WO2015108101A1 - 塩化ビニル樹脂組成物、及び塩化ビニル樹脂成形体 - Google Patents
塩化ビニル樹脂組成物、及び塩化ビニル樹脂成形体 Download PDFInfo
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- WO2015108101A1 WO2015108101A1 PCT/JP2015/050928 JP2015050928W WO2015108101A1 WO 2015108101 A1 WO2015108101 A1 WO 2015108101A1 JP 2015050928 W JP2015050928 W JP 2015050928W WO 2015108101 A1 WO2015108101 A1 WO 2015108101A1
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Definitions
- the present invention relates to a vinyl chloride resin composition and a vinyl chloride resin molded article.
- This application claims priority based on Japanese Patent Application No. 2014-006906 filed in Japan on January 17, 2014, the contents of which are incorporated herein by reference.
- Vinyl chloride resin which is a thermoplastic resin, is widely used as a general-purpose resin material with high utility value because it is excellent in chemical resistance, impact resistance, weather resistance and the like and is inexpensive.
- a stabilizer is usually used in combination with the vinyl chloride resin.
- As stabilizers used for vinyl chloride resins lead-based stabilizers have been most widely used so far, but there have been problems in terms of working environment and handling.
- non-foamed vinyl chloride resin composition such as vinyl chloride resin pipes for drinking water and vinyl chloride resin pipes for sewage. When used, the use of lead-based stabilizers is prohibited or restricted.
- Patent Document 1 discloses a vinyl chloride resin composition using a Ca—Zn stabilizer.
- stabilizers that are compounds containing at least one of calcium and zinc, such as Ca stabilizers, Zn stabilizers, and Ca-Zn stabilizers, are compared to conventional lead stabilizers and organotin stabilizers. Tend to be inferior in thermal stability. For this reason, when molding a vinyl chloride resin composition containing a vinyl chloride resin and the stabilizer, the molding temperature cannot be increased. As a result, the disintegration of the vinyl chloride resin particles does not proceed sufficiently, and when the vinyl chloride resin composition contains an impact strength modifier, the impact strength modifier is not sufficiently dispersed, leading to lead-based stability. Compared with the case where an agent and an organotin stabilizer were used, the resulting molded article was sometimes inferior in mechanical properties.
- the vinyl chloride resin composition described in Patent Document 1 has a high possibility that the kneading of vinyl chloride resin particles and the dispersion of the impact strength modifier are insufficient, and the performance of the vinyl chloride resin composition is sufficiently exhibited. It cannot be said that it is done. Furthermore, the vinyl chloride resin composition described in Patent Document 1 has poor processability. In Patent Document 1, the processing aid is not particularly considered.
- the present invention has been made in view of the above circumstances, and even when a stabilizer, which is a compound containing at least one of calcium and zinc, is used, a molded article having excellent mechanical properties can be obtained, and the processability is good.
- An object is to provide a resin composition and a vinyl chloride resin molded article having excellent mechanical properties.
- a vinyl chloride resin composition comprising a vinyl chloride resin (A), a stabilizer (B) which is a compound containing at least one of calcium and zinc, and a processing aid (C), wherein the processing aid
- the agent (C) contains 19 to 95% by mass of the methyl methacrylate monomer (c1) unit and 5 to 81 units of the methacrylic acid alkyl ester monomer (c2) unit having an alkyl group having 3 to 5 carbon atoms.
- a vinyl chloride resin composition which is a copolymer containing mass%.
- Methacrylic acid alkyl ester monomer (c2) in which the processing aid (C) has a methyl methacrylate monomer (c1) unit of 19 to 94% by mass and an alkyl group having 3 to 5 carbon atoms The vinyl chloride resin composition according to [1], which is a copolymer containing 5 to 80% by mass of units and 1 to 20% by mass of other monomer (c3) units.
- the processing aid (C) is a copolymer containing 5 to 60% by mass of a methacrylic acid alkyl ester monomer (c2) unit having an alkyl group having 3 to 5 carbon atoms.
- the processing aid (C) is a copolymer containing 18 to 50% by mass of a methacrylic acid alkyl ester monomer (c2) unit having an alkyl group having 3 to 5 carbon atoms.
- the processing aid (C) is a copolymer containing 1 to 20% by mass of an acrylate monomer unit as the other monomer (c3) unit.
- [1] to [5] The vinyl chloride resin composition according to any one of the above.
- [7] The chlorination according to any one of [1] to [6], wherein the processing aid (C) is a copolymer containing 1 to 10% by mass of other monomer (c3) units.
- Vinyl resin composition [8] The vinyl chloride resin composition according to [7], wherein the processing aid (C) is a copolymer containing 1 to 5% by mass of other monomer (c3) units.
- the vinyl chloride resin composition according to [14] comprising 4.0 to 10.0 parts by mass of the impact strength modifier (D) with respect to 100 parts by mass of the vinyl chloride resin (A).
- the total of the body (c3) units shall not exceed 100% by mass.
- the stabilizer which is a compound containing at least one of calcium and zinc is used for the vinyl chloride resin composition of this invention, the molded object which is excellent in a mechanical characteristic is obtained, and also workability is favorable.
- the vinyl chloride resin molded article of the present invention is excellent in mechanical properties.
- molded body refers to a vinyl chloride resin molded body obtained by molding the vinyl chloride resin composition of the present invention.
- (Meth) acrylic acid is a general term for acrylic acid and methacrylic acid.
- Vinyl chloride resin composition contains a vinyl chloride resin (A), a stabilizer (B), and a processing aid (C). Moreover, it is preferable that a vinyl chloride resin composition further contains an impact strength modifier (D).
- the vinyl chloride resin (A) is a copolymer the content of the vinyl chloride monomer (a1) unit is 100% by mass when the total of all the structural units constituting the copolymer is 100% by mass. 10 to 99% by mass is preferable, and 50 to 99% by mass is more preferable.
- the monomer (a2) copolymerizable with vinyl chloride may be any monomer having a reactive double bond in the molecule, such as ⁇ -olefins such as ethylene, propylene and butene; vinyl acetate and propion.
- Vinyl esters such as vinyl acid; vinyl ethers such as butyl vinyl ether and cetyl vinyl ether; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, Esters of acrylic acid or methacrylic acid such as butyl methacrylate, phenyl acrylate and phenyl methacrylate; vinyl halides other than vinyl chloride such as vinylidene chloride and vinyl fluoride; N-phenylmaleimide, N-cyclohexylmaleimide, etc. N-substituted maleimides And the like.
- the homopolymer or copolymer of the vinyl chloride monomer (a1) may be obtained by any known polymerization method such as suspension polymerization method, emulsion polymerization, solution polymerization method, bulk polymerization and the like.
- a vinyl chloride resin (A) may be used independently and may use 2 or more types together.
- the average degree of polymerization of the vinyl chloride resin (A) is preferably 500 to 3000, more preferably 500 to 2000, and even more preferably 500 to 1500.
- the average degree of polymerization of the vinyl chloride resin (A) is 500 or more, the mechanical properties of the obtained molded body are further improved.
- the average degree of polymerization of the vinyl chloride resin (A) is 3000 or less, the processability of the vinyl chloride resin composition tends to be better.
- the value of the average degree of polymerization of the vinyl chloride resin (A) is a value obtained by using the manufacturer's catalog value or the well-known Mark-Houwink-Sakurada formula.
- the stabilizer (B) imparts thermal stability during the molding process of the vinyl chloride resin composition.
- the stabilizer (B) is a compound containing at least one of calcium and zinc.
- the stabilizer (B) is preferably a compound containing both calcium and zinc from the viewpoint that high thermal stability can be imparted to the vinyl chloride resin composition.
- a metal soap containing at least one of calcium and zinc is preferable as the stabilizer (B) in that high thermal stability can be imparted to the vinyl chloride resin composition, and both a Ca-based metal soap and a Zn-based metal soap are used.
- a Ca—Zn-based stabilizer containing is more preferable.
- a long-chain fatty acid calcium salt Ca-based stabilizer
- a long-chain fatty acid zinc salt Zn-based stabilizer
- Ca-Zn stabilizer a mixture of a Ca-based stabilizer and a Zn-based stabilizer
- long chain fatty acids examples include butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, linoleic acid
- examples include acid, ricinoleic acid, octylic acid, arachidic acid, arachidonic acid, behenic acid, lignoceric acid, and montanic acid.
- a stabilizer (B) may be used independently and may use 2 or more types together.
- the content of the stabilizer (B) is preferably from 0.1 to 10.0 parts by weight, more preferably from 0.5 to 10.0 parts by weight, based on 100 parts by weight of the vinyl chloride resin (A).
- the amount is more preferably 5 to 8.0 parts by mass, and particularly preferably 1.0 to 6.0 parts by mass. If content of a stabilizer (B) is 0.1 mass part or more, the improvement effect of the thermal stability of a vinyl chloride resin (A) will become easier to be obtained. On the other hand, if content of a stabilizer (B) is 10.0 mass parts or less, coloring of a molded object can be suppressed. Moreover, since the vinyl chloride resin (A) is sufficiently melted and kneaded, the mechanical properties of the molded body are further improved.
- the processing aid (C) shortens the gelation time of the vinyl chloride resin composition, imparts melt elasticity during molding processing, and improves processability and appearance of the molded product.
- the processing aid (C) includes a methyl methacrylate monomer (c1), a methacrylic acid alkyl ester monomer (c2) having an alkyl group having 3 to 5 carbon atoms, and other monomers as required. It is a copolymer of (c3). That is, the processing aid (C) contains 19 to 95% by mass of the methyl methacrylate monomer (c1) unit and the methacrylic acid alkyl ester monomer (c2) unit having an alkyl group having 3 to 5 carbon atoms.
- the methyl methacrylate monomer (c1) has good compatibility with the vinyl chloride resin (A).
- the content of the methyl methacrylate monomer (c1) unit is 19 to 95% by mass when the total of all the structural units constituting the copolymer (processing aid (C)) is 100% by mass. 19 to 94% by mass, preferably 40 to 94% by mass, and more preferably 50 to 82% by mass. If the content of the methyl methacrylate monomer (c1) unit is 19% by mass or more, the compatibility with the vinyl chloride resin (A) tends to be good, and the vinyl chloride resin (A) is sufficiently kneaded. Therefore, processability is improved.
- the content of the methyl methacrylate monomer (c1) unit is 95% by mass or less, the molecules of the processing aid (C) are easily dispersed in the vinyl chloride resin (A), and the machine of the molded body Improved characteristics.
- Examples of the methacrylic acid alkyl ester monomer (c2) having an alkyl group with 3 to 5 carbon atoms include propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate and the like. Among these, from the viewpoint of further improving the workability of the vinyl chloride resin composition, n-butyl methacrylate and isobutyl methacrylate are preferable, and n-butyl methacrylate is more preferable. These alkyl methacrylates may be used alone or in combination of two or more depending on the purpose.
- the content of the methacrylic acid alkyl ester monomer (c2) unit having an alkyl group having 3 to 5 carbon atoms is 100 masses of the total of all the constituent units constituting the copolymer (processing aid (C)). % Is 5 to 81% by mass, preferably 5 to 80% by mass, more preferably 5 to 60% by mass, still more preferably 10 to 60% by mass, and particularly preferably 12 to 50% by mass. Most preferred is ⁇ 50 mass%. If the content of the methacrylic acid alkyl ester monomer (c2) unit having an alkyl group having 3 to 5 carbon atoms is 5% by mass or more, the molecule of the processing aid (C) is contained in the vinyl chloride resin (A).
- the molded appearance of the molded body is improved.
- the content of the methacrylic acid alkyl ester monomer (c2) unit having an alkyl group having 3 to 5 carbon atoms is 81% by mass or less, the compatibility with the vinyl chloride resin (A) is improved. Since the vinyl chloride resin (A) can be sufficiently kneaded, processability is improved.
- a methacrylic acid-n-butyl monomer unit as a methacrylic acid alkyl ester monomer (c2) unit having an alkyl group having 3 to 5 carbon atoms constitutes a copolymer (processing aid (C)).
- the total of all the structural units is 100% by mass, it is preferably contained in an amount of 5 to 81% by mass, more preferably 5 to 80% by mass, still more preferably 5 to 60% by mass, and still more preferably Is 10 to 60% by mass, particularly preferably 12 to 50% by mass, and most preferably 18 to 50% by mass.
- Other monomers (c3) may be copolymerized with methyl methacrylate monomer (c1) and methacrylic acid alkyl ester monomer (c2) having an alkyl group having 3 to 5 carbon atoms.
- acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, phenyl acrylate, etc .
- Aromatic vinyl compounds such as styrene, ⁇ -methylstyrene and vinyltoluene
- Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile
- Vinyl esters such as vinyl acetate; Maleic anhydride, etc.
- acrylic acid esters such as ethyl acrylate, acrylic acid-n-butyl, acrylic acid-2-ethylhexyl, benzyl acrylate, phenyl acrylate, etc. are used for the processability of the vinyl chloride resin composition and the molded article obtained. It is preferable in terms of mechanical properties. In particular, it is more preferable that 50 to 100% by mass of n-butyl acrylate is contained in 100% by mass of the other monomer (c3) as the other monomer (c3). These monomers may be used alone or in combination of two or more according to the purpose.
- the content of the other monomer (c3) unit is preferably 0 to 20% by mass when the total of all the structural units constituting the copolymer (processing aid (C)) is 100% by mass. It is more preferably 1 to 20% by mass, further preferably 1 to 10% by mass, and particularly preferably 1 to 5% by mass. If the content rate of another monomer (c3) unit is 1 mass% or more, the heat-resistant decomposition property of a processing aid (C) will become favorable. On the other hand, if the content of other monomer (c3) units is 20% by mass or less, the vinyl chloride resin (A) can be efficiently melted and kneaded, and the processability of the vinyl chloride resin composition can be improved. The mechanical properties of the molded body are improved.
- the content is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, and still more preferably 1 to 5% by mass.
- Method for producing processing aid (C) Various methods can be used as a method for producing the processing aid (C), and examples thereof include various polymerization methods such as emulsion polymerization, suspension polymerization, and solution polymerization. Furthermore, any method such as batch addition of monomers, dropwise addition, divided addition of monomers, etc. may be used, and methods such as random copolymerization and block copolymerization may be used, but as processing aid (C), A random copolymer obtained by a method of batch addition of monomers is preferred.
- the emulsifier used in the emulsion polymerization method is not particularly limited, and various types can be used, for example, fatty acid salts, alkyl sulfate salts, alkylbenzene sulfones.
- Anionic surfactants such as acid salts, alkyl phosphate esters, dialkylsulfosuccinates; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan acid fatty esters, glycerin fatty acid esters; alkyls And cationic surfactants such as amine salts.
- These emulsifiers may be used independently and may use 2 or more types together.
- pH adjusters include boric acid-potassium chloride-potassium hydroxide, potassium dihydrogen phosphate-disodium hydrogen phosphate, boric acid-potassium chloride-potassium carbonate, citric acid-potassium hydrogen citrate, potassium dihydrogen phosphate -Borax, disodium hydrogen phosphate-citric acid and the like.
- examples of the polymerization initiator used for the production of the processing aid (C) include water-soluble and oil-soluble single-type or redox-type polymerization initiators.
- an inorganic polymerization initiator such as normal persulfate is used alone, or an inorganic polymerization initiator is combined with sulfite, bisulfite, thiosulfate, etc. as a redox initiator. It can also be used.
- organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, azo compounds, etc. are used alone, or these are combined with sodium formaldehyde sulfoxylate etc. to form a redox system.
- the present invention is not limited to these specific examples.
- the method for recovering the processing aid (C) in powder form is not particularly limited.
- the processing aid (C) is produced by an emulsion polymerization method
- the obtained latex of the copolymer is cooled.
- the copolymer was precipitated by acid coagulation or salting out with an acid such as sulfuric acid, hydrochloric acid, phosphoric acid, or a salt such as aluminum chloride, calcium chloride, magnesium sulfate, aluminum sulfate, calcium acetate, etc.
- the processing aid (C) can be obtained by further filtration, washing and drying.
- the processing aid (C) can be recovered in powder form by various methods such as spray drying and freeze drying.
- spray drying is preferable because a molded article having a good appearance can be easily obtained.
- spray drying can be performed under any conditions.
- the inside of the particles are fused and become homogeneous.
- the condition is such that the content of the powder is less than 50% by mass, more preferably less than 25% by mass.
- the molecular weight of the processing aid (C) is not particularly limited, but in order to exert a more excellent effect, the reduced viscosity ⁇ sp is preferably 0.1 to 1.5, more preferably 0.2 to 1.0, more preferably 0.3 to 0.9.
- the “reduced viscosity ⁇ sp” in the present invention is a value measured by dissolving 0.1 g of a polymer or copolymer in 100 mL of chloroform and measuring at 25 ° C.
- a method for adjusting the reduced viscosity ⁇ sp conventional methods such as adjustment of the amount of chain transfer agent and polymerization initiator used during polymerization and adjustment of the polymerization temperature can be used.
- the processing aid (C) may be used alone or in combination of two or more.
- the content of the processing aid (C) is preferably 0.1 to 10.0 parts by weight, more preferably 0.3 to 7.0 parts by weight, with respect to 100 parts by weight of the vinyl chloride resin (A). More preferably, it is in the range of 0.5 to 6.0 parts by mass. If content of a processing aid (C) is 0.1 mass part or more, the workability of a vinyl chloride resin composition will improve more. On the other hand, if the content of the processing aid (C) is 10.0 parts by mass or less, the mechanical properties of the molded article can be maintained well.
- Examples of the impact strength modifier (D) include rubber-based graft copolymers, NBR (acrylonitrile-butadiene rubber), EVA (ethylene-vinyl acetate copolymer), chlorinated polyethylene, thermoplastic elastomer, and the like.
- Examples of rubber-based graft copolymers include acrylic rubber-based graft copolymers, silicone rubber-based graft copolymers, composite rubber-based graft copolymers of silicone rubber and acrylic rubber, and MBS (methyl methacrylate-butadiene-styrene). Copolymer), ABS (acrylonitrile-butadiene-styrene copolymer), AES (acrylonitrile-ethylenepropylene rubber-styrene copolymer), and the like.
- the impact strength modifier (D) contains at least one of acrylic rubber and silicone rubber in that the weatherability of the molded article can be maintained satisfactorily.
- Specific examples of such impact strength modifiers (D) include acrylic rubber-based graft copolymers, silicone rubber-based graft copolymers, and composite rubber-based graft copolymers of silicone rubber and acrylic rubber. Can be mentioned.
- the acrylic rubber-based graft copolymer includes a rubber part made of acrylic rubber and a graft part bonded to the rubber part.
- the acrylic rubber is obtained by polymerizing (meth) acrylic acid ester and, if necessary, other vinyl monomers that can be copolymerized with (meth) acrylic acid ester.
- (Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylic acid-n-butyl, (meth) acrylic acid-isobutyl, (meth ) 2-ethylhexyl acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
- vinyl monomers examples include aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, and vinyl toluene; vinyl cyanide monomers such as (meth) acrylonitrile; fluorine-containing vinyl monomers. Can be mentioned.
- a monomer (graft monomer) copolymerizable with acrylic rubber is used as the monomer constituting the graft portion.
- graft monomers include aromatic vinyl monomers such as styrene and ⁇ -methylstyrene; acrylic esters such as ethyl acrylate and acrylic acid-n-butyl; methyl methacrylate and ethyl methacrylate.
- methacrylic acid esters such as (meth) acrylonitrile; crosslinkable monomers such as (meth) acrylallyl, diallyl phthalate, diallyl sebacate, and triallyl triazine.
- the acrylic rubber-based graft copolymer can be obtained by adding one or more graft monomers constituting the graft portion in the presence of acrylic rubber latex and performing graft polymerization.
- the silicone rubber-based graft copolymer includes a rubber part made of silicone rubber and a graft part bonded to the rubber part.
- the silicone rubber include polyorganosiloxane.
- the polyorganosiloxane can be obtained, for example, by polymerizing dimethylsiloxane, vinyl polymerizable functional group-containing siloxane, and, if necessary, a siloxane-based crosslinking agent.
- dimethylsiloxane include dimethylsiloxane-based cyclics having three or more members, and those having three to seven members are preferable.
- vinyl-polymerizable functional group-containing siloxane examples include methacryloyloxysilane such as ⁇ -methacryloyloxyethyldimethoxymethylsilane and ⁇ -methacryloyloxypropyldimethoxymethylsilane; vinylsiloxane such as tetramethyltetravinylcyclotetrasiloxane; p-vinyl Examples thereof include vinylphenyl silanes such as phenyldimethoxymethylsilane; mercaptosiloxanes such as ⁇ -mercaptopropyldimethoxymethylsilane and ⁇ -mercaptopropyltrimethoxysilane.
- siloxane-based crosslinking agent a trifunctional or tetrafunctional silane-based crosslinking agent is preferable, and examples thereof include trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane.
- a monomer constituting the graft portion a monomer (graft monomer) copolymerizable with silicone rubber is used.
- graft monomer the graft monomers exemplified in the description of the acrylic rubber-based graft copolymer can be used.
- the silicone rubber-based graft copolymer can be obtained by adding one or more graft monomers constituting the graft portion in the presence of silicone rubber latex and graft polymerization.
- the composite rubber-based graft copolymer includes a rubber part made of a composite rubber of silicone rubber and acrylic rubber, and a graft part bonded to the rubber part.
- the composite rubber can be prepared, for example, by adding a (meth) acrylic acid ester component to a polyorganosiloxane latex and polymerizing with a normal polymerization initiator.
- a polyorganosiloxane the polyorganosiloxane exemplified in the above description of the silicone rubber can be used.
- the (meth) acrylic acid ester component the (meth) acrylic acid ester exemplified in the description of the acrylic rubber can be used.
- a monomer (graft monomer) copolymerizable with a composite rubber of silicone rubber and acrylic rubber is used.
- graft monomer the graft monomers exemplified in the description of the acrylic rubber-based graft copolymer can be used.
- the composite rubber-based graft copolymer is obtained by adding one or more graft monomers constituting the graft portion and performing graft polymerization in the presence of a latex of composite rubber of silicone rubber and acrylic rubber.
- the impact strength modifier (D) may be used alone or in combination of two or more.
- the impact strength modifier (D) is preferably 0.5 to 30.0 parts by mass, more preferably 1.0 to 20.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A). More preferred is 10.0 parts by mass.
- the content of the impact strength modifier (D) is 0.5 parts by mass or more, the mechanical properties of the molded body are improved.
- the content of the impact strength modifier (D) is 30.0 parts by mass or less, it is possible to suppress a decrease in fluidity and a modulus of elasticity of the molded body when the vinyl chloride resin composition is melted.
- the vinyl chloride resin composition may contain other additives other than the vinyl chloride resin (A), the stabilizer (B), the processing aid (C), and the impact strength modifier (D).
- other additives include fillers, heat stabilizers (excluding the stabilizer (B)), plasticizers, lubricants, flame retardants, heat resistance improvers, mold release agents, fluidity improvers, Coloring agents, antistatic agents, conductivity imparting agents, antifogging agents, antibacterial agents and the like can be mentioned.
- a vinyl chloride resin composition does not contain a foaming agent.
- the filler examples include carbonates such as heavy calcium carbonate; inorganic fillers such as titanium oxide, clay, talc, mica, silica, and glass beads; carbon-based fillers such as carbon black and graphite; Natural organic substances; organic fillers such as silicone; inorganic fibers such as glass fibers and metal fibers; carbon fibers; organic fibers such as polyamides.
- a filler may be used independently and may use 2 or more types together.
- the heat stabilizer is preferably at least one selected from the group consisting of hydrotalcite heat stabilizers, tin heat stabilizers, and zeolite heat stabilizers.
- the heat stabilizer is used to improve thermal decomposition during molding, long run property, and appearance of a molded product.
- the heat stabilizer is preferably 0.1 to 10.0 parts by weight, and more preferably 0.2 to 5.0 parts by weight with respect to 100 parts by weight of the vinyl chloride resin (A).
- the hydrotalcite-based heat stabilizer is a hydrotalcite compound, specifically, a composite salt compound composed of magnesium and / or an alkali metal and aluminum, or a composite salt compound composed of zinc, magnesium and aluminum, There is a dehydrated crystal water.
- the hydrotalcite compound may be a natural product or a synthetic product, and the synthetic method of the synthetic product may be a conventionally known method.
- a heat stabilizer may be used independently and may use 2 or more types together.
- plasticizer examples include phthalate plasticizers such as diheptyl phthalate, dioctyl phthalate and diisononyl phthalate; adipate plasticizers such as dioctyl adipate, diisononyl adipate and di (butyl diglycol) adipate; phosphate plasticizers; Plasticizers; Chlorinated paraffinic plasticizers; Trimellitic plasticizers such as trioctyl trimellitate and tri (C7-9 mixed alkyl) trimellitate; Pyromellitic plasticizers such as tetraoctyl pyromellitate; Biphenyl tetracarboxylate plastics Agents and the like.
- a plasticizer may be used independently and may use 2 or more types together.
- the lubricant examples include pure hydrocarbon lubricants such as liquid paraffin, natural paraffin, micro wax, synthetic paraffin, and low molecular weight polyethylene wax; halogenated hydrocarbon lubricants; fatty acid lubricants such as higher fatty acids and oxy fatty acids; fatty acid amides , Fatty acid amide-based lubricants such as bis-fatty acid amides; ester-based lubricants such as lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids (ester waxes); metal soaps (Excluding the stabilizer (B)), fatty alcohol, polyhydric alcohol, polyglycol, polyglycerol, fatty acid and polyhydric alcohol partial ester, fatty acid and polyglycol, polyglycerol partial ester, and the like.
- a lubricant may be used independently and may use 2 or more types together.
- Examples of the flame retardant include chlorinated paraffin, aluminum hydroxide, antimony trioxide, and halogen compounds.
- a flame retardant may be used independently and may use 2 or more types together.
- heat resistance improver examples include (meth) acrylate copolymers, imide copolymers, styrene-acrylonitrile copolymers, and the like.
- a heat resistance improver may be used independently and may use 2 or more types together.
- the vinyl chloride resin composition comprises the above-described vinyl chloride resin (A), stabilizer (B), processing aid (C), and impact strength modifier (D) and other additives as necessary. Further, the mixture is obtained by melting and kneading. Examples of the mixing method include a method using a super mixer, a Henschel mixer and the like. Examples of the melting / kneading method include a method using an extruder, a Banbury mixer, a roller, a kneader and the like.
- Mixing, melting and kneading operations may be performed batchwise or continuously.
- the order of mixing the vinyl chloride resin (A), the stabilizer (B), the processing aid (C), the impact strength modifier (D), and other additives is not particularly limited.
- the vinyl chloride resin composition of the present invention described above contains the above-mentioned specific processing aid (C), a molded article having excellent mechanical properties even when a stabilizer which is a compound containing at least one of calcium and zinc is used. Is obtained, and the processability is good. Moreover, since the vinyl chloride resin composition of this invention contains the stabilizer (B) which is a compound containing at least one of the calcium and zinc mentioned above as a stabilizer, it is excellent in work environment and handleability.
- Vinyl chloride resin molding The vinyl chloride resin molded article of the present invention is obtained by molding the vinyl chloride resin composition of the present invention.
- the molding method include profile extrusion molding, injection molding, vacuum molding, blow molding, roll molding, and press molding. Of these, profile extrusion molding is preferred.
- the vinyl chloride resin molded article of the present invention is obtained by molding the vinyl chloride resin composition of the present invention, it is excellent in mechanical properties.
- the vinyl chloride resin molded body can be used in a wide range of fields such as building materials such as window frames, pipes, rain gutters, odd-shaped molded products, automobile materials, toys, stationery and other miscellaneous goods, OA equipment, and home appliances.
- the pellets were pelletized under the condition of a screw speed of 50 rpm to obtain a pellet-like vinyl chloride resin composition.
- Square bars were formed using a die having a width of 10 mm and a thickness of 5 mm under the conditions of ⁇ 160 ° C. ⁇ 170 ° C. ⁇ 180 ° C. ⁇ 190 ° C. ⁇ 190 ° C. ⁇ 190 ° C. ⁇ 190 ° C. and a screw rotation speed of 30 rpm.
- the obtained square bar was cut into a length of 80 mm, and Charpy impact strength was measured based on JIS K 7111-1: 2012 (ISO 179-1).
- MMA methyl methacrylate
- nBMA methacrylate n-butyl
- iBMA isobutyl methacrylate
- nBA acrylic acid
- n-butyl n-octyl mercaptan
- Example 1 100 parts of a vinyl chloride resin having an average polymerization degree of 1000 (manufactured by Shin-Etsu Chemical Co., Ltd., “TK-1000”), 2 parts of a mixture of calcium stearate and zinc stearate as a Ca—Zn-based stabilizer (manufactured by San Ace) , 1 part of processing aid (C-1), 7 parts of acrylic rubber-based graft copolymer (Mitsubishi Rayon Co., Ltd., “METABBRENE W-450A”) as impact strength modifier (D), ester-based lubricant as lubricant (Emery Oleo Chemicals Japan Co., Ltd., “LOXIOL VPN933”) 0.4 part and polyethylene wax (Emery Oleo Chemicals Japan Co., Ltd., “LOXIOL VPN233”) 0.4 part are mixed and dried to 110 ° C.
- Examples 2 to 6, Comparative Examples 1 to 4 A vinyl chloride resin composition was prepared in the same manner as in Example 1 except that the type and amount of processing aid (C) and the amount of impact strength modifier (D) were changed as shown in Table 2. The processability and mechanical properties were evaluated. The results are shown in Table 2.
- the vinyl chloride resin compositions obtained in each Example had a short gel time and good workability. Further, from these vinyl chloride resin compositions, molded articles having excellent mechanical properties were obtained.
- Examples 1 to 3 using a processing aid (C-1), a processing aid (C-2) or a processing aid (C-3) containing a predetermined amount of other monomer (c3) units The vinyl chloride resin compositions of Nos. 5 and 6 have a longer gelation time than the vinyl chloride resin composition of Example 4 using the processing aid (C-6) containing no other monomer (c3) unit. A compact which was short and superior in mechanical properties was obtained. Therefore, with the vinyl chloride resin composition of the present invention, a molded article having excellent mechanical properties can be obtained even when a stabilizer which is a compound containing at least one of calcium and zinc is used, and the workability is good. It has been shown.
- Comparative Example 1 using a processing aid (C-4) or a processing aid (C-5) not containing a methacrylic acid alkyl ester monomer (c2) unit having an alkyl group having 3 to 5 carbon atoms The vinyl chloride resin compositions (1) to (4) had a long gel time and poor processability. Moreover, the molded object obtained from this vinyl chloride resin composition was inferior also in the mechanical characteristic.
- the vinyl chloride resin composition of the present invention is useful as a material for, for example, building materials such as window frames, pipes, rain gutters, odd-shaped molded articles, automobile materials, toys, stationery and other miscellaneous goods, OA equipment, home appliances, and the like. .
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Abstract
Description
本願は、2014年1月17日に、日本に出願された特願2014-006906号、に基づき優先権を主張し、その内容をここに援用する。
塩化ビニル樹脂には、通常、安定剤が併用される。塩化ビニル樹脂に用いられる安定剤としては、これまで鉛系安定剤が最も幅広く用いられていたが、作業環境や取り扱い性の面で問題があった。特に、発泡剤を含まない硬質塩化ビニル樹脂組成物(以下、「非発泡塩化ビニル樹脂組成物」ともいう。)の分野、例えば、上水用塩化ビニル樹脂管及び下水用塩化ビニル樹脂管などに用いる場合には、鉛系安定剤の使用が禁止あるいは使用規制がされている。
例えば特許文献1には、Ca-Zn系安定剤を用いた塩化ビニル樹脂組成物が開示されている。
また、特許文献1に記載の塩化ビニル樹脂組成物は、塩化ビニル樹脂粒子の混練及び衝撃強度改質剤の分散が不充分である可能性が高く、塩化ビニル樹脂組成物の性能が充分に発揮されているとはいえない。さらに、特許文献1に記載の塩化ビニル樹脂組成物は、加工性にも劣るものであった。また、特許文献1では、加工助剤については特に考慮されていない。
[1] 塩化ビニル樹脂(A)と、カルシウム及び亜鉛の少なくとも一方を含む化合物である安定剤(B)と、加工助剤(C)とを含む塩化ビニル樹脂組成物であって、前記加工助剤(C)が、メタクリル酸メチル単量体(c1)単位を19~95質量%、及び炭素数が3~5のアルキル基を有するメタクリル酸アルキルエステル単量体(c2)単位を5~81質量%含む共重合体である、塩化ビニル樹脂組成物。
[2] 前記加工助剤(C)が、メタクリル酸メチル単量体(c1)単位を19~94質量%、炭素数が3~5のアルキル基を有するメタクリル酸アルキルエステル単量体(c2)単位を5~80質量%、及びその他の単量体(c3)単位を1~20質量%含む共重合体である、[1]に記載の塩化ビニル樹脂組成物。
[3] 前記加工助剤(C)が、炭素数が3~5のアルキル基を有するメタクリル酸アルキルエステル単量体(c2)単位として、メタクリル酸-n-ブチル単量体単位を含む共重合体である、[1]又は[2]に記載の塩化ビニル樹脂組成物。
[4] 前記加工助剤(C)が、炭素数が3~5のアルキル基を有するメタクリル酸アルキルエステル単量体(c2)単位を5~60質量%含む共重合体である、[1]~[3]のいずれか1つに記載の塩化ビニル樹脂組成物。
[5] 前記加工助剤(C)が、炭素数が3~5のアルキル基を有するメタクリル酸アルキルエステル単量体(c2)単位を18~50質量%含む共重合体である、[4]に記載の塩化ビニル樹脂組成物。
[7] 前記加工助剤(C)が、その他の単量体(c3)単位を1~10質量%含む共重合体である、[1]~[6]のいずれか1つに記載の塩化ビニル樹脂組成物。
[8] 前記加工助剤(C)が、その他の単量体(c3)単位を1~5質量%含む共重合体である、[7]に記載の塩化ビニル樹脂組成物。
[9] 前記安定剤(B)が、カルシウム及び亜鉛の両方を含む化合物である、[1]~[8]のいずれか1つに記載の塩化ビニル樹脂組成物。
[10] 発泡剤を含まない、[1]~[9]のいずれか1つに記載の塩化ビニル樹脂組成物。
[12] 前記衝撃強度改質剤(D)が、アクリルゴム及びシリコーンゴムの少なくとも一方を含む、[11]に記載の塩化ビニル樹脂組成物。
[13] 前記塩化ビニル樹脂(A)100質量部に対し、前記安定剤(B)を0.1~10.0質量部、前記加工助剤(C)を0.1~10.0質量部含む、[1]~[12]のいずれか1つに記載の塩化ビニル樹脂組成物。
[14] 前記塩化ビニル樹脂(A)100質量部に対し、前記安定剤(B)を0.1~10.0質量部、前記加工助剤(C)を0.1~10.0質量部、前記衝撃強度改質剤(D)を0.5~30.0質量部含む、[11]又は[12]に記載の塩化ビニル樹脂組成物。
[15] 前記塩化ビニル樹脂(A)100質量部に対し、前記衝撃強度改質剤(D)を4.0~10.0質量部含む、[14]に記載の塩化ビニル樹脂組成物。
[16] [1]~[15]のいずれか1つに記載の塩化ビニル樹脂組成物を成形して得られる、塩化ビニル樹脂成形体。
なお、前記加工助剤(C)において、メタクリル酸メチル単量体(c1)単位、炭素数が3~5のアルキル基を有するメタクリル酸アルキルエステル単量体(c2)単位、及びその他の単量体(c3)単位の合計が100質量%を超えないものとする。
本発明の塩化ビニル樹脂成形体は、機械特性に優れる。
なお、以下の説明において、「成形体」とは、本発明の塩化ビニル樹脂組成物を成形して得られる塩化ビニル樹脂成形体のことである。
また、「(メタ)アクリル酸」は、アクリル酸及びメタクリル酸の総称である。
本発明の塩化ビニル樹脂組成物は、塩化ビニル樹脂(A)と、安定剤(B)と、加工助剤(C)とを含む。また、塩化ビニル樹脂組成物は、衝撃強度改質剤(D)をさらに含むことが好ましい。
塩化ビニル樹脂(A)としては、塩化ビニル単量体(a1)の単独重合体、又は塩化ビニル単量体(a1)を主成分とする、塩化ビニル単量体(a1)及び塩化ビニルと共重合可能な単量体(a2)の共重合体が挙げられる。
塩化ビニル樹脂(A)が共重合体である場合、塩化ビニル単量体(a1)単位の含有率は、該共重合体を構成する全ての構成単位の合計を100質量%としたときに、10~99質量%が好ましく、50~99質量%がより好ましい。
塩化ビニル樹脂(A)は単独で用いてもよいし、2種以上を併用してもよい。
塩化ビニル樹脂(A)の平均重合度の値は、メーカーのカタログ値もしくは、公知のMark-Houwink-桜田の式等を用いて得られる値である。
安定剤(B)は、塩化ビニル樹脂組成物の成形加工時に熱安定性を付与するものである。
安定剤(B)は、カルシウム及び亜鉛の少なくとも一方を含む化合物である。塩化ビニル樹脂組成物により高い熱安定性を付与できる点で、安定剤(B)としてはカルシウム及び亜鉛の両方を含む化合物であることが好ましい。
また、塩化ビニル樹脂組成物により高い熱安定性を付与できる点で、安定剤(B)としてはカルシウム及び亜鉛の少なくとも一方を含む金属石鹸が好ましく、Ca系金属石鹸及びZn系金属石鹸の両方を含むCa-Zn系安定剤がより好適である。
安定剤(B)を構成する化合物としては、長鎖脂肪酸のカルシウム塩(Ca系安定剤)、長鎖脂肪酸の亜鉛塩(Zn系安定剤)、Ca系安定剤及びZn系安定剤の混合物(Ca-Zn系安定剤)が挙げられる。
安定剤(B)の含有量は、塩化ビニル樹脂(A)100質量部に対して、0.1~10.0質量部が好ましく、0.5~10.0質量部がより好ましく、0.5~8.0質量部がさらに好ましく、1.0~6.0質量部が特に好ましい。安定剤(B)の含有量が0.1質量部以上であれば、塩化ビニル樹脂(A)の熱安定性の向上効果がより得られやすくなる。一方、安定剤(B)の含有量が10.0質量部以下であれば、成形体の着色を抑制できる。また、塩化ビニル樹脂(A)が充分に溶融・混練されるため、成形体の機械特性がより向上する。
加工助剤(C)は、塩化ビニル樹脂組成物のゲル化時間を短縮させるとともに、成形加工時に溶融弾性を付与し、加工性及び成形品の外観を向上させるものである。
加工助剤(C)は、メタクリル酸メチル単量体(c1)、炭素数が3~5のアルキル基を有するメタクリル酸アルキルエステル単量体(c2)、及び必要に応じてその他の単量体(c3)の共重合体である。すなわち加工助剤(C)は、メタクリル酸メチル単量体(c1)単位を19~95質量%、及び炭素数が3~5のアルキル基を有するメタクリル酸アルキルエステル単量体(c2)単位を5~81質量%含む共重合体であり、好ましくは、メタクリル酸メチル単量体(c1)単位を19~94質量%、炭素数が3~5のアルキル基を有するメタクリル酸アルキルエステル単量体(c2)単位を5~80質量%、及びその他の単量体(c3)単位を1~20質量%を含む共重合体である。
メタクリル酸メチル単量体(c1)単位の含有率は、共重合体(加工助剤(C))を構成する全ての構成単位の合計を100質量%としたときに、19~95質量%であり、19~94質量%が好ましく、40~94質量%がより好ましく、50~82質量%がさらに好ましい。メタクリル酸メチル単量体(c1)単位の含有率が19質量%以上であれば、塩化ビニル樹脂(A)との相溶性が良好となる傾向にあり、塩化ビニル樹脂(A)を充分に混練できるため、加工性が向上する。一方、メタクリル酸メチル単量体(c1)単位の含有率が95質量%以下であれば、加工助剤(C)の分子が塩化ビニル樹脂(A)中に分散しやすくなり、成形体の機械特性が向上する。
これらメタクリル酸アルキルエステルは、目的に応じて単独で用いてもよいし、2種以上を併用してもよい。
これら単量体は、目的に応じて単独で用いてもよいし、2種以上を併用してもよい。
加工助剤(C)を製造する方法としては、種々の方法を用いることができ、例えば乳化重合、懸濁重合、溶液重合等の各種重合方法が挙げられる。さらに、モノマーの一括添加、滴下、モノマーの分割添加等いずれの方法も用いてもよく、またランダム共重合、ブロック共重合等の方法を用いてもよいが、加工助剤(C)としては、モノマーの一括添加による方法で得られるランダム共重合体が好ましい。
pH調節剤としては、ホウ酸-塩化カリウム-水酸化カリウム、リン酸二水素カリウム-リン酸水素二ナトリウム、ホウ酸-塩化カリウム-炭酸カリウム、クエン酸-クエン酸水素カリウム、リン酸二水素カリウム-ホウ砂、リン酸水素二ナトリウム-クエン酸などが挙げられる。
また、噴霧乾燥、凍結乾燥等の種々の方法によっても、加工助剤(C)を粉体状で回収することできる。中でも、良好な外観の成形体が得られやすい点で、噴霧乾燥が好ましい。
噴霧乾燥の条件に特に制限はなく、任意の条件で噴霧乾燥することができるが、好ましいのは噴霧乾燥により形成された粉体のうち、その粒子内部が融着して均質な状態になった粉体の含有量が50質量%未満、より好ましくは25質量%未満となる条件である。
なお、本発明における「還元粘度ηsp」とは、重合体または共重合体0.1gを100mLのクロロホルムに溶解し、25℃で測定した値のことである。
還元粘度ηspを調節する方法としては、重合時の連鎖移動剤、重合開始剤の使用量の調節、及び重合温度の調節等の常用の方法を用いることができる。
加工助剤(C)の含有量は、塩化ビニル樹脂(A)100質量部に対して、0.1~10.0質量部が好ましく、0.3~7.0質量部がより好ましく、0.5~6.0質量部がさらに好ましい。加工助剤(C)の含有量が0.1質量部以上であれば、塩化ビニル樹脂組成物の加工性がより向上する。一方、加工助剤(C)の含有量が10.0質量部以下であれば、成形体の機械特性を良好に維持できる。
衝撃強度改質剤(D)としては、例えば、ゴム系グラフト共重合体、NBR(アクリロニトリル-ブタジエンゴム)、EVA(エチレン-酢酸ビニル共重合体)、塩素化ポリエチレン、熱可塑性エラストマーなどが挙げられる。
ゴム系グラフト共重合体としては、例えばアクリルゴム系グラフト共重合体、シリコーンゴム系グラフト共重合体、シリコーンゴムとアクリルゴムとの複合ゴム系グラフト共重合体、MBS(メタクリル酸メチル-ブタジエン-スチレン共重合体)、ABS(アクリロニトリル-ブタジエン-スチレン共重合体)、AES(アクリロニトリル-エチレンプロピレンゴム-スチレン共重合体)などが挙げられる。
アクリルゴムは、(メタ)アクリル酸エステルと、及び必要に応じて、(メタ)アクリル酸エステルと共重合し得る他のビニル単量体とを重合することにより得られる。
(メタ)アクリル酸エステルとしては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸-n-ブチル、(メタ)アクリル酸-イソブチル、(メタ)アクリル酸-2-エチルヘキシル、(メタ)アクリル酸-4-ヒドロキシブチルなどが挙げられる。
他のビニル単量体としては、例えば、スチレン、α-メチルスチレン、ビニルトルエン等の芳香族ビニル単量体;(メタ)アクリロニトリル等のシアン化ビニル単量体;フッ素含有ビニル単量体などが挙げられる。
このようなグラフト単量体としては、例えば、スチレン、α-メチルスチレン等の芳香族ビニル単量体;アクリル酸エチル、アクリル酸-n-ブチル等のアクリル酸エステル;メタクリル酸メチル、メタクリル酸エチル等のメタクリル酸エステル;(メタ)アクリロニトリル等のシアン化ビニル単量体;(メタ)アクリルアリル、ジアリルフタレート、ジアリルセバケート、トリアリルトリアジン等の架橋性単量体などが挙げられる。
シリコーンゴムとしては、ポリオルガノシロキサンが挙げられる。ポリオルガノシロキサンは、例えば、ジメチルシロキサンと、ビニル重合性官能基含有シロキサンと、必要に応じてシロキサン系架橋剤とを重合することで得られる。
ジメチルシロキサンとしては、3員環以上のジメチルシロキサン系環状体が挙げられ、3~7員環のものが好ましい。具体的にはヘキサメチルシクロトリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサシロキサンなどが挙げられる。
ビニル重合性官能基含有シロキサンとしては、例えば、β-メタクリロイルオキシエチルジメトキシメチルシラン、γ-メタクリロイルオキシプロピルジメトキシメチルシラン等のメタクリロイルオキシシラン;テトラメチルテトラビニルシクロテトラシロキサン等のビニルシロキサン;p-ビニルフェニルジメトキシメチルシラン等のビニルフェニルシラン;γ-メルカプトプロピルジメトキシメチルシラン、γ-メルカプトプロピルトリメトキシシラン等のメルカプトシロキサンなどが挙げられる。
シロキサン系架橋剤としては、3官能性又は4官能性のシラン系架橋剤が好ましく、例えば、トリメトキシメチルシラン、トリエトキシフェニルシラン、テトラメトキシシラン、テトラエトキシシラン、テトラブトキシシランなどが挙げられる。
このようなグラフト単量体としては、先のアクリルゴム系グラフト共重合体の説明において例示したグラフト単量体を用いることができる。
複合ゴムは、例えば、ポリオルガノシロキサンのラテックス中に(メタ)アクリル酸エステル成分を添加し、通常の重合開始剤を作用させて重合することによって調製することができる。
ポリオルガノシロキサンとしては、先のシリコーンゴムの説明において例示したポリオルガノシロキサンを用いることができる。
(メタ)アクリル酸エステル成分としては、先のアクリルゴムの説明において例示した(メタ)アクリル酸エステルを用いることができる。
このようなグラフト単量体としては、先のアクリルゴム系グラフト共重合体の説明において例示したグラフト単量体を用いることができる。
衝撃強度改質剤(D)は、塩化ビニル樹脂(A)100質量部に対し、0.5~30.0質量部が好ましく、1.0~20.0質量部がより好ましく、4.0~10.0質量部がさらに好ましい。衝撃強度改質剤(D)の含有量が0.5質量部以上であれば、成形体の機械特性が向上する。一方、衝撃強度改質剤(D)の含有量が30.0質量部以下であれば、塩化ビニル樹脂組成物の溶融時の流動性及び成形体の弾性率の低下を抑制できる。
塩化ビニル樹脂組成物は、塩化ビニル樹脂(A)、安定剤(B)、加工助剤(C)、及び衝撃強度改質剤(D)以外の、その他の添加剤を含むことができる。
その他の添加剤としては、例えば、充填剤、熱安定剤(ただし、安定剤(B)を除く。)、可塑剤、滑剤、難燃剤、耐熱性向上剤、離型剤、流動性改良剤、着色剤、帯電防止剤、導電性付与剤、防曇剤、抗菌剤などが挙げられる。
また、塩化ビニル樹脂組成物を非発泡分野において用いる場合には、塩化ビニル樹脂組成物は発泡剤を含まないことが好ましい。
充填剤は、単独で用いてもよいし、2種以上を併用してもよい。
熱安定剤は、塩化ビニル樹脂(A)100質量部に対して、0.1~10.0質量部が好ましく、0.2~5.0質量部がより好ましい。
ハイドロタルサイト系熱安定剤はハイドロタルサイト化合物であり、具体的には、マグネシウム及び/又はアルカリ金属とアルミニウムとからなる複合塩化合物、あるいは亜鉛とマグネシウムとアルミニウムとからなる複合塩化合物であり、結晶水を脱水したものがある。また、ハイドロタルサイト化合物は、天然物であっても合成品であってもよく、合成品の合成方法は、従来公知の方法でよい。
熱安定剤は、単独で用いてもよいし、2種以上を併用してもよい。
可塑剤は、単独で用いてもよいし、2種以上を併用してもよい。
滑剤は、単独で用いてもよいし、2種以上を併用してもよい。
難燃剤は、単独で用いてもよいし、2種以上を併用してもよい。
耐熱性向上剤は、単独で用いてもよいし、2種以上を併用してもよい。
塩化ビニル樹脂組成物は、上述した塩化ビニル樹脂(A)と安定剤(B)と加工助剤(C)と、必要に応じて衝撃強度改質剤(D)やその他の添加剤とを混合し、さらに混合物を溶融・混練して得られる。
混合方法としては、例えば、スーパーミキサー、ヘンシェルミキサーなどを用いる方法が挙げられる。
溶融・混練方法としては、例えば、押出し機、バンバリーミキサー、ローラー、ニーダーなどを用いる方法が挙げられる。
以上説明した本発明の塩化ビニル樹脂組成物は、上述した特定の加工助剤(C)を含むので、カルシウム及び亜鉛の少なくとも一方を含む化合物である安定剤を用いても機械特性に優れる成形体が得られ、しかも加工性が良好である。
また、本発明の塩化ビニル樹脂組成物は、安定剤として、上述したカルシウム及び亜鉛の少なくとも一方を含む化合物である安定剤(B)を含むので、作業環境や取り扱い性に優れる。
本発明の塩化ビニル樹脂成形体は、本発明の塩化ビニル樹脂組成物を成形して得られる。
成形方法としては、例えば、異型押出し成形、射出成形、真空成形、ブロー成形、ロール成形、プレス成形などが挙げられる。これらの中では、異型押出し成形が好ましい。
塩化ビニル樹脂成形体は、窓枠等の建材、パイプ、雨樋、異型成形品、自動車材料、玩具、文房具等の雑貨、OA機器、家電機器等の広い分野に用いることができる。
なお、各実施例、比較例中「部」とあるのは「質量部」を示す。各種測定・評価方法を以下に示す。
<還元粘度の測定>
加工助剤0.1gを100mLのクロロホルムに溶解し、25℃でウベローデ型粘度計を用いて、還元粘度(ηsp)を測定した。
170℃に設定したブラベンダープラスチコーダーに、塩化ビニル樹脂組成物を100mLになるように充填させ、2分間保持した後、測定温度170℃、回転数30rpmの条件にてゲル化を観察した。ゲル化の観察開始後、トルクが30N・mを超えるまでに要した時間をゲル化時間として読み取った。ゲル化時間が短いほど、加工性が良好であることを意味する。
塩化ビニル樹脂組成物を25mm単軸押出機(サーモ・プラスティックス工業株式会社製)に投入し、シリンダー温度をC1-C2-C3-D=160℃-180℃-190℃-190℃に設定し、スクリュー回転数50rpmの条件にてペレタイズを行い、ペレット状の塩化ビニル樹脂組成物を得た。
得られたペレット状の塩化ビニル樹脂組成物を30mm単軸押出機(株式会社ジー・エム・エンジニアリング製)に投入し、シリンダー温度をC1-C2-C3-C4-C5-A-D=60℃-160℃-170℃-180℃-190℃-190℃-190℃に設定し、スクリュー回転数30rpmの条件にて、幅10mm、厚さ5mmのダイを用いて角棒を成形した。
得られた角棒を長さ80mmに切断し、JIS K 7111-1:2012(ISO 179-1)に基づきシャルピー衝撃強さを測定した。
<加工助剤(C-1)の製造>
攪拌機及び環流冷却器付きの反応容器にイオン交換水180部を仕込み、そこに無水炭酸ナトリウム0.1部、メタクリル酸メチル68部、アクリル酸-n-ブチル3部、メタクリル酸-n-ブチル29部、及びn-オクチルメルカプタン0.004部を加えて、反応容器内を窒素で置換した。その後、乳化剤としてラウリル硫酸ナトリウム(花王株式会社製、「エマール2F」)1.1部を加え、攪拌下で反応容器を45℃まで昇温し、重合開始剤として過硫酸カリウム0.15部を仕込み重合反応を開始させ、2時間加熱攪拌して重合を終了し、エマルジョンを得た。
得られたエマルジョンを冷却後、入口温度160℃及び出口温度70℃条件で噴霧乾燥を行い、粉末状の加工助剤(C-1)を得た。
得られた加工助剤(C-1)の還元粘度を測定した。結果を表1に示す。
各単量体の仕込み量を表1に示すように変更した以外は、加工助剤(C-1)と同様にして、粉末状の加工助剤(C-2)~(C-6)を得た。
得られた加工助剤(C-2)~(C-6)の還元粘度を測定した。結果を表1に示す。
・「MMA」:メタクリル酸メチル
・「nBMA」:メタクリル酸-n-ブチル
・「iBMA」:メタクリル酸イソブチル
・「nBA」:アクリル酸-n-ブチル
・「nOM」:n-オクチルメルカプタン
平均重合度1000の塩化ビニル樹脂(信越化学工業株式会社製、「TK-1000」)100部、Ca-Zn系安定剤としてステアリン酸カルシウム塩とステアリン酸亜鉛塩の混合物(株式会社サンエース製)2部、加工助剤(C-1)1部、衝撃強度改質剤(D)としてアクリルゴム系グラフト共重合体(三菱レイヨン株式会社製、「メタブレンW-450A」)7部、滑剤としてエステル系滑剤(エメリーオレオケミカルズジャパン株式会社製、「LOXIOL VPN933」)0.4部及びポリエチレンワックス(エメリーオレオケミカルズジャパン株式会社製、「LOXIOL VPN233」)0.4部を混合し、ヘンシェルミキサーで110℃までドライアップを行い、塩化ビニル樹脂組成物を得た。
得られた塩化ビニル樹脂組成物について加工性を評価した。また、塩化ビニル樹脂組成物を用いて成形体(角棒)を作製し、機械特性を評価した。これらの結果を表2に示す。
加工助剤(C)の種類及び添加量、衝撃強度改質剤(D)の添加量を表2に示すように変更した以外は、実施例1と同様にして塩化ビニル樹脂組成物を調製し、加工性及び機械特性の評価を行った。結果を表2に示す。
よって、本発明の塩化ビニル樹脂組成物であれば、カルシウム及び亜鉛の少なくとも一方を含む化合物である安定剤を用いても、機械特性に優れる成形体が得られ、しかも加工性が良好であることが示された。
Claims (16)
- 塩化ビニル樹脂(A)と、カルシウム及び亜鉛の少なくとも一方を含む化合物である安定剤(B)と、加工助剤(C)とを含む塩化ビニル樹脂組成物であって、
前記加工助剤(C)が、メタクリル酸メチル単量体(c1)単位を19~95質量%、及び炭素数が3~5のアルキル基を有するメタクリル酸アルキルエステル単量体(c2)単位を5~81質量%含む共重合体である、塩化ビニル樹脂組成物。 - 前記加工助剤(C)が、メタクリル酸メチル単量体(c1)単位を19~94質量%、炭素数が3~5のアルキル基を有するメタクリル酸アルキルエステル単量体(c2)単位を5~80質量%、及びその他の単量体(c3)単位を1~20質量%含む共重合体である、請求項1に記載の塩化ビニル樹脂組成物。
- 前記加工助剤(C)が、炭素数が3~5のアルキル基を有するメタクリル酸アルキルエステル単量体(c2)単位として、メタクリル酸-n-ブチル単量体単位を含む共重合体である、請求項1に記載の塩化ビニル樹脂組成物。
- 前記加工助剤(C)が、炭素数が3~5のアルキル基を有するメタクリル酸アルキルエステル単量体(c2)単位を5~60質量%含む共重合体である、請求項1に記載の塩化ビニル樹脂組成物。
- 前記加工助剤(C)が、炭素数が3~5のアルキル基を有するメタクリル酸アルキルエステル単量体(c2)単位を18~50質量%含む共重合体である、請求項4に記載の塩化ビニル樹脂組成物。
- 前記加工助剤(C)が、その他の単量体(c3)単位として、アクリル酸エステル単量体単位を1~20質量%含む共重合体である、請求項2に記載の塩化ビニル樹脂組成物。
- 前記加工助剤(C)が、その他の単量体(c3)単位を1~10質量%含む共重合体である、請求項2に記載の塩化ビニル樹脂組成物。
- 前記加工助剤(C)が、その他の単量体(c3)単位を1~5質量%含む共重合体である、請求項7に記載の塩化ビニル樹脂組成物。
- 前記安定剤(B)が、カルシウム及び亜鉛の両方を含む化合物である、請求項1に記載の塩化ビニル樹脂組成物。
- 発泡剤を含まない、請求項1に記載の塩化ビニル樹脂組成物。
- さらに衝撃強度改質剤(D)を含む、請求項1に記載の塩化ビニル樹脂組成物。
- 前記衝撃強度改質剤(D)が、アクリルゴム及びシリコーンゴムの少なくとも一方を含む、請求項11に記載の塩化ビニル樹脂組成物。
- 前記塩化ビニル樹脂(A)100質量部に対し、前記安定剤(B)を0.1~10.0質量部、前記加工助剤(C)を0.1~10.0質量部含む、請求項1に記載の塩化ビニル樹脂組成物。
- 前記塩化ビニル樹脂(A)100質量部に対し、前記安定剤(B)を0.1~10.0質量部、前記加工助剤(C)を0.1~10.0質量部、前記衝撃強度改質剤(D)を0.5~30.0質量部含む、請求項11に記載の塩化ビニル樹脂組成物。
- 前記塩化ビニル樹脂(A)100質量部に対し、前記衝撃強度改質剤(D)を4.0~10.0質量部含む、請求項14に記載の塩化ビニル樹脂組成物。
- 請求項1に記載の塩化ビニル樹脂組成物を成形して得られる、塩化ビニル樹脂成形体。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018526502A (ja) * | 2015-08-31 | 2018-09-13 | ローム アンド ハース カンパニーRohm And Haas Company | 発泡成形用の加工助剤、これを含む塩化ビニル樹脂系発泡成形組成物、及び発泡成形製品 |
US10696836B2 (en) | 2016-01-26 | 2020-06-30 | Rohm And Haas Company | Thermoplastic compositions containing acrylic copolymers as melt strength and clarity process aids |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11685827B2 (en) | 2017-10-16 | 2023-06-27 | Kaneka Corporation | Vinyl chloride resin composition for powder molding, vinyl chloride resin molded body and laminate |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001200120A (ja) * | 2000-01-14 | 2001-07-24 | Kanegafuchi Chem Ind Co Ltd | 塩化ビニル系樹脂組成物 |
JP2003171526A (ja) * | 2001-09-25 | 2003-06-20 | Sekisui Chem Co Ltd | ポリ塩化ビニル系樹脂組成物 |
JP2005255717A (ja) * | 2004-03-09 | 2005-09-22 | Mitsubishi Rayon Co Ltd | 発泡成形用加工助剤、塩化ビニル系発泡成形用樹脂組成物、および発泡成形体 |
JP2007277529A (ja) * | 2006-03-15 | 2007-10-25 | Kaneka Corp | (メタ)アクリル系共重合体粉体、及びこれを含有する塩化ビニル系樹脂組成物 |
JP2010058438A (ja) * | 2008-09-05 | 2010-03-18 | Mitsubishi Plastics Inc | 樹脂積層体 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS604543A (ja) | 1983-06-22 | 1985-01-11 | Nippon Carbide Ind Co Ltd | 半硬質塩化ビニル樹脂成形用組成物 |
JPS63139927A (ja) | 1986-12-02 | 1988-06-11 | Kanegafuchi Chem Ind Co Ltd | 軟質押出発泡用塩化ビニル系樹脂組成物 |
JPH02218732A (ja) | 1989-02-20 | 1990-08-31 | Kanegafuchi Chem Ind Co Ltd | 難燃性塩化ビニル系樹脂組成物及び該組成物を保護層材とする難燃性電線・ケーブル |
US5658980A (en) | 1994-11-08 | 1997-08-19 | Mitsubishi Chemical Mkv Company | Vinyl chloride resin composition |
JP3106922B2 (ja) | 1994-11-08 | 2000-11-06 | 三菱化学エムケーブイ株式会社 | 塩化ビニル樹脂組成物 |
JPH1160868A (ja) | 1997-08-19 | 1999-03-05 | Chisso Corp | 発泡押出し成形用塩化ビニル系樹脂組成物 |
JP3631361B2 (ja) * | 1997-12-04 | 2005-03-23 | 株式会社カネカ | 塩化ビニル系樹脂組成物 |
EP1197524A4 (en) | 1999-05-19 | 2003-08-06 | Mitsubishi Rayon Co | PROCESS TOOLS, VINYL CHLORIDE RESIN COMPOSITION THAT CONTAINS THIS AND METHOD FOR PRODUCING A MOLDED OBJECT THAT CONTAINS THIS |
JP2001234014A (ja) | 2000-02-22 | 2001-08-28 | Sumitomo Bakelite Co Ltd | 塩化ビニル系樹脂組成物及びそれを用いたケーブル |
JP2002179868A (ja) | 2000-12-13 | 2002-06-26 | Shin Etsu Polymer Co Ltd | 遠赤外線素子入り塩化ビニル系樹脂組成物及びこれを被覆した電線 |
CN101528793A (zh) * | 2006-11-22 | 2009-09-09 | 赢创罗姆有限责任公司 | 改进的用于增塑溶胶的粘结剂的制备方法 |
DE102006057145A1 (de) * | 2006-11-22 | 2008-05-29 | Evonik Röhm Gmbh | Verfahren zur Herstellung verbesserter Bindemittel für Plastisole |
JP5067558B2 (ja) | 2007-02-02 | 2012-11-07 | 日産化学工業株式会社 | 硬質押出用塩化ビニル樹脂組成物及びその安定剤 |
DE102008033834A1 (de) | 2008-07-19 | 2010-01-21 | Lanxess Deutschland Gmbh | Weichmacherzubereitungen |
RU2011146076A (ru) * | 2009-04-13 | 2013-05-20 | Мицубиси Рэйон Ко., Лтд. | Технологическая добавка для формования без вспенивания, композиция смолы и формованное изделие |
JP5928795B2 (ja) | 2012-04-23 | 2016-06-01 | 三菱レイヨン株式会社 | 発泡成形用塩化ビニル系樹脂組成物及びその成形体 |
JP6327471B2 (ja) * | 2013-09-25 | 2018-05-23 | 三菱ケミカル株式会社 | 電線被覆材及び被覆された電線 |
CN105722913B (zh) | 2013-09-25 | 2018-03-16 | 三菱化学株式会社 | 软质氯乙烯系树脂组合物、成形体、电线包覆材及经包覆的电线 |
-
2015
- 2015-01-15 KR KR1020167021054A patent/KR101909359B1/ko active IP Right Grant
- 2015-01-15 US US15/111,210 patent/US9902848B2/en active Active
- 2015-01-15 WO PCT/JP2015/050928 patent/WO2015108101A1/ja active Application Filing
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001200120A (ja) * | 2000-01-14 | 2001-07-24 | Kanegafuchi Chem Ind Co Ltd | 塩化ビニル系樹脂組成物 |
JP2003171526A (ja) * | 2001-09-25 | 2003-06-20 | Sekisui Chem Co Ltd | ポリ塩化ビニル系樹脂組成物 |
JP2005255717A (ja) * | 2004-03-09 | 2005-09-22 | Mitsubishi Rayon Co Ltd | 発泡成形用加工助剤、塩化ビニル系発泡成形用樹脂組成物、および発泡成形体 |
JP2007277529A (ja) * | 2006-03-15 | 2007-10-25 | Kaneka Corp | (メタ)アクリル系共重合体粉体、及びこれを含有する塩化ビニル系樹脂組成物 |
JP2010058438A (ja) * | 2008-09-05 | 2010-03-18 | Mitsubishi Plastics Inc | 樹脂積層体 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018526502A (ja) * | 2015-08-31 | 2018-09-13 | ローム アンド ハース カンパニーRohm And Haas Company | 発泡成形用の加工助剤、これを含む塩化ビニル樹脂系発泡成形組成物、及び発泡成形製品 |
US10696836B2 (en) | 2016-01-26 | 2020-06-30 | Rohm And Haas Company | Thermoplastic compositions containing acrylic copolymers as melt strength and clarity process aids |
Also Published As
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KR20160105851A (ko) | 2016-09-07 |
KR101909359B1 (ko) | 2018-10-17 |
US9902848B2 (en) | 2018-02-27 |
US20160333177A1 (en) | 2016-11-17 |
JP6536399B2 (ja) | 2019-07-03 |
CN106062070A (zh) | 2016-10-26 |
TW201531511A (zh) | 2015-08-16 |
TWI652295B (zh) | 2019-03-01 |
JPWO2015108101A1 (ja) | 2017-03-23 |
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