxyethylene nonylphenyl. These emulsifiers are not limited to these emulsifiers. Such an emulsifier may be used in an amount of 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the monomer mixture.
According to one embodiment of the present invention, an additive such as a molecular weight modifier, an activator, an oxidation-reduction catalyst, and ionized water commonly known in the art in emulsion polymerization may be further included.
The molecular weight regulator is not particularly limited, and examples thereof include mercaptans such as a-methylstyrene dimer, t-octenyl mercaptan, n-dodecyl mercaptan and octyl mercaptan; Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, and methylene bromide; Containing sulfur compounds such as tetraethyldiallyldisulfide, dipentamethylenediuramydisulfide, and diisopropylkantogen disulfide, and may be used in an amount of 0.1 part by weight 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 hydrogensulfate, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, lactose, dextrose, sodium lorolene, and sodium sulfate. Based on 100 parts by weight of the total of the monomers, within the range of 0.01 to 0.15 parts by weight.
The redox catalyst may be, for example, sodium formaldehyde sulfoxylate, ferrous sulfate, disodium ethylenediamine tetraacetate, and cupric sulfate, and may be used in an amount of 0.01 to 0.1 parts by weight per 100 parts by weight of the monomer mixture. Parts by weight.
The polymerization can be carried out at 40 to 80 ° C for 2 to 12 hours.
In the present invention, the monomer mixture may be added all at once to polymerize, or the monomer mixture may be separately added, and the mixture may be polymerized in stages. When the monomer mixture is polymerized stepwise, 60 to 90% by weight of the total monomer mixture and 10 to 40% by weight of the total monomer mixture are added in the first stage and the second stage, respectively.
According to a preferred embodiment of the invention, the polymerization is carried out in the presence of a water-soluble initiator and an emulsifier in an amount of 60 to 90% by weight of the monomer mixture comprising methyl methacrylate, C2 to C8 alkyl acrylate, aromatic vinyl monomer, Lt; / RTI > And a second step of polymerizing 10 to 40% by weight of the remaining monomer mixture in the presence of a water-soluble initiator and an emulsifier. The reason for the two-step polymerization is to improve the processing aid properties, surface characteristics and the like, and to show the best properties. In addition, since the melting of the mounds is smooth, the unmelted phenomenon is remarkably reduced.
Further, in the solidifying step, an antioxidant may be added to the polymer latex before solidification. Methods for solidifying the polymer latex are well known to those of ordinary skill in the art to which the present invention pertains. For example, the methyl methacrylate-alkyl acrylate-epoxide-based copolymer resin prepared above may aggregate with calcium chloride. The coagulated copolymer can be dehydrated and dried in a conventional manner to obtain a processing aid in powder form.
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 the foam formability may become poor. On the other hand, if the acrylic copolymer exceeds 5,000,000, .
Vinyl chloride resin composition
The acrylic processing aid according to the present invention can be obtained in powder form and used in the foaming molding process of a vinyl chloride resin.
Such an acrylic processing aid is used as a processing aid in the foaming molding of a vinyl chloride resin, and improves the dispersibility of the processing aid during the foaming molding of the vinyl chloride resin and shortens the melting time of the vinyl chloride resin, Minimize the occurrence. In addition, due to high compatibility with the vinyl chloride resin, the friction can be increased to promote the processing, and the melt pressure of the vinyl chloride resin composition can be increased to improve the workability. Also, it can reduce the specific gravity of the foam, and 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 a vinyl chloride resin in an amount of 0.5 to 5.0% by weight, and various molded articles are produced through foam molding.
If the content of the acrylic processing aid is less than the above range, the processability, formability and thermal stability of the processing aid are low, and the quality of the produced molded article is deteriorated. Conversely, if the content exceeds the above range, And chemical properties are deteriorated, it is appropriately used within the above range.
If necessary, various additives commonly used in this field may be further included. Examples of the additive include heat stabilizers, lubricants, impact modifiers, plasticizers, UV stabilizers, flame retardants, colorants, fillers, flame retardants, antimicrobials, mold release agents, heat stabilizers, antioxidants, light stabilizers, compatibilizers, dyes, , Additives such as a binder, a filler, a plasticizer, an impact modifier, an admixture, a colorant, a stabilizer, a lubricant, an antistatic agent, a pigment and a flame retardant may be added alone or in admixture of two or more.
The foaming molding using the vinyl chloride resin composition is not particularly limited in the present invention, and the known method is followed.
The foamed product obtained by foam molding has improved foam expansion ratio and stability of the foamed cell during foaming, so that a foam having a low specific gravity of 0.4 to 0.5 g / cm 3 can be obtained, and a uniform foamed cell is obtained.
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 to 5 and Comparative Examples 1 to 3: Preparation of acrylic type processing aid
(1) Production of acrylic copolymer
A reactor of a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a circulating condenser was prepared, and 70 parts by weight of deionized water, 0.002 part by weight of ferrous sulfate and disodium ethylenediamine tetraethoxide 0.04 part by weight of disodium ethylenediaminetetraacetate) was added and the temperature inside the reactor was maintained at 40 캜 under a nitrogen atmosphere.
Separately from the reactor, 60 parts by weight of ionized water, 0.60 part by weight of sodium lauryl sulfonate (SLS) and 100 parts by weight of the monomer described in Table 1 were added to prepare a monomer pre-emulsion to prepare a monomer pre-emulsion Respectively.
When the internal temperature of the reactor reached 40 ° C, 50 parts by weight of the monomer pre-emulsion, 0.002 parts by weight of t-butyl hydroperoxide (TBHP) and 0.03 part by weight of sodium formaldehyde sulfoxylate (SFS) Respectively.
After completion of the first reaction, 0.001 part by weight of TBHP and 0.002 part by weight of SFS were added to 50% of the remaining monomer pre-emulsion, and secondary polymerization was carried out.
After 120 minutes of monomer-free pre-emulsion injection, 0.002 parts by weight of initiator TBHP and 0.004 parts by weight of SFS were added and aged for 1 hour.
The prepared acrylic copolymer latex TSC was measured at about 40% and the latex particle size at 120 nm.
(2) Measurement of weight average molecular weight
The acrylic copolymer latex was dried at room temperature, and 0.03 g of a solid component was dissolved in 10 ml of tetrahydrofuran (THF) for 24 hours, and the weight average molecular weight was measured by Gel Permeation Chromatography (GPC). The weight average molecular weight of the prepared acrylic copolymer was 380,000.
(3) Manufacture of Acrylic Processing Aids 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 the above Examples and Comparative Examples to agglomerate to obtain a slurry, and the slurry was washed three times with ionized water to remove by-products. Thereafter, the ionized water was removed by filtration and dried at 80 DEG C for 3 hours using a small fluid bed dryer to obtain an acrylic processing assistant powder.
MMA: methyl methacrylate
BA: butyl acrylate
2EHA: 2-ethylhexyl acrylate
SM: Styrene
SMAS: sodium methallylsulfonate
DVPM: 1,2-dimethyl 5-vinyl-pyridinium methylsulfate
Experimental Example: Preparation of vinyl chloride resin and measurement of physical properties
(1) Production of vinyl chloride resin
After adding 6.0 g of a complex stabilizer KD-105 (monotone industry, a composite heat stabilizer obtained by uniformly mixing a heat stabilizer and a lubricant) and 15 g of a filler (CaCO3) to 100 g of a vinyl chloride resin (LS080, manufactured by LG Chemical) 5 g of the acrylic processing auxiliary composition prepared in 1 and 0.8 g of azodicarbonamide as a foaming agent were added and mixed by raising the temperature to 115 캜 using a Henschel mixer to obtain a vinyl chloride resin composition containing an acrylic copolymer .
(2) Measurement of physical properties
- Melting time: 55 g of the vinyl chloride resin composition prepared above was processed using a Brabender under the conditions of 175 캜 and 40 rpm, and the time taken from the minimum load to the maximum load was measured.
- Fish eye phenomenon: A vinyl chloride resin composition was prepared without adding a filler in the production of a vinyl chloride resin composition, and then a 20 mm single screw extruder equipped with a T-die was used At the cylinder temperature of 180 ° C and at a screw speed of 30 rpm, the film was pulled out with a film of 0.2 mm thickness. The number of fish eyes present in the predetermined area of the film surface was visually observed. When there was little fish eye, 3 points for slightly generated fish, and 1 point for fish eyes.
- Foam Properties: The prepared vinyl chloride resin composition was melt-kneaded using a Haake twin extruder at a cylinder temperature of 180 ° C and a screw speed of 30 rpm at a slit die size of 2 mm (thickness) X 30 mm (width) And the extruded amount and the melt pressure value were measured. And then cut into a length of 30 mm, and the density of the foams was measured using a plastic specific gravity meter. At this time, the higher the foaming density, the lower the expansion ratio, indicating that the foaming property is insufficient. The cross-section of the foamed molded article obtained above was observed with an optical microscope, and it was found that when the foamed cells were uniform, 5 points, when the foamed cells were slightly uneven, 3 points, and when most foamed cells were not uniform, The sex was evaluated.
(s)
(point)
(bar)
(g / min)
(g / cm3)
(5 pt)
Melting time: 70 to 100 seconds
Micro-dispersion melts: 4 ~ 5 points
Melt pressure: 130 ~ 150 bar
Extrusion amount: 180 to 200 g / min
Foaming Specific Gravity: 0.40 to 0.50 g / cm3
Referring to Table 1, it was confirmed that the vinyl chloride resin using the processing aid of the embodiment having the monomer system proposed in the present invention falls within an appropriate range of the melting time and foam processed properties. Further, it was confirmed that there was almost no fine dispersion melt.
On the other hand, when the water-soluble comonomer of Comparative Example 1 was not used, the microdispersed melt was seriously generated, and the melt pressure, compression amount and cell uniformity were lowered and the specific gravity of the foam was increased.
Also, in the case of Comparative Examples 2 and 3, the tendency was similar even when the content was outside the range of the water-soluble comonomer. From these results, the properties of the vinyl chloride resin can be largely changed by the content of the water-soluble comonomer .
As shown in the results of the above Experimental Examples, the acrylic processing aid according to the present invention effectively suppresses the generation of a finely dispersed melt after the foaming molding of the vinyl chloride resin by using the water-soluble comonomer in a specific range, Can be increased to an appropriate range to improve foaming processability as well as to reduce foam specific gravity and increase cell uniformity to increase foaming moldability.
INDUSTRIAL APPLICABILITY The acrylic processing aid of the present invention can be used as a processing aid in the production of various molded articles using a vinyl chloride resin, thereby making it possible to produce molded articles having excellent physical properties.
Claims (8)
70 to 85% by weight of methyl methacrylate,
From 10 to 25% by weight of C2 to C8 alkyl acrylates,
0.5 to 10% by weight of an aromatic vinyl monomer, and
And an acrylic copolymer copolymerized with 0.5 to 5.0% by weight of a water-soluble comonomer.
Wherein the C2 to C8 alkyl acrylate is one selected from the group consisting of ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, and combinations thereof. .
Wherein the aromatic vinyl monomer is one selected from the group consisting of styrene,? -Methylstyrene, o-ethylstyrene, p-ethylstyrene, vinyltoluene, and combinations thereof.
Wherein the water-soluble comonomer is an anionic comonomer or a cationic comonomer.
The anionic comonomer is selected from the group consisting of acrylic acid, methacrylic acid, sodium p-styrene sulfonate, sodium metallyl sulfonate, sodium salt of 2-sulfoethyl methacrylate, 2-sulfoethyl methacrylate, sodium undecylenic isethionate, and combinations thereof. 2. The acryl-based processing aid according to claim 1,
The cationic comonomer is selected from the group consisting of acrylamide, 1,2-dimethyl 5-vinyl-pyridinium methylsulfate and 1-methyl 2-ethyl 5-vinylpyridinium bromide (1 -methyl 2-ethyl-5-vinyl pyridinium bromide), and combinations thereof.
Wherein the acrylic copolymer has a weight average molecular weight (MW) of 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 of any one of claims 1 to 7.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150130885A KR102006716B1 (en) | 2015-09-16 | 2015-09-16 | Acrylic processing aid and vinyl chloride resin composition containing thereof |
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| KR1020150130885A KR102006716B1 (en) | 2015-09-16 | 2015-09-16 | Acrylic processing aid and vinyl chloride resin composition containing thereof |
Publications (2)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102399151B1 (en) * | 2021-05-21 | 2022-05-18 | 주식회사 리한 | Repairing method of crack in concrete using putty for restoration of the cover |
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| KR20040020963A (en) * | 2001-07-10 | 2004-03-09 | 카네카 코포레이션 | Processability improver and vinyl chloride resin composition containing the same |
| KR20060124307A (en) * | 2005-05-31 | 2006-12-05 | 주식회사 엘지화학 | Pvc processing-aids and process for manufacturing thereof |
| KR20130106824A (en) * | 2010-08-20 | 2013-09-30 | 가부시키가이샤 아데카 | Vinyl chloride resin composition |
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| KR20040020963A (en) * | 2001-07-10 | 2004-03-09 | 카네카 코포레이션 | Processability improver and vinyl chloride resin composition containing the same |
| KR20060124307A (en) * | 2005-05-31 | 2006-12-05 | 주식회사 엘지화학 | Pvc processing-aids and process for manufacturing thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102399151B1 (en) * | 2021-05-21 | 2022-05-18 | 주식회사 리한 | Repairing method of crack in concrete using putty for restoration of the cover |
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