Classifications

• • 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
• • 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
  • C08L25/08—Copolymers of styrene
  • C08L25/12—Copolymers of styrene with unsaturated nitriles
• • 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
  • 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

Definitions

• the present invention relates to a processing aid for a vinyl chloride resin composition, a vinyl chloride resin composition, and a molded product thereof.
• vinyl chloride-based resins are widely used in various molded products by taking advantage of their characteristics, they have various problems related to processing such as the processing temperature being close to the thermal decomposition temperature and poor fluidity.
• a method of blending a copolymer containing methyl methacrylate as a main component as a processing aid has been generally proposed.
• gelation can be promoted without deteriorating the characteristics of the vinyl chloride resin, and a molded product having excellent transparency and surface gloss of the molded product can be obtained.
• flow marks and fish eyes are generated on the surface of the calendar sheet and the film during calendar processing, which reduces the commercial value of the molded product.
• methyl methacrylate is relatively expensive among commonly used (meth) acrylic acid esters, and there has been a demand for a processing aid using an inexpensive raw material.
• Patent Document 1 a processing aid containing a first polymer containing a vinyl cyanide compound and an aromatic vinyl compound and a second polymer containing an alkyl acrylate and having a low Tg is provided in a vinyl chloride resin composition.
• a method of adding to is proposed. In this method, the gelation time is shortened while maintaining a low cost by using styrene, which is an inexpensive aromatic vinyl compound.
• a processing aid containing a first polymer and a second polymer having a specific composition and weight average molecular weight is an inexpensive raw material.
• the surface properties and gloss of a molded product can be suitably compatible with each other while maintaining good transparency and yellowness by using a large amount of aromatic vinyl compounds, and have completed the present invention.
• the present invention includes the following aspects.
• the total weight of the first polymer is 000, which is 100% by weight, and is composed of 60 to 100% by weight of alkyl methacrylate and 0 to 40% by weight of other copolymerizable vinyl-based compounds, and the second polymer is by weight.
• the average molecular weight is 10,000 to 400,000
• the total weight of the second polymer is 100% by weight, and 30 to 90% by weight of the aromatic vinyl-based compound and 10 to 70% by weight of other copolymerizable vinyl-based compounds.
• the total of the first polymer and the second polymer is 100% by weight, the ratio of the first polymer is 20 to 90% by weight, and the ratio of the second polymer is 20 to 90% by weight.
• the processing aid is 10 to 80% by weight, the processing aid is 100% by weight, and the proportion of the aromatic vinyl-based compound is 20% by weight or more. Agent.
• the first polymer and / or the third polymer which is the outermost layer covering the second polymer is contained, and the third polymer has a Tg of ⁇ 40 to 60 ° C. and is said to be the first.
• the first polymer has a weight average molecular weight of 1,000,000 to 2,000,000, the entire first polymer is 100% by weight, and the alkyl methacrylate is 80 to 100% by weight.
• the second polymer is composed of 0 to 20% by weight of other polymerizable vinyl-based compounds, and the weight average molecular weight of the second polymer is 15,000 to 150,000, the total weight of the second polymer is 100% by weight, and cyanide. It is composed of 5 to 40% by weight of a vinyl compound, 60 to 85% by weight of an aromatic vinyl compound, and 0 to 20% by weight of other copolymerizable vinyl compounds, and the processing aid is the first weight.
• the total of the coalescence and the second polymer is 100% by weight, the ratio of the first polymer is 40 to 80% by weight, and the ratio of the second polymer is 20 to 60% by weight, ⁇ 1> or ⁇ .
• the first polymer is composed of 90 to 100% by weight of alkyl methacrylate and 0 to 10% by weight of other copolymerizable vinyl compounds, wherein the entire first polymer is 100% by weight.
• the weight average molecular weight of the two polymers is 20,000 to 80,000, and the processing aid has a total of the first polymer and the second polymer as 100% by weight, and the first polymer has a weight average of 100% by weight.
• processing of a vinyl chloride resin composition that achieves both surface properties (flow marks, fish eyes) and gloss of a molded product of a vinyl chloride resin composition while maintaining good transparency and yellowness.
• Auxiliary agents can be provided.
• the processing aid for the vinyl chloride resin composition of the present invention (hereinafter, also simply referred to as a processing aid) comprises a first polymer having a structural unit composed of an alkyl methacrylate and a structural unit composed of an aromatic vinyl compound. It contains at least the second polymer having.
• the "processing aid for a vinyl chloride resin composition” means gelation of a vinyl chloride resin composition during molding without substantially deteriorating the characteristics of the vinyl chloride resin. It is intended as an additive that can promote the above-mentioned effect and improve the surface property of the molded product.
• the total of the first polymer and the second polymer is 100% by weight, the ratio of the first polymer is 20 to 90% by weight, and the ratio of the second polymer is 10 to 80% by weight.
• the proportion of the first polymer is 40 to 80% by weight
• the proportion of the second polymer is 20 to 60% by weight
• the proportion of the first polymer is 50 to 70% by weight, the second.
• the proportion of the polymer is 30 to 50% by weight.
• the processing aid is 100% by weight, and the proportion of the aromatic vinyl compound is 20% by weight or more from the viewpoint of maintaining the superiority of the raw material price and the improvement of the surface property of the molded product.
• the ratio of the aromatic vinyl compound is preferably 22 to 60% by weight, more preferably 23 to 50% by weight, further preferably 24 to 40% by weight, and particularly preferably 25 to 35% by weight.
• the aromatic vinyl-based compound referred to in this paragraph refers to the entire aromatic vinyl-based compound contained in the processing aid, and in addition to the aromatic vinyl-based compound contained in the second polymer, the first polymer and When the / or tertiary polymer contains an aromatic vinyl-based compound, the aromatic vinyl-based compound contained in the primary polymer and / or the tertiary polymer is also included.
• the present inventor has made the gloss and surface properties (flow) of the obtained molded product when a processing aid consisting of only one of the first polymer and the second polymer is used for the vinyl chloride resin composition. It was found that it is difficult to achieve both marks and fish eyes. And if it is a processing aid having both a first polymer and a second polymer and they have a specific composition, ratio, and weight average molecular weight, the gloss and surface property of the obtained molded product are suitably compatible. I found that I could do it.
• the "flow mark” means a streak on the surface of a molded product when a part of the molten resin mass generated in the gap of the roll when molding the vinyl chloride resin composition passes through the gap. Refers to the part that remains as a pattern or striped pattern.
• the “fisheye” is defined as a spherical or elliptical foreign substance in which the processing aid is aggregated without being dispersed in the vinyl chloride resin and has a maximum length L of 50 ⁇ m or more.
• the processing aid preferably has a granular structure, more preferably contains the first polymer and the second polymer in one particle, and the first polymer and the second polymer are chemically bonded to each other. It is particularly preferable that they exist independently in one particle. That is, it is preferable that the processing aid does not have a crosslinked structure.
• the structure of the processing aid in the vinyl chloride resin composition is not particularly limited, and may be a granular structure or a linear structure.
• the volume average particle size of the processing aid is preferably 0.05 ⁇ m to 0.5 ⁇ m from the viewpoint of particle stability and polymerization rate (productivity) during production. 07 ⁇ m to 0.3 ⁇ m is more preferable, and 0.1 ⁇ m to 0.2 ⁇ m is even more preferable.
• the volume average particle size the powdered processing aid may be measured, or the processing aid in the latex may be measured as described later.
• the processing aid may be composed of only the first polymer and the second polymer, but from the viewpoint of the granulation property of the processing aid, the third polymer is added to the first polymer and the second polymer. May further be included. In that case, the tertiary polymer becomes the outermost layer covering the primary polymer and / or the secondary polymer.
• each polymer may have a single-layer structure or a multi-layer structure. That is, each of the first polymer, the second polymer, and the third polymer may have a single-layer structure or a multi-layer structure.
• the content of the tertiary polymer is 1 to 50 parts by weight, with the total of the first polymer and the second polymer being 100 parts by weight from the viewpoint of the balance between granulation property and cost. It is preferably present, more preferably 5 to 30 parts by weight, still more preferably 8 to 15 parts by weight.
• the first polymer has a weight average molecular weight of 600,000 to 4,000,000.
• the weight average molecular weight of the first polymer is preferably 700,000 to 3,500,000, preferably 800,000 to 2, from the viewpoint of achieving both workability and gloss and surface properties of the molded product. It is more preferably 500,000, and even more preferably 1,000,000 to 2,000,000.
• the entire first polymer is 100% by weight, and 60 to 100% by weight of alkyl methacrylate and other vinyl-based compounds copolymerizable (that is, other vinyl-based compounds copolymerizable with alkyl methacrylate).
• Compound) Consists 0-40% by weight.
• the first polymer contains alkyl methacrylate having high compatibility with the vinyl chloride resin, the processability and the gloss of the molded product can be improved.
• the total content of the first polymer is preferably 100% by weight, preferably 70 to 100% by weight of alkyl methacrylate and 0 to 30% by weight of other copolymerizable vinyl compounds, and 80 to 30% by weight of alkyl methacrylate.
• it is 100% by weight and 0 to 20% by weight of the other copolymerizable vinyl compound, and 90 to 100% by weight of the alkyl methacrylate and 0 to 10% by weight of the other copolymerizable vinyl compound. It is more preferable to have.
• alkyl methacrylates methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, Linear alkyl methacrylates having 1 to 20 carbon atoms such as pentadecyl methacrylate, hexadecyl methacrylate, and octecyl methacrylate; isopropyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, isopentyl methacrylate, 2-ethylhex
• the alkyl group of the alkyl methacrylate has preferably 1 to 14 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 10 carbon atoms, still more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
• linear alkyl methacrylate is more preferable, and methyl methacrylate and ethyl methacrylate are further preferable.
• vinyl compounds that can be copolymerized with alkyl methacrylate include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, and dodecyl.
• Linear alkyl acrylates having 1 to 20 carbon atoms such as acrylates, tridecyl acrylates, tetradecyl acrylates, pentadecyl acrylates and hexadecyl acrylates; isopropyl acrylates, isobutyl acrylates, s-butyl acrylates, t-butyl acrylates, isopentyl acrylates, 2-Ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate, isodecyl acrylate, isoundecyl acrylate, isododecyl acrylate, isotridecyl acrylate, isotetradecyl acrylate, isopentadecyl acrylate, isohexadecyl acrylate, isoheptadecyl acrylate.
• Branched chain alkyl acrylate having 3 to 20 carbon atoms such as isooctadecyl acrylate; Cyclic alkyl acrylate having 3 to 20 carbon atoms such as cyclopropyl acrylate, cyclobutyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, cyclooctyl acrylate, and cyclodecyl acrylate.
• Aryl methacrylates such as phenyl methacrylate and methyl phenyl methacrylate; Aralkyl methacrylates such as benzyl methacrylate; Unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; unsaturated acids such as acrylic acid and methacrylic acid; maleimide , N-Methylmaleimide, N-butylmaleimide, N- (p-methylphenyl) maleimide, N-phenylmaleimide, N-cyclohexylmaleimide and other ⁇ , ⁇ -unsaturated dicarboxylic acid imide compounds; glycidyl methacrylate, allyl glycidyl ether.
• Epoxy group-containing unsaturated compounds such as acrylamide, unsaturated carboxylic acid amides such as methacrylamide; amino group-containing unsaturated compounds such as acrylic amine, aminomethyl methacrylate, amino ether methacrylate, aminopropyl methacrylate, aminostyrene; 3-Hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, tiger Hydroxazoline-containing unsaturated compounds such as s-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and hydroxystyrene; oxazoline groups such as vinyl oxazoline. Examples thereof include unsaturated compounds contained therein. These may be used alone or in combination of two or more.
• the alkyl group of the alkyl acrylate has preferably 1 to 14 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 10 carbon atoms, still more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
• linear alkyl acrylates are more preferred, ethyl acrylates, propyl acrylates, butyl acrylates and 2-ethylhexyl acrylates are even more preferred, and butyl acrylates are particularly preferred.
• the second polymer has a weight average molecular weight of 10,000 to 400,000.
• the first polymer which is a high molecular weight substance
• the melt viscosity tends to be too high and the flow mark and fisheye tend to deteriorate.
• the weight average molecular weight of the second polymer is preferably 15,000 to 150,000, more preferably 15,000 to 120,000, still more preferably 15,000 to 100,000, and even more preferably 20,000 to 20,000. 80,000 is particularly preferable.
• the second polymer is 100% by weight of the entire second polymer, and is copolymerized with an aromatic vinyl compound of 30 to 90% by weight and another copolymerizable vinyl compound (that is, an aromatic vinyl compound).
• an aromatic vinyl compound that is, an aromatic vinyl compound.
• Other possible vinyl compounds Consists of 10-70% by weight.
• the second polymer can reduce the melt viscosity and reduce flow marks and fish eyes as compared with, for example, a processing aid containing a large amount of methyl methacrylate.
• the total amount of the second polymer is 100% by weight, and it is preferable that the aromatic vinyl compound is 50 to 90% by weight and the other copolymerizable vinyl compound is 10 to 50% by weight.
• aromatic vinyl compound examples include styrene, ⁇ -methylstyrene, p-methylstyrene, monobromostyrene, dibromostyrene, tribromostyrene, chlorstyrene and the like. Styrene is preferable from the viewpoint of raw material price. These may be used alone or in combination of two or more.
• Examples of other vinyl compounds that can be copolymerized with the aromatic vinyl compound include the compounds exemplified in the above-mentioned first polymer and vinyl cyanide compounds.
• the vinyl cyanide compound acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is more preferable. These can be used alone or in combination of two or more.
• the second polymer has 100% by weight of the entire second polymer, 5 to 40% by weight of the vinyl cyanide-based compound, and an aromatic vinyl-based compound. It may consist of 60 to 85% by weight and 0 to 20% by weight of other copolymerizable vinyl compounds (ie, vinyl cyanide compounds and other vinyl compounds copolymerizable with aromatic vinyl compounds). preferable.
• the proportion of the vinyl cyanide compound is more preferably 10 to 28% by weight, still more preferably 15 to 25% by weight.
• the proportion of the aromatic vinyl compound is more preferably 65 to 85% by weight, still more preferably 70 to 85% by weight.
• the Tg of the tertiary polymer is preferably in the range of ⁇ 40 ° C. to 60 ° C., more preferably ⁇ 30 ° C. to 40 ° C., and further preferably ⁇ 25 ° C. to 20 ° C. from the viewpoint of improving the granulation property of the processing aid. preferable.
• the third polymer is copolymerizable with 30 to 90% by weight of the alkyl acrylate, with the entire tertiary polymer as 100% by weight.
• a vinyl-based compound that is, other vinyl-based compound that can be copolymerized with an alkyl acrylate
• the alkyl acrylate the compounds exemplified in the above-mentioned first polymer and second polymer can be similarly used.
• other vinyl compounds copolymerizable with the alkyl acrylate the compounds exemplified in the above-mentioned second polymer and aromatic vinyl compounds can be similarly used.
• the processing aid is, for example, a water-based polymerization method such as an emulsion polymerization method or a suspension polymerization method from the viewpoints of ease of recovery, low odor of the polymer, handleability, blocking resistance and economy. Can be obtained by Of these, the emulsion polymerization method is more preferable from the viewpoint of dispersibility in the vinyl chloride resin. Further, an emulsification polymerization method, a soap-free emulsification polymerization method, and a drop suspension polymerization method capable of obtaining a particle structure are particularly preferable polymerization methods for obtaining two or more polymer structures.
• a monomer, an emulsifier, a radical polymerization agent, etc. constituting the first polymer are added to water to carry out polymerization to form a particulate first polymer.
• a monomer, an emulsifier, a radical polymerizer, a chain transfer agent, etc. constituting the second polymer are added to the system containing the particulate first polymer and further polymerized to form the second polymer. do.
• a monomer, an emulsifier, a radical polymerization agent and the like constituting the tertiary polymer are added to further carry out the polymerization to form the tertiary polymer as the outermost layer.
• the processing aid can be manufactured.
• the order of formation of the first polymer and the second polymer is not limited to this, and the first polymer may be formed after the second polymer is formed.
• emulsifier used in the emulsification polymerization method conventionally known emulsifiers can be used, and anionic emulsifiers such as fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkylphosphate ester salts, and sulfosuccinic acid diester salts; alkylamine salts and the like.
• anionic emulsifiers such as fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkylphosphate ester salts, and sulfosuccinic acid diester salts; alkylamine salts and the like.
• Cationic emulsifiers; nonionic emulsifiers such as polyoxyethylene alkyl ethers and polyoxyethylene fatty acid esters can be mentioned.
• anionic emulsifiers are preferable, fatty acid salts and sulfosuccinic acid diester salts are more preferable, and semi-cured beef tallow fatty acid potassium and sodium dioctyl sulfosuccinate are more preferable from the viewpoint of polymerization stability.
• anionic emulsifiers are preferable, fatty acid salts and sulfosuccinic acid diester salts are more preferable, and semi-cured beef tallow fatty acid potassium and sodium dioctyl sulfosuccinate are more preferable from the viewpoint of polymerization stability.
• ethylenediamine tetraacetate disodium salt, sodium formaldehyde sulfoxylate, ferrous sulfate and the like may be used as an auxiliary catalyst for polymerization, sodium sulfate and the like may be used as a latex viscosity regulator, and sodium hydroxide and the like may be used as a pH adjuster.
• the weight average molecular weights of the first polymer and the second polymer can be adjusted by changing the ratio of the monomers contained therein. Further, these weight average molecular weights can be adjusted by changing the amount of the radical polymerization agent and the chain transfer agent used as needed, the polymerization temperature, the polymerization time and the like.
• radical polymerizing agent used in the emulsification polymerization method examples include organic hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentan hydroperoxide, and t-butylperoxylaurate; A redox-based initiator by combining the oxidizing agent composed of organic hydroperoxides with a reducing agent such as sulfate, hydrogen sulfite, thiosulfate, primary metal salt, sodium formaldehyde sulfoxylate; potassium persulfate, Persulfates such as ammonium persulfate; azo compounds such as azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate, 2-carbamoyl azaisobutyronitrile; benzoyl peroxide, lauroyl peroxide and the like. Organic peroxides and the like can be used.
• the amount of the radical polymerizer used is, for example, 0.0001 to 1.0 part by weight, preferably 0.0005 to 0.5 part by weight, and more preferably 0, based on 100 parts by weight of the monomer used. It is 0.01 to 0.1 parts by weight.
• the amount of the radical polymerizer is large, the weight average molecular weight tends to decrease, and when the amount of the radical polymerizer is small, the weight average molecular weight tends to increase.
• Chain transfer agent When emulsifying and polymerizing the second polymer, it is preferable to use a chain transfer agent.
• the chain transfer agent include octyl mercaptans, n-dodecyl mercaptans, t-dodecyl mercaptans, n-hexyl mercaptans, n-hexadecyl mercaptans, n-tetradecyl mercaptans, t-tetradecyl mercaptans and other mercaptans, and tetraethylthium sulfides.
• Hydrocarbon salts such as carbon tetrachloride, ethylene bromide, pentanphenylethane, terpenes, or achlorein, metachlorine, allyl alcohol, 2-ethylhexylthioglycol, ⁇ -methylstyrene dimer and the like.
• the chain transfer agent is preferably mercaptans, more preferably t-dodecyl mercaptan. These chain transfer agents can be used alone or in combination of two or more.
• the amount of the chain transfer agent used is usually 0 to 1 part by weight with respect to 100 parts by weight of the monomer component.
• the amount of the chain transfer agent used is, for example, 0.001 to 3 parts by weight, preferably 0.01 to 1 part by weight, from the balance of flow mark, fisheye and gloss. , More preferably 0.05 to 0.5 parts by weight.
• the polymerization time can be changed depending on the monomer used, the emulsifier, the radical polymerization agent, the chain transfer agent used as needed, and the amount thereof, and is, for example, 1 hour to 50 hours or 5 hours to 24 hours. ..
• the polymerization temperature can be adjusted according to the monomer used, the emulsifier, the radical polymerization agent, the chain transfer agent used as needed, and the amount thereof, and is, for example, 10 ° C to 90 ° C, preferably 30 ° C to 30 ° C. It is 80 ° C.
• the volume average particle size of the processing aid in the latex is, for example, 0.100 ⁇ m or more and 0.500 ⁇ m or less.
• the volume average particle size can be calculated by a particle size analyzer (Nanotracwave, manufactured by Nikkiso Co., Ltd.).
• the obtained latex containing the processing aid may be pulverized by, for example, a coagulation method.
• a coagulation method such as salt coagulation or acid coagulation (inorganic salts (preferably divalent inorganic salts, more preferably calcium chloride), acids and the like.
• a method of contacting with a coagulant (), a method of spray-drying the latex to obtain a powder, or the like may be used.
• a processing aid may be prepared by further performing heat treatment, dehydration, washing, drying and the like.
• the vinyl chloride resin composition of the present invention contains 100 parts by weight of the vinyl chloride resin and 0.1 to 20 parts by weight of the processing aid.
• the amount of the processing aid is preferably 0.1 part by weight or more from the viewpoint of obtaining a good effect by adding the processing aid, and 20 weight by weight from the viewpoint of improving the dispersibility of the processing aid in the vinyl chloride resin.
• the part or less is preferable.
• the amount of the processing aid is preferably 0.2 to 18 parts by weight, more preferably 0.3 to 15 parts by weight, and further preferably 0.5 to 12 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. be.
• an impact resistance improver a stabilizer, a lubricant, a plasticizer, a colorant, a filler, a foaming agent and the like may be added to the vinyl chloride resin composition.
• the vinyl chloride resin composition can be obtained by mixing various components and kneading them at, for example, 100 to 200 ° C. using a kneader such as a Banbury mixer, a kneader, a roll, a ribbon blender, or a Henschel mixer.
• a kneader such as a Banbury mixer, a kneader, a roll, a ribbon blender, or a Henschel mixer.
• the molded product of the present invention is obtained by molding the above-mentioned vinyl chloride resin composition.
• a molded body of a vinyl chloride resin composition can be obtained by molding a kneaded vinyl chloride resin composition by extrusion molding, blow molding, injection molding, calendar molding, vacuum molding, inflation molding or the like.
• the molded product is, for example, a sheet having a thickness of 0.2 to 1.0 mm or a film having a thickness of 0.01 to 0.2 mm.
• the above-mentioned vinyl chloride-based resin composition can be used for producing a molded product of another known vinyl chloride-based resin composition.
• it can be suitably used for wall materials, floor materials, window frames, wall materials, building materials such as corrugated sheets; interior / exterior materials for automobiles; packings, gaskets, hoses, pipes, joints, electric wires, cables and the like.
• AN Acrylonitrile St: Styrene BA: Butyl acrylate MMA: Methyl methacrylate t-DM: t-dodecyl mercaptan
• ⁇ Weight average molecular weight of the first polymer or the second polymer> Dissolve the first polymer or the second polymer in tetrahydrofuran (THF), and use gel permeation chromatography (manufactured by Toso Co., Ltd., HLC-8220GPC) based on polystyrene for the soluble component.
• THF tetrahydrofuran
• HLC-8220GPC gel permeation chromatography
• Tg of tertiary polymer "Polymer Handbook Fourth Edition" by J. Brand, published by Wiley in 1998, the Tg of each monomer was calculated from the Tg of the homopolymer, and based on this. The Tg of the tertiary polymer was calculated.
• the sheet gloss of the vinyl chloride resin composition was evaluated as an index of the sheet physical characteristics.
• 100 parts by weight of vinyl chloride resin (trade name: Kanevinyl S-1008 average degree of polymerization 800), 1 part by weight of processing aid of each example or comparative example, impact resistance improving agent (manufactured by Kaneka Co., Ltd.) , Product name Kaneace B-625) 6.0 parts by weight, butyl tin mercapto stabilizer (manufactured by Nitto Kasei Co., Ltd .: TVS # 1360) 1.0 part by weight, internal lubricant (manufactured by Emery OleoChemicals, product name: GH4) 0 .5 parts by weight and 0.4 parts by weight of external lubricant (trade name: G70S manufactured by Emery OleoChemicals) were mixed in a powder state.
• vinyl chloride resin trade name: Kanevinyl S-1008 average degree of polymerization 800
• impact resistance improving agent manufactured
• the obtained mixture was kneaded using an 8-inch test roll (test roll manufactured by Kansai Roll Co., Ltd.) at a rotation speed of 17 rpm at 198 ° C. for 2 minutes to prepare a test piece having a thickness of 0.4 mm.
• a gloss meter manufactured by BYK Gardener was used for the obtained test piece, and the reflectance of 60 ° light rays was measured at five points in the center of the test piece, and the average value was calculated.
• HAZE values at both ends of the roll-molded sheet were measured in order to evaluate the flow mark of the vinyl chloride resin composition.
• the HAZE values at both ends of the sheet are indicators of the presence or absence of flow marks, and the lower the HAZE values at both ends of the sheet, the more the occurrence of flow marks is suppressed.
• Vinyl chloride resin (Product name: Kanevinyl S-1008, average degree of polymerization 800) 100 parts by weight, 1.6 parts by weight of processing aid of each example or comparative example, impact resistance improving agent (Co., Ltd.) Made by Kaneka, trade name Kaneace B-625) 6.0 parts by weight, butyl tin mercapto stabilizer (manufactured by Nitto Kasei Co., Ltd .: TVS # 1360) 1.0 part by weight, internal lubricant (manufactured by Emery OleoChemicals) Product name: GH4 ) 0.5 parts by weight and 0.4 parts by weight of an external lubricant (trade name: G70S manufactured by Emery OleoChemicals) were mixed in a powder state.
• impact resistance improving agent Co., Ltd.
• Butyl tin mercapto stabilizer manufactured by Nitto Kasei Co., Ltd .: TVS # 1360
• internal lubricant manufactured by Emery
• the obtained mixture is kneaded using an 8-inch test roll (test roll manufactured by Kansai Roll Co., Ltd.) at a rotation speed of 17 rpm and 207 ° C. for 2 minutes to prepare a test piece (sheet) having a thickness of 0.5 mm. bottom.
• test roll manufactured by Kansai Roll Co., Ltd.
• HAZE values were measured at a total of 18 locations at both ends of the sheet using a haze meter (trade name: NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd.), and the average value was calculated.
• ⁇ Number of fish eyes> As an index of surface properties, the number of fish eyes in the molded product of the vinyl chloride resin composition was measured. 100 parts by weight of vinyl chloride resin (trade name: Kanevinyl S-1008 average degree of polymerization 800), 10 parts by weight of processing aid of each example or comparative example, plasticizer (manufactured by J-Plus Co., Ltd.) : DOP) 50 parts by weight, Ba / Zn-based stabilizer (manufactured by ADEKA Co., Ltd .: AC-186) 3.0 parts by weight, plasticizer (manufactured by Sakai Chemical Co., Ltd .: H-St) 0.5 parts by weight, titanium oxide ( 0.4 parts by weight of Sakai Chemical Industry Co., Ltd .: R-62N) and 0.02 parts by weight of carbon black (manufactured by Tokai Carbon Co., Ltd .: Seast 3H) were mixed in a powder state.
• vinyl chloride resin trade name: Kaneviny
• the obtained mixture was kneaded using an 8-inch test roll (test roll manufactured by Kansai Roll Co., Ltd.) at a rotation speed of 18 rpm and 170 ° C. for 1 minute to prepare a test piece having a thickness of 0.4 mm.
• the number of fish eyes in the area of the test piece 3 cm ⁇ 3 cm was visually counted.
• Total light transmittance As an index related to transparency, the total light transmittance of the vinyl chloride resin composition was measured. 100 parts by weight of vinyl chloride resin (trade name: Kanevinyl S-1008 average degree of polymerization 800), 3 parts by weight of processing aid of each example or comparative example, butyl tin mercapto stabilizer (Nitto Kasei) Made by Co., Ltd .: TVS # 1380) 1.0 part by weight, internal lubricant (manufactured by Emery OleoChemicals, trade name: GH4) 0.5 part by weight, and external lubricant (manufactured by Emery OleoChemicals, trade name: G70S) 0.4 parts by weight It was mixed in a powder state.
• vinyl chloride resin trade name: Kanevinyl S-1008 average degree of polymerization 800
• processing aid of each example or comparative example butyl tin mercapto stabilizer (Nitto Kasei) Made by Co., Ltd .
• the obtained mixture was kneaded using an 8-inch test roll (test roll manufactured by Kansai Roll Co., Ltd.) at a rotation speed of 17 rpm at 165 ° C. for 5 minutes, and then pressed and molded by a press at 180 ° C. for 15 minutes. , A press plate having a thickness of 1.0 mm was produced.
• a transparency test test piece having a thickness of 5.0 mm, a length of 30 mm, and a width of 40 mm was produced from this press plate.
• the total light transmittance was measured at 23 ° C. as an index of transparency according to JIS K 7375 standard "Plastic-How to determine the total light transmittance and the total light reflectance".
• YI yellowness (reflection YI) of the vinyl chloride resin composition
• 100 parts by weight of vinyl chloride resin (trade name: Kanevinyl S-1008 average degree of polymerization 800), 3 parts by weight of processing aid of each example or comparative example, butyl tin mercapto stabilizer (Nitto Kasei) Made by Co., Ltd .: TVS # 1380) 1.0 part by weight, internal lubricant (manufactured by Emery OleoChemicals, trade name: GH4) 0.5 part by weight, and external lubricant (manufactured by Emery OleoChemicals, trade name: G70S) 0.4 parts by weight It was mixed in a powder state.
• vinyl chloride resin trade name: Kanevinyl S-1008 average degree of polymerization 800
• processing aid of each example or comparative example butyl tin mercapto stabilizer (Nitto Kasei) Made by Co., Ltd .: TVS # 1380
• the obtained mixture was kneaded using an 8-inch test roll (test roll manufactured by Kansai Roll Co., Ltd.) at a rotation speed of 17 rpm at 165 ° C. for 5 minutes, and then pressed and molded by a press at 180 ° C. for 15 minutes.
• a press plate having a thickness of 1.0 mm was produced.
• a test piece for yellowness test having a thickness of 5.0 mm, a length of 30 mm, and a width of 40 mm was produced.
• the yellowness was measured at 23 ° C. according to JIS K 7373 standard "Plastic-How to determine yellowness and yellowing".
• Example 1 ⁇ Comparison of weight average molecular weight of first polymer> (Example 1) 1.2 parts of sodium dioctylsuccinate (parts by weight, the same applies hereinafter) and 0.05 part of sodium sulfate dissolved in water in advance were placed in a reactor with a stirrer, and water was further added to make the total amount of water 200 parts. After the inside of the reactor was replaced with nitrogen to remove oxygen in the space and water, the temperature of the contents was raised to 75 ° C. with stirring.
• Coagulation was performed by adding the obtained latex of the processing aid to 4 parts of a calcium chloride aqueous solution diluted to a concentration of 1% by weight under a temperature condition of 70 ° C. Then, it was heat-treated, dehydrated, washed and dried to obtain a powder of a processing aid. Using the obtained powder of the processing aid, the above-mentioned vinyl chloride resin composition was evaluated as a molded product.
• Examples 2 to 3 and Comparative Example 1 The processing aid powders of Examples 2 to 3 and Comparative Example 1 were obtained in the same manner as in Example 1 except that the weight average molecular weight of the first polymer was changed according to the composition shown in Table 1. Using the obtained powder of the processing aid, the above-mentioned vinyl chloride resin composition was evaluated as a molded product. The weight average molecular weight of the first polymer was adjusted by changing the amount of potassium persulfate added during the production of the first polymer.
• Examples 4 to 7 The processing aid powders of Examples 4 to 7 were obtained in the same manner as in Example 1 except that the ratio and / or composition of the first polymer was changed according to the composition shown in Table 2. Using the obtained powder of the processing aid, the above-mentioned vinyl chloride resin composition was evaluated as a molded product.
• Examples 8 to 12, Comparative Examples 2 to 3 The processing aid powders of Examples 8 to 12 were obtained in the same manner as in Example 1 except that the composition and / or weight average molecular weight of the second polymer was changed according to the composition shown in Table 3. Using the obtained powder of the processing aid, the above-mentioned vinyl chloride resin composition was evaluated as a molded product. The weight average molecular weight of the second polymer was adjusted by changing the amount of t-dodecyl mercaptan added during the production of the second polymer.
• a processing aid corresponding to Patent Document 1 was prepared as follows. 0.5 parts of sodium dioctylsuccinate (weight part, the same applies hereinafter) and 0.058 parts of ferrous sulfate (FeSO 4.7H 2 O) dissolved in water in advance, 0.0032 parts of ethylenediamine tetraacetate disodium salt and formaldehyde. 0.06 part of sodium succinate was placed in a reactor with a stirrer, and water was further added to bring the total amount of water to 200 parts.
• the lower the weight average molecular weight of the second polymer the better the flow mark and fisheye characteristics.
• the processing aids obtained in Examples 1 and 10 are used, the balance of gloss and flow mark is balanced while maintaining good transparency and yellowness. A sheet with better quality and excellent fisheye characteristics was obtained.
• the processing aids obtained in Comparative Examples 2 and 3 in which the weight average molecular weight of the second polymer was increased beyond the range of the present invention was used, the fisheye characteristics were significantly deteriorated.
• the processing aid obtained in Comparative Example 4 in which the first polymer and the second polymer are outside the range of the present invention can be used.
• the gloss and fisheye characteristics deteriorated.
• One aspect of the present invention can be suitably used for producing a vinyl chloride resin composition having excellent surface properties and gloss while maintaining good transparency and yellowness, and a molded product thereof.

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