WO2015045930A1 - 軟質塩化ビニル系樹脂組成物、成形体、電線被覆材及び被覆された電線 - Google Patents
軟質塩化ビニル系樹脂組成物、成形体、電線被覆材及び被覆された電線 Download PDFInfo
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- WO2015045930A1 WO2015045930A1 PCT/JP2014/074319 JP2014074319W WO2015045930A1 WO 2015045930 A1 WO2015045930 A1 WO 2015045930A1 JP 2014074319 W JP2014074319 W JP 2014074319W WO 2015045930 A1 WO2015045930 A1 WO 2015045930A1
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- vinyl chloride
- chloride resin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/04—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C09D127/06—Homopolymers or copolymers of vinyl chloride
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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- 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
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/447—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from acrylic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
Definitions
- the present invention relates to a soft vinyl chloride resin composition, and in particular, a soft vinyl chloride resin that can provide a molded article having excellent surface smoothness and excellent flexibility even under high production rate conditions.
- the present invention relates to a resin composition, a molded body thereof, an electric wire covering material, and a covered electric wire.
- Vinyl chloride resin is widely used as a general-purpose resin material with high utility value because it has excellent chemical and physical properties such as chemical resistance, weather resistance, flame resistance, and electrical insulation, and is inexpensive. It is used. Soft vinyl chloride compositions are widely used because they have excellent properties and can be easily given flexibility by adding plasticizers. Sheets such as coated wires and flooring, tapes and agriculture There are a wide variety of suitable uses, such as films. On the other hand, since vinyl chloride resins are inexpensive, demands on product costs are severe, and production at higher production speeds has been attempted in order to improve productivity.
- the soft molding with the addition of a plasticizer has a faster production speed than the hard molding without the addition of a plasticizer, and a new method that can improve the kneading state in response to the demand for higher production speed. The proposal is awaited.
- Patent Documents 1 to 3 disclose that workability and dispersibility can be improved by blending a vinyl chloride resin-coated electric wire with an acrylic resin mainly composed of methyl methacrylate as a processing aid.
- Patent Document 4 discloses that a molded article suitable for metal coating having excellent shape followability can be obtained by blending an acrylic resin as a modifier with a soft vinyl chloride resin.
- the conventional technology is insufficient because, for example, a molded product that is satisfactory in terms of surface smoothness under high production rate conditions cannot be obtained, and flexibility is impaired by adding a high glass transition temperature component. From the above situation, there is a demand for a soft vinyl chloride resin composition capable of obtaining a molded article having excellent surface smoothness and excellent flexibility even under high production rate conditions.
- An object of the present invention is to provide a soft vinyl chloride resin composition capable of obtaining a molded article having excellent surface smoothness and excellent flexibility even under high production rate conditions, a molded article thereof, a wire coating material, and It is to provide a covered electric wire.
- a vinyl chloride resin composition in which a specific amount of a powdery processing aid and a plasticizer made of a specific alkyl methacrylate copolymer are added to a vinyl chloride resin. It was found to be done. That is, the present invention relates to the following [1] to [10].
- (C) Plasticizer [2] The soft vinyl chloride system according to [1], containing 0.5 to 20 parts by mass of a processing aid for soft vinyl chloride resin (B) with respect to 100 parts by mass of the vinyl chloride resin (A).
- the plasticizer (C) is a phthalic acid compound, trimellitic acid compound, phosphoric acid compound, adipic acid compound, citric acid compound, ether compound, polyester compound, and soybean oil compound.
- Vinyl chloride polymer in which vinyl chloride resin (A) has an average chlorine content of 56 to 75% by mass, vinyl chloride copolymer obtained by copolymerizing vinyl chloride polymer and elastic body and / or elastomer The soft vinyl chloride resin composition according to any one of [1] to [5], which is at least one selected from the group consisting of: [7] A molded article formed from the soft vinyl chloride resin composition according to any one of [1] to [6]. [8] The molded article according to [7], wherein the surface hardness is 75 or less (durometer D hardness). [9] The molded body according to [7] or [8], wherein the molded body is a wire covering material. [10] An electric wire covered with the electric wire covering material according to [9].
- a soft vinyl chloride resin molding capable of producing a molded article such as a wire covering material having stable and excellent surface smoothness even under high production rate conditions.
- the body can be provided.
- the present invention is described in detail below.
- ⁇ Vinyl chloride resin (A)> The type of the vinyl chloride resin of the vinyl chloride resin (A) used in the present invention is not particularly limited. For example, a homopolymer of vinyl chloride, a post-chlorinated vinyl chloride polymer, a partially crosslinked vinyl chloride polymer Or the copolymer with vinyl chloride which contains the other vinyl compound copolymerizable with vinyl chloride in 30 mass% or less, a mixture thereof, etc. are mentioned.
- vinyl compounds that can be copolymerized with the vinyl chloride are not particularly limited, but specific examples include fatty acid vinyl esters such as vinyl acetate and vinyl propionate; alkyl methacrylates such as methyl methacrylate and ethyl methacrylate; acrylic Alkyl esters such as ethyl acrylate and butyl acrylate; ⁇ -olefins such as ethylene, propylene and styrene; alkyl vinyl ethers such as vinyl methyl ether and vinyl butyl ether; unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride Or the acid anhydride etc. are mentioned, You may use these combining 1 type (s) or 2 or more types. If the copolymerization amount of the other vinyl compound that can be copolymerized is 30% by mass or less, the original characteristics of the vinyl chloride resin are not impaired.
- the vinyl chloride resin is selected from a vinyl chloride polymer having an average chlorine content of 56 to 75% by mass and a vinyl chloride copolymer obtained by copolymerizing a vinyl chloride polymer and an elastic body and / or an elastomer. At least one resin is preferred. Furthermore, these vinyl chloride resins may be used alone or in combination of two or more.
- the average degree of polymerization of the vinyl chloride resin (A) used in the present invention is preferably in the range of 300 to 5,000, more preferably 500 to 3,000. By setting the average degree of polymerization to 300 or more, the mechanical properties of the molded article are improved. Moreover, workability becomes favorable because an average degree of polymerization shall be 5,000 or less.
- the production method of the vinyl chloride resin (A) used in the present invention is not particularly limited, and those produced by various polymerization methods such as an emulsion polymerization method, a suspension polymerization method, and a bulk polymerization method can be used.
- the processing aid (B) of the present invention comprises a methacrylic acid alkyl ester (b-1) (hereinafter referred to as monomer (b-1)) in which the alkyl group in the alkyl ester portion is a branched alkyl group having 3 to 5 carbon atoms.
- the alkyl group of the alkyl ester portion is a branched alkyl group having 3 to 5 carbon atoms. If the number of carbon atoms of the branched alkyl group is 3 or more, the bulkiness of the molecular chain will be sufficient, the dispersibility of the processing aid (B) will be improved, the appearance of the molded product will be improved, and the bulkiness will be sufficient As a result, the effect of extending the distance between the vinyl chloride resin molecular chains becomes sufficient, and the molded product can be given flexibility.
- the fall of the glass transition temperature of a processing aid (B) can be suppressed by making carbon number of a branched alkyl group 5 or less, and powder recoverability can be improved.
- the branched alkyl group preferably has 4 carbon atoms. By setting the number of carbon atoms to 4, the balance between the dispersibility and flexibility improvement effect of the processing aid (B) and the powder recoverability becomes better.
- the alkyl group in the alkyl ester portion of the monomer (b-1) has a branch, the bulkiness of the molecular chain is efficiently imparted, and the interaction between the molecular chains is weakened, thereby reducing the processing aid ( The dispersibility of B) is improved.
- the bulk of the molecular chain is imparted to the processing aid (B) by having a branch, and the processing aid (B) is generated by the plasticizer when added to the soft vinyl chloride resin.
- the monomer (b-1) for example, methacrylic acid-i-propyl, methacrylic acid-i-butyl, methacrylic acid-i-pentyl, methacrylic acid-t-butyl, methacrylic acid-t-pentyl, methacrylic acid- Examples include s-butyl and methacrylic acid-neo-pentyl. Among them, since the appearance improving ability and powder recoverability of the molded article are good, methacrylate-i-butyl, methacrylate-t-butyl, methacrylate-s-butyl having 4 carbon atoms in the branched alkyl group. Is preferred, and i-butyl methacrylate is more preferred because of its superior thermal stability. These alkyl methacrylates can be used alone or in combination of two or more depending on the purpose.
- methyl methacrylate is used as the monomer (b-2). By using methyl methacrylate, high gloss can be imparted to the molded body.
- the monomer (b-3) is not particularly limited as long as it is a monomer that can be copolymerized with the monomer (b-1), and examples thereof include ethyl acrylate, butyl acrylate, and -2-ethylhexyl acrylate.
- Acrylic acid esters such as benzyl acrylate and phenyl acrylate; alkyl methacrylates other than (b-1) such as ethyl methacrylate, hexyl methacrylate, octyl methacrylate, and 2-ethylhexyl methacrylate; benzyl methacrylate; Methacrylic acid aromatic esters such as phenyl methacrylate; 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. Of the acid anhydride. These can be used alone or in combination of two or more.
- the amount of the monomer (b-1) used is 10 to 100% by mass, preferably 30 to 100% by mass, based on 100% by mass of all monomers that are the raw materials for the polymer ( ⁇ ). %, More preferably 40 to 100% by mass, still more preferably 50 to 100% by mass, still more preferably 60 to 100% by mass, particularly preferably 65 to 100% by mass, and most preferably 80 to 100% by mass.
- the monomer (b-1) in an amount of 10% by mass or more the bulk of the molecular chain becomes sufficient, the appearance of the molded body can be improved, and flexibility can be imparted to the molded body. .
- the amount of the monomer (b-2) used is 0 to 90% by mass, preferably 0 to 70% by mass, based on 100% by mass of the total monomer as a raw material for the polymer ( ⁇ ). More preferably, it is 0 to 60% by mass, still more preferably 0 to 50% by mass, still more preferably 0 to 40% by mass, particularly preferably 0 to 35% by mass, and most preferably 0 to 20% by mass.
- the amount of the monomer (b-2) used is 90% by mass or less, the soft vinyl chloride resin composition can be efficiently melted and kneaded, and an effect of improving the appearance of the molded product can be obtained.
- the amount of the monomer (b-3) to be used is 0 to 20% by mass, preferably 0 to 10% by mass, based on 100% by mass of the total monomer as a raw material for the polymer ( ⁇ ). is there.
- the proportion of the monomer (b-3) is 20% by mass or less, the soft vinyl chloride resin composition which is the object of the present invention can be efficiently melted and kneaded, and the molded article has a high appearance. Does not hinder the achievement of
- a polyfunctional monomer such as divinylbenzene, allyl methacrylate, 1,3-butanediol dimethacrylate, triallyl cyanurate may be used.
- the amount is preferably from 0.1 to 2% by mass, more preferably from 0.2 to 1% by mass, based on 100% by mass of the total monomer as a raw material for the polymer ( ⁇ ). If the amount of the polyfunctional monomer used is 2% by mass or less, it is preferable because it does not impair the desired molded appearance of the processing aid (B) of the present invention.
- Various methods can be used as a method for producing the polymer ( ⁇ ).
- the polymerization method include emulsion polymerization, suspension polymerization, and solution polymerization.
- any method such as batch addition of monomers, dropping, divided addition of monomers, etc. may be used, and methods such as random copolymerization and block copolymerization may be used.
- the random copolymer obtained by the method by addition is preferable.
- the emulsifier that can be used when applying the emulsion polymerization method is not particularly limited, and various types of emulsifiers can be used.
- fatty acid salts alkyl sulfate esters, alkylbenzene sulfonates, alkyl phosphate esters, Anionic surfactants such as dialkylsulfosuccinates, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan acid fatty esters, glycerin fatty acid esters, and cationic interfaces such as alkylamine salts Activators can be used. These emulsifiers can be used alone or in combination.
- 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, etc. can be used.
- the polymerization initiator may be a water-soluble, oil-soluble single type or redox type.
- an inorganic initiator such as a normal persulfate may be used alone, or a sulfite, bisulfite, It can also be used as a redox initiator in combination with thiosulfate.
- organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, azo compounds, etc. are used alone or in combination with sodium formaldehyde sulfoxylate as a redox initiator. Although it can be used, the present invention is not limited to these specific examples.
- the method for recovering the polymer ( ⁇ ) in powder form is not particularly limited.
- the polymer ( ⁇ ) is produced by an emulsion polymerization method, the obtained methacrylic acid alkyl ester polymer latex is cooled, and then sulfuric acid is used.
- the polymer is precipitated by acid coagulation or salting out with an electrolyte such as acid such as hydrochloric acid or phosphoric acid, or a salt such as aluminum chloride, calcium chloride, magnesium sulfate, aluminum sulfate, or calcium acetate. It can be obtained by washing and drying.
- good powder recoverability means that the polymer ( ⁇ ) does not become coarse powder or ultrafine powder under general pulverization conditions, and powder recovery is easy.
- Spray drying refers to drying by spraying latex of the present polymer into fine droplets in a spray drying apparatus and then applying hot air.
- Examples of the method for spraying the latex of the present polymer in the form of fine droplets in the spray drying apparatus include a rotating disk type, a pressure nozzle type, a two-fluid nozzle type, and a pressurized two-fluid nozzle type.
- the capacity of the spray drying apparatus may be any of a small capacity used in a laboratory and a large capacity industrially used. What is necessary is just to select suitably the structure of the supply part of the heating gas for drying in a spray-drying apparatus, and the structure of the discharge part of the heating gas for drying and dry powder according to the objective.
- the temperature of the heating gas for drying is preferably 200 ° C. or less, and more preferably 120 to 180 ° C.
- the molecular weight of the polymer ( ⁇ ) is not particularly limited, but the reduced viscosity ⁇ sp / c is preferably 0.2 to 15, and more preferably 0.3 to 14.
- ⁇ sp / c is preferably 0.2 to 15, and more preferably 0.3 to 14.
- the reduced viscosity ⁇ sp / c referred to in the present invention refers to a value measured by dissolving 0.1 g of (co) polymer in 100 mL of chloroform and measuring at 25 ° C.
- a method for adjusting the reduced viscosity ⁇ sp / c conventional methods such as adjustment of the amount of chain transfer agent and initiator used in the polymerization and adjustment of the polymerization temperature can be used.
- the chain transfer agent examples include alkyl mercaptans such as n-octyl mercaptan and t-dodecyl mercaptan.
- the amount of the chain transfer agent is not particularly limited.
- the amount is preferably 0 to 2 parts by mass, and preferably 0 to 1 part by mass with respect to 100 parts by mass of the total monomer of the polymer ( ⁇ ). More preferred is 0 to 0.5 parts by mass.
- processing aid (B) of the present invention may contain an additive as required in addition to the polymer ( ⁇ ).
- the additive include powder fluidity modifiers such as inorganic salts and Aerosil.
- the plasticizer (C) When added to a vinyl chloride resin, the plasticizer (C) is an effect of inhibiting the strong interaction between vinyl chloride polymer molecular chains and extending the distance between vinyl chloride polymer molecular chains. This imparts flexibility to the resin.
- it is at least one selected from compounds and soybean oil-based compounds, such as dialkyl phthalates such as dioctyl phthalate, diisononyl phthalate and diisodecyl phthalate; alkyl benzyl phthalates such as butyl benzyl phthalate; alkyl phthalates Diaryl phthalate; Diaryl phthalate; Triaryl trimellitic acid such as tris (2-ethylhexyl) trimellitic acid; Triaryl phosphate such as tricresyl phosphate; Trialkyl phosphate; Alkyl aryl phosphate; Adipic acid ester Acetyl citrate tribute Ether compounds such as
- the soft vinyl chloride resin composition of the present invention contains a vinyl chloride resin (A), a processing aid (B), and a plasticizer (C). At this time, when the processing aid (B) and the plasticizer (C) are present at the same time, the flexibility improving effect of the processing aid (B) is exhibited.
- the plasticizer (C) is composed of a highly polar part that can interact with the vinyl chloride resin and a low polarity and bulky part, and the high polarity part electrostatically interacts with the vinyl chloride resin. Prevents the interaction between the vinyl chloride polymer molecular chains.
- the bulky part of the plasticizer (C) enters between the vinyl chloride polymer molecular chains at the same time, the distance between the vinyl chloride polymer molecular chains is widened, and the interaction between the vinyl chloride polymer molecular chains is further increased. Since it weakens, mobility improves and a softness
- the polymer ( ⁇ ) contained in the processing aid (B) has a bulky structure because it contains a methacrylic acid alkyl ester whose alkyl group is a branched alkyl group having 3 to 5 carbon atoms.
- the polymer ( ⁇ ) alone does not have the force to enter between the molecular chains because it does not have a site that can inhibit the interaction between the polymer molecular chains.
- the plasticizer (C) enters between the vinyl chloride polymer molecular chains, thereby preventing the interaction between the vinyl chloride polymer molecular chains.
- the plasticizer (C) Since the low-polar part and the polymer ( ⁇ ) have a hydrophobic interaction, the polymer ( ⁇ ) can enter between the vinyl chloride polymer molecular chains. As a result, the distance between the vinyl chloride polymer molecular chains is further increased by the bulkiness of the polymer ( ⁇ ), thereby improving the mobility of the vinyl chloride polymer and increasing the flexibility of the vinyl chloride resin. That is, the plasticizing efficiency is improved by using the processing aid (B) and the plasticizer (C) in combination.
- the content of the processing aid (B) in the vinyl chloride resin composition of the present invention is 0.1 to 20 parts by mass, and 0.5 to 20 parts per 100 parts by mass of the vinyl chloride resin (A).
- the amount is preferably part by mass, and more preferably 0.5 to 15 parts by mass.
- the content of the plasticizer (C) is 10 to 150 parts by mass, preferably 30 to 150 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A).
- the content of the plasticizer (C) is 10 to 150 parts by mass, preferably 30 to 150 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A).
- the vinyl chloride resin composition of the present invention includes various stabilizers, fillers, flame retardants, lubricants, impact modifiers and the like depending on the purpose, as long as the effects of the present invention are not impaired. Additives can be added as needed.
- stabilizers include lead-based stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, and lead silicate, and metals such as potassium, magnesium, barium, zinc, cadmium, and lead.
- lead-based stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, and lead silicate
- metals such as potassium, magnesium, barium, zinc, cadmium, and lead.
- Metal soap stabilizers derived from fatty acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, behenic acid; alkyl Group, ester group, fatty acid group, maleic acid group, organosulfide-based stabilizer having a sulfide-containing group, etc .; Ba—Zn, Ca—Zn, Ba—Ca—Sn, Ca—Mg—Sn , Ca—Zn—Sn, Pb—Sn, Pb—Ba—Ca and other complex metal soap stabilizers; metal groups such as barium and zinc and 2-ethylhexanoic acid, Acids, branched fatty acids such as trialkylacetic acid, unsaturated fatty acids such as oleic acid, ricinoleic acid, lino
- the addition amount of the stabilizer is not particularly limited, but is preferably 1 to 15 parts by mass, more preferably 1 to 8 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A). By setting it as 1 mass part or more, the thermal decomposition at the time of a process can be suppressed, and the fall of the mechanical physical property of a molded object can be prevented by setting it as 15 mass parts or less.
- carbonates such as talc, heavy calcium carbonate, precipitated calcium carbonate, colloidal calcium carbonate, aluminum hydroxide, magnesium hydroxide, titanium oxide, clay, mica, wollastonite, zeolite, silica
- inorganic materials such as zinc oxide, magnesium oxide, carbon black, graphite, glass beads, glass fibers, carbon fibers, and metal fibers
- organic fibers such as polyamide can also be used. These are used alone or in combination. Can be used.
- the addition amount of the filler is not particularly limited, but is preferably 1 to 150 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A). By setting it as 1 mass part or more, moderate rigidity can be provided to a molded object, and the fall of the softness
- flame retardant examples include metal hydroxide, bromine compound, triazine ring-containing compound, zinc compound, phosphorus compound, halogen flame retardant, silicon flame retardant, intomes flame retardant, and antimony oxide. Can be used. These can be used alone or in combination of two or more.
- the amount of the flame retardant added is not particularly limited, it is preferably 1 to 150 parts by weight and more preferably 10 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride resin (A).
- the flame retardance of a molded object can be improved by setting it as 1 mass part or more, and the fall of the softness
- the lubricant examples include liquid hydrocarbon, natural paraffin, micro wax, synthetic paraffin, pure hydrocarbon lubricant such as low molecular weight polyethylene, halogenated hydrocarbon lubricant, fatty acid lubricant such as higher fatty acid and oxy fatty acid, fatty acid amide
- fatty acid amide lubricants such as bis-fatty acid amides, fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters such as glycerides, fatty acid polyglycol esters, fatty acid fatty alcohol esters (ester waxes) and other ester lubricants, Metal soap, fatty alcohol, polyhydric alcohol, polyglycol, polyglycerol, partial ester of fatty acid and polyhydric alcohol, fatty acid and polyglycol, partial ester of polyglycerol, etc. It can be used.
- the addition amount of the lubricant is not particularly limited, but is preferably 0.1 to 15 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A). By setting it as 0.1 mass part or more, adhesion to the molding machine of a resin composition can be reduced, and the fall of workability can be prevented by setting it as 15 mass parts or less.
- an impact modifier for example, chlorinated polyethylene, polybutadiene, polyisoprene, polychloroprene, fluororubber, styrene-butadiene copolymer rubber, acrylonitrile-styrene-butadiene copolymer rubber, methacryl Acrylic core-shell type rubber such as methyl acid-styrene-butadiene copolymer rubber, acrylic ester-methacrylic ester copolymer, silicone-acrylic ester-methacrylic ester copolymer, silicone-acrylic ester-acrylonitrile- Silicone core-shell rubber such as styrene copolymer, styrene-butadiene-styrene block copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-ethylene-butylene-styrene block copolymer Coalescing
- EPDM diene of EPDM
- 1,4-hexadiene, dicyclopentadiene, methylene norbornene, ethylidene norbornene, propenyl norbornene and the like can be used.
- These impact modifiers can be used alone or in combination of two or more.
- the addition amount of the impact modifier is not particularly limited, but is preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A). By setting it as 1 mass part or more, the impact strength of a molded object can be improved, and the fall of a molded external appearance can be prevented by setting it as 20 mass parts or less.
- a release agent, a fluidity improver, a colorant, an antistatic agent, a surfactant, an antifogging agent, an antibacterial agent, a foaming agent, and the like are arbitrarily selected depending on the purpose as long as the effects of the present invention are not impaired. Can be blended.
- the method for obtaining the soft vinyl chloride resin composition of the present invention is not particularly limited, and generally known methods can be used.
- a predetermined amount of vinyl chloride resin (A) and processing aid (B) can be used.
- the plasticizer (C) can be obtained by mixing with a Henschel mixer, a Banbury mixer, a V-type mixer, a ribbon blender or the like.
- the obtained soft vinyl chloride-based resin composition can be used for ordinary molding methods such as injection molding, hollow molding, roll processing, etc., in addition to extrusion molding using a kneading extruder such as a single screw extruder or twin screw extruder.
- various desired molded articles can be obtained.
- the surface hardness (durometer D hardness) of the molded product obtained by molding the soft vinyl chloride resin composition of the present invention is preferably 75 or less, and more preferably 70 or less.
- durometer D hardness is 75 or less, it is suitable for use as a soft molded body.
- the surface hardness can be arbitrarily adjusted by commonly known methods such as the amount of plasticizer added, the type of plasticizer, the degree of polymerization of the vinyl chloride resin, and the amount of filler added.
- the soft vinyl chloride resin composition of the present invention can be suitably used as a wire coating material, and can achieve a good appearance of the wire coating material even under high linear velocity production conditions (high production rate conditions).
- the high linear velocity production condition is, for example, a case where extrusion coating is performed at 1000 m / min or more for a thin wire having a diameter of about 1 to 5 mm ⁇ and 15 to 30 m / min for a thick wire having a diameter of about 50 mm ⁇ .
- the shear rate at this time may reach, for example, 5000 to 15000 / s.
- the soft vinyl chloride resin composition of the present invention When used as a wire coating material, the soft vinyl chloride resin composition may be coated directly on a conductor, or coated on a normal insulated wire as a sheath material. Also good. There is no special limitation when manufacturing a covered electric wire using a resin composition, and it may be manufactured by an ordinary method. For example, a vinyl chloride resin composition is kneaded with a roll, a Banbury mixer, an extruder, etc., and the resulting pellet compound and conductor are extrusion-coated with a conventionally known electric wire extruder equipped with a crosshead die. Etc.
- the vinyl chloride resin composition according to the present invention was converted into a 25 mm single screw extruder (manufactured by Thermo Plastics, 130-145-160-160 ° C (C1-C2-C3-D), screw rotation Number: 80 rpm), and extrusion and pelletizing were performed.
- the obtained pellets were filled in a capillary rheometer (Malvern, barrel: ⁇ 15 mm, 160 ° C., die: ⁇ 1.0 mm * 16 mm) and extruded at a shear rate of 10,000 / s.
- the obtained strand surface was observed, and the number of irregularities on the surface per 5 cm of the compact was counted with the naked eye.
- a predetermined amount of various plasticizers vinyl chloride resin (TK-1300, manufactured by Shin-Etsu Chemical Co., Ltd., average polymerization degree 1300, average chlorine content 57 mass%) 100 parts, stabilizer 4 parts of Ca—Zn composite stabilizer (RUP-103, manufactured by ADEKA), 40 parts of calcium carbonate (whiten SSB blue, manufactured by Shiraishi Calcium) as filler, and aluminum hydroxide (Hydrite H-31) as a flame retardant 30 parts by Showa Denko Co., Ltd.) and 0.5 parts montanic acid ester (OP-Wax, produced by Hoechst) as a lubricant were supplied to a Henschel mixer and mixed uniformly to obtain a vinyl chloride resin composition.
- TK-1300 manufactured by Shin-Etsu Chemical Co., Ltd., average polymerization degree 1300, average chlorine content 57 mass
- stabilizer 4 parts of Ca—Zn composite stabilizer ROP-103, manufactured by ADEKA
- Processing aid (B-1) A reaction vessel equipped with a stirrer and a reflux condenser was charged with 180 parts of ion-exchanged water, into which 0.1 part of anhydrous sodium carbonate and 98 parts of methacrylate-i-butyl methacrylate Then, 2 parts of n-butyl acrylate and 1.0 part of n-octyl mercaptan were added, and the inside of the container was replaced with nitrogen. Thereafter, 1.1 parts of sodium lauryl sulfate was added, the reaction vessel was heated to 45 ° C.
- i-BMA methacrylate-i-butyl MMA: methyl methacrylate
- n-BA acrylic acid-n-butyl
- the polymerization rate was calculated by quantifying the amount of residual monomer in the latex solution after polymerization by gas chromatography.
- plasticizers were used. Diisononyl phthalate (DINP, manufactured by J Plus) Trimellitic acid tris (2-ethylhexyl) (TOTM, Monosizer W-705, manufactured by DIC Corporation) Tricresyl phosphate (TCP, manufactured by Daihachi Chemical Industry Co., Ltd.) Acetyl tributyl citrate (ATBC, Monosizer ATBC, manufactured by DIC) Epoxidized soybean oil (ESBO, EMBILIZER NF-3200, manufactured by Tokyo Fine Chemical Co., Ltd.) Polyester plasticizer (W230S, Polycizer W-230-S, manufactured by DIC)
- any of Examples 1 to 6 containing the component (b-1) within the scope of the present invention has no processing aid (Comparative Example 1) and the addition of processing aid outside the scope of the present invention ( Compared with Comparative Examples 2 to 9), the kneading / dispersion is good and the molding appearance is remarkably improved. This is considered due to the use of a specific amount of the component (b-1).
- Comparative Examples 2 to 9 using processing aids (B-7) to (B-14) containing no component (b-1) were not recognized to have an appearance improving effect. It is considered that kneading did not proceed sufficiently with these processing aids. Further, Comparative Examples 2 to 9 containing no component (b-1) lose flexibility as compared with Examples 1 to 6 containing the component (b-1) and no processing aid (Comparative Example 1). , Plasticization efficiency is reduced. This is because the processing aid molecules are not bulky enough, and even if they enter between the polyvinyl chloride molecular chains together with the plasticizer, they cannot contribute to the distance extension between the vinyl chloride resin molecular chains (that is, plasticization). This is probably because there is no contribution to efficiency.
- Examples 7 and 8 containing the component (b-1) within the scope of the claims show no processing aid (Comparative Example 1) and processing outside the scope of the claims even in the low addition part region.
- auxiliary agents Comparative Examples 10 and 11
- the molding appearance is improved and the plasticization efficiency is also improved. This is presumably because the use of a specific amount of the component (b-1) improved the kneading and dispersion and sufficiently widened the distance between the vinyl chloride resin molecular chains.
- Examples 9 and 10 containing the component (b-1) within the scope of the claims do not depend on the amount of plasticizer, and there is no processing aid of the same composition (Comparative Examples 12 and 14). Compared with the addition of processing aids outside the claims of the blending (Comparative Examples 13 and 15), the molding appearance is improved and the plasticization efficiency is also improved. This is presumably because the use of a specific amount of component (b-1) improved the kneading and dispersion, and the distance between the vinyl chloride resin molecular chains was sufficiently widened.
- Examples 11 to 15 containing the component (b-1) within the scope of the claims do not depend on the type of plasticizer and have no processing aid of the same composition (Comparative Examples 16, 18, 20, 22). 24) and addition of processing aids outside the scope of claims of the same composition (Comparative Examples 17, 19, 21, 23, 25), the molding appearance is improved and the plasticization efficiency is also improved. This is presumably because the use of a specific amount of the component (b-1) improved the kneading and dispersion and sufficiently widened the distance between the vinyl chloride resin molecular chains.
- the surface appearance improving ability and the plasticizing efficiency improving ability can be clearly determined by the presence or absence of alkyl methacrylate whose alkyl group is a branched alkyl group having 3 to 5 carbon atoms. You can see that there is a difference.
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Abstract
Description
一方で、塩化ビニル系樹脂は安価であるが故に製品コストへの要求は厳しく、より生産性を向上させるべくより高生産速度での生産が試みられている。
しかし、高生産速度条件での成形加工では、成形機内における樹脂の滞在混練時間が極端に短いため溶融・混練が不十分となり易く、また塩化ビニル系樹脂の許容成形条件幅の狭さから成形加工条件の変更のみでは満足な成形体を得ることは困難である。
中でも、可塑剤を添加した軟質系の成形は、可塑剤を添加しない硬質系に比べて生産速度が速く、更なる高生産速度化への要求に対して、混練状態を改善し得る新たな手法の提案が待たれている。
一般的に、塩化ビニル系樹脂の混練状態を向上させるべく、主に溶融促進・溶融粘度の付与を目的として、高分子量のアクリル系樹脂を添加する手法が種々提案されている。
例えば、特許文献1乃至3には、塩化ビニル樹脂被覆電線に加工助剤としてメタクリル酸メチルを主成分とするアクリル樹脂を配合することにより、加工性、分散性を向上し得ることが開示されている。
また、特許文献4には、軟質塩化ビニル系樹脂に改質剤としてアクリル樹脂を配合することにより、形状追随性に優れる金属被覆に適した成形体が得られることが開示されている。
しかしながら、高生産速度条件において表面平滑性等で満足できる成形体を得られず、また高ガラス転移温度成分を添加することで柔軟性が損なわれる等、従来の技術では不十分であった。
以上の状況から、高生産速度条件においても、優れた表面平滑性を有し、柔軟性に優れる成形体を得ることができる軟質塩化ビニル系樹脂組成物が求められている。
即ち、本発明は、以下の[1]~[10]に関する。
[1]下記(A)100質量部に対して、(B)を0.1~20質量部及び(C)を10~150質量部を含有する、軟質塩化ビニル系樹脂組成物。
(A)塩化ビニル系樹脂、
(B)アルキルエステル部のアルキル基が炭素数3~5の分岐アルキル基からなるメタクリル酸アルキルエステル10~100質量%、メタクリル酸メチル0~90質量%及びその他の共重合し得る単量体0~20質量%を重合して得られるメタクリル酸アルキルエステル系共重合体を含む粉体状の軟質塩化ビニル系樹脂用加工助剤、
(C)可塑剤。
[2]塩化ビニル系樹脂(A)100質量部に対して、軟質塩化ビニル系樹脂用加工助剤(B)を0.5~20質量部を含有する、[1]記載の軟質塩化ビニル系樹脂組成物。
[3]前記炭素数3~5の分岐アルキル基が炭素数4の分岐アルキル基である[1]又は[2]記載の軟質塩化ビニル系樹脂組成物。
[4]アルキルエステル部のアルキル基が炭素数3~5の分岐アルキル基からなるメタクリル酸アルキルエステルがメタクリル酸-i-ブチルである、[1]~[3]のいずれか1に記載の軟質塩化ビニル系樹脂組成物。
[5]可塑剤(C)が、フタル酸系化合物、トリメリット酸系化合物、リン酸系化合物、アジピン酸系化合物、クエン酸系化合物、エーテル系化合物、ポリエステル系化合物、及び大豆油系化合物から選ばれる少なくとも1種である、[1]~[4]のいずれか1に記載の軟質塩化ビニル系樹脂組成物。
[6]塩化ビニル系樹脂(A)が、平均塩素含有量が56~75質量%である塩化ビニル重合体、塩化ビニル重合体と弾性体及び/又はエラストマーを共重合した塩化ビニル系共重合体から選ばれる少なくとも1種である、[1]~[5]のいずれか1に記載の軟質塩化ビニル系樹脂組成物。
[7][1]~[6]のいずれか1に記載の軟質塩化ビニル系樹脂組成物から成形された成形体。
[8]表面硬度が75以下(デュロメーターD硬度)である、[7]に記載の成形体。
[9]成形体が電線被覆材である、[7]または[8]記載の成形体。
[10][9]に記載の電線被覆材で被覆された電線。
<塩化ビニル系樹脂(A)>
本発明に用いる塩化ビニル系樹脂(A)の塩化ビニル系樹脂の種類については特に制限されるものではなく、例えば塩化ビニルの単独重合体、後塩素化塩化ビニル重合体、部分架橋塩化ビニル重合体あるいは塩化ビニルと共重合し得る他のビニル化合物を、30質量%以下の範囲で含有してなる塩化ビニルとの共重合体、及びこれらの混合物等が挙げられる。
本発明に用いる塩化ビニル系樹脂(A)の製造方法は特に制限はなく、乳化重合法、懸濁重合法、塊状重合法等の種々の重合法で製造したものを使用することができる。
本発明の加工助剤(B)は、アルキルエステル部のアルキル基が炭素数3~5の分岐アルキル基からなるメタクリル酸アルキルエステル(b-1)(以下単量体(b-1)という)10~100質量%、メタクリル酸メチル(b-2)(以下単量体(b-2)という)0~90質量%及びその他の共重合し得る単量体(b-3)(以下単量体(b-3)という)0~20質量%を重合して得られるメタクリル酸アルキルエステル系共重合体(以下重合体(β)という)を含む粉体状の加工助剤である。
また、分岐を有することによって加工助剤(B)に高い分子鎖の嵩高さが付与され、軟質塩化ビニル系樹脂に添加された際、加工助剤(B)が可塑剤によって生じた塩化ビニル系樹脂分子鎖間の間隙に入り込むことで塩化ビニル系樹脂分子鎖間の距離をさらに広げ、可塑化効率を向上させ、柔軟性を付与することができる。
これらメタクリル酸アルキルエステルは、目的に応じて1種あるいは2種以上組み合わせて用いることができる。
単量体(b-3)としては、単量体(b-1)と共重合し得る単量体であれば特に限定されないが、例えばアクリル酸エチル、アクリル酸ブチル、アクリル酸‐2‐エチルヘキシル、アクリル酸ベンジル、アクリル酸フェニル等のアクリル酸エステル;メタクリル酸エチル、メタクリル酸ヘキシル、メタクリル酸オクチル、メタクリル酸‐2‐エチルヘキシル等の(b-1)以外のメタクリル酸アルキルエステル;メタクリル酸ベンジル、メタクリル酸フェニル等のメタクリル酸芳香族エステル;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化合物;アクリロニトリル、メタクリロニトリル等のシアン化ビニル化合物;酢酸ビニル等のビニルエステル;無水マレイン酸等の酸無水物が挙げられる。これらは1種あるいは2種以上を組み合わせて用いることができる。
単量体(b-3)の割合を20質量%以下とすることで、本発明の目的である軟質塩化ビニル系樹脂組成物の溶融及び混練を効率よく行うことができ、成形体の高外観の達成を阻害しない。
噴霧乾燥は、噴霧乾燥装置中に本重合体のラテックスを微小液滴状に噴霧した後に熱風を当てることによる乾燥をいう。
噴霧乾燥装置の容量としては、実験室で使用するような小規模な容量から工業的に使用するような大規模な容量までのいずれであってもよい。
噴霧乾燥装置における乾燥用加熱ガスの供給部の構造、乾燥用加熱ガス及び乾燥粉末の排出部の構造は、目的に応じて適宜選択すればよい。
乾燥用加熱ガスの温度は200℃以下が好ましく、120~180℃がより好ましい。
連鎖移動剤の量は特に制限されないが、例えば、重合体(β)の全単量体100質量部に対して、0~2質量部であることが好ましく、0~1質量部であることがより好ましく、0~0.5質量部であることが更に好ましい。
可塑剤(C)とは、塩化ビニル系樹脂に添加した際に、塩化ビニル系ポリマー分子鎖同士の強固な相互作用を阻害し、塩化ビニル系ポリマー分子鎖間距離を拡張する効果により、塩化ビニル系樹脂に対して柔軟性を付与せしめるものである。
これらは、1種を単独で用いることもできるし、また、2種以上を組合せて併用することもできる。
可塑剤(C)は、塩化ビニル系樹脂と相互作用し得る高極性部位と、低極性かつ嵩高い部位から構成されており、高極性部位が塩化ビニル系樹脂と静電的に相互作用することによって、塩化ビニル系ポリマー分子鎖同士の相互作用を妨げる。また、可塑剤(C)が有する嵩高い部位が同時に塩化ビニル系ポリマー分子鎖間に入り込むため、塩化ビニル系ポリマー分子鎖間の距離が広げられ、さらに塩化ビニル系ポリマー分子鎖同士の相互作用が弱まるために運動性が向上し、柔軟性が付与される。
しかし可塑剤(C)が存在すると、可塑剤(C)が塩化ビニル系ポリマー分子鎖間に入り込むことで塩化ビニル系ポリマー分子鎖同士の相互作用を妨げ、さらに、入り込んだ可塑剤(C)の低極性部位と重合体(β)とが疎水的な相互作用を持つことにより、重合体(β)が塩化ビニル系ポリマー分子鎖間に入りこむことが可能となる。
このことで、重合体(β)の持つ嵩高さによりさらに塩化ビニル系ポリマー分子鎖間距離が広げられることで塩化ビニル系ポリマーの運動性が向上し、塩化ビニル系樹脂の柔軟性が高まる。すなわち、加工助剤(B)と可塑剤(C)を併用することで可塑化効率が向上する。
可塑剤の添加量を10質量部以上とすることで、塩化ビニル系樹脂分子鎖同士の相互作用の阻害が充分となり、塩化ビニル系樹脂分子鎖間の距離が充分広がることで、柔軟性を付与することができる。加えて、塩化ビニル系樹脂分子鎖同士の強固な相互作用を妨げることで、加工助剤(B)が塩化ビニル系樹脂分子鎖間に入り込めるようになり、加工助剤(B)の持つ可塑化効率向上能を発現することができる。
また、150質量部以下とすることで、機械物性・難燃性・電気特性の低下を防ぐことができる。
得られた軟質塩化ビニル系樹脂組成物は、単軸押出機、二軸押機等の混練押出機による押出成形の他、通常の公知の成形方法、例えば、射出成形、中空成形、ロール加工等にも適用して各種所望の成形体を得ることができる。
デュロメータD硬度が75以下であることで、軟質成形体としての使用に好適となる。
表面硬度は、本発明の効果を損なわない限りにおいて、可塑剤添加量、可塑剤種、塩化ビニル系樹脂の重合度、充填材添加量等の通常公知の方法により任意に調整可能である。
たとえば、塩化ビニル系樹脂組成物をロール、バンバリーミキサー、押出機等で混練し、得られたペレットコンパウンドと導体とをクロスヘッドダイを付設した従来公知の電線用押出機で電線被覆押出成形すること等により行うことができる。
なお、各実施例、比較例中「部」とあるのは「質量部」を示し、評価は下記により行った。
本発明における塩化ビニル系樹脂組成物を、25mm単軸押出機(サーモ・プラスティックス工業社製、130‐145‐160‐160℃ (C1‐C2‐C3‐D)、スクリュー回転数:80rpm)に供給し、押出・ペレタイズを行った。
得られたペレットをキャピラリーレオメーター(マルバーン社製、バレル:φ15mm、160℃、ダイ:φ1.0mm*16mm)に充填し、せん断速度10000/sで押出した。得られたストランド表面を観察し、成形体5cm当たりの表面の凹凸数を肉眼でカウントした。
上記25mm単軸押出機による押し出しにて得られたペレットを、8インチロールを用い、160℃にて3分間溶融混練し、約1mm厚の塩化ビニル系樹脂組成物シートを得た。得られた約1mm厚の塩化ビニル系樹脂組成物シートを8枚重ね、160℃・5MPaにて3分間、加熱プレスすることにより、8mm厚板の成形体を得た。
得られた成形体について、JIS K7215に基づき、タイプAデュロメータ(高分子計器社製、「デジタルゴム硬度計DD2-A型」)を用い、4秒保持後の表面硬度を測定した。タイプAデュロメータでの測定値が90を超えた場合は、タイプDデュロメータ(上島製作所社製、「HD-104N型」)を用いて同様に測定した。いずれも値が低いほど柔軟性が良好となる。
(2)で得られた1mm厚板から、JIS K6723に基づき、JIS2号ダンベルを打ち抜き200mm/minにて引張試験を行い測定した。引張弾性率が低いほど柔軟性が良好となる。
所定量の各種加工助剤の他に、所定量の各種可塑剤、塩化ビニル樹脂(TK-1300、信越化学工業社製、平均重合度1300、平均塩素含有率57質量%)100部、安定剤としてCa-Zn複合安定剤(RUP-103、ADEKA社製)4部、充填材として炭酸カルシウム(ホワイトンSSB青、白石カルシウム社製)40部、難燃剤として水酸化アルミニウム(ハイジライトH-31、昭和電工社製)30部、滑剤としてモンタン酸エステル(OP-Wax、ヘキスト社製)0.5部を、ヘンシェルミキサーに供給して均一に混合し、塩化ビニル系樹脂組成物を得た。
[製造例1]加工助剤(B-1)の製造
攪拌機及び環流冷却器つき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‐i‐ブチル98部、アクリル酸‐n‐ブチル2部及びn‐オクチルメルカプタン1.0部を加えて、容器内を窒素で置換した。その後、ラウリル硫酸ナトリウム1.1部を加え、攪拌下で反応容器を45℃まで昇温し、過硫酸カリウム0.15部を仕込み重合反応を開始させた後、2時間加熱攪拌して重合を終了した。得られたラテックスを冷却後、入口温度150℃及び出口温度65℃条件で噴霧乾燥を行い、加工助剤(B-1)を得た。
単量体成分の組成及びn‐オクチルメルカプタンの添加量を表1に記載の通りに変更した以外は製造例1と同様にして、各加工助剤の製造を行った。
B-10~14として以下の加工助剤を用いた。
(B-10)アクリル系加工助剤 P530(三菱レイヨン社製、メタクリル酸メチル系高分子量ポリマー/(b-1)成分を含まない)
(B-11)アクリル系加工助剤 P531(三菱レイヨン社製、メタクリル酸メチル系高分子量ポリマー/(b-1)成分を含まない)
(B-12)アクリル系加工助剤 P551(三菱レイヨン社製、メタクリル酸メチル系高分子量ポリマー/(b-1)成分を含まない)
(B-13)アクリル系加工助剤 PA40(カネカ社製、メタクリル酸メチル・アクリル酸ブチル共重合体)
(B-14)アクリル系加工助剤 K125(Dow社製、メタクリル酸メチル・アクリル酸エチル・メタクリル酸-n-ブチル・メタクリル酸エチル共重合体/メタクリル酸-n-ブチル含量10質量%未満)
i-BMA:メタクリル酸-i-ブチル
MMA:メタクリル酸メチル
n-BA:アクリル酸-n-ブチル
n-BMA:メタクリル酸-n-ブチル
n-OM:n-オクチルメルカプタン
フタル酸ジイソノニル(DINP、ジェイ・プラス社製)
トリメリット酸トリス(2-エチルヘキシル)(TOTM、モノサイザーW-705、DIC社製)
リン酸トリクレジル(TCP、大八化学工業社製)
アセチルクエン酸トリブチル(ATBC、モノサイザーATBC、DIC社製)
エポキシ化大豆油(ESBO、EMBILIZER NF-3200、東京ファインケミカル社製)
ポリエステル系可塑剤(W230S、ポリサイザーW-230-S、DIC社製)
表2の結果より、(b-1)成分を本発明の範囲で含有する実施例1~6はいずれも、加工助剤なし(比較例1)及び本発明の範囲外の加工助剤添加(比較例2~9)に比べ、混練・分散が良好となり、成形外観が顕著に向上している。これは特定量の(b-1)成分の使用によるものと考えられる。
(b-1)成分を含まない加工助剤(B-7)~(B-14)を用いた比較例2~9は、外観向上効果があるとは認められなかった。これらの加工助剤では混練が充分に進まなかったとめと考えられる。また(b-1)成分を含まない比較例2~9は、(b-1)成分を含む実施例1~6及び加工助剤が無い場合(比較例1)と比べて柔軟性が失われ、可塑化効率が低下している。これは、加工助剤の分子の嵩高さが充分ではなく、可塑剤とともにポリ塩化ビニル分子鎖間へ入り込んだとしても、塩化ビニル系樹脂分子鎖間の距離拡張には寄与できないため(つまり可塑化効率への寄与が無いため)と考えられる。また、加工助剤が塩化ビニル系樹脂より高いガラス転移温度を有することから、加工助剤なし(比較例1)に比べても柔軟性が失われたものと考えられる。
以上の結果から、アルキル基が炭素数3~5の分岐アルキル基からなるメタクリル酸アルキルエステルの有無によって表面外観向上能及び可塑化効率向上能に明確な差があることがわかる。
表3の結果より、(b-1)成分を請求項の範囲で含有する実施例7及び8は、低添加部数領域においても、加工助剤なし(比較例1)及び請求項範囲外の加工助剤添加(比較例10、11)に比べ、成形外観が向上し、可塑化効率も向上している。これは特定量の(b-1)成分の使用により、混練・分散が良好となり、また塩化ビニル系樹脂分子鎖間の距離が充分広げられたためと考えられる。
表3の結果より、(b-1)成分を請求項の範囲で含有する実施例9及び10は可塑剤量によらず、同配合の加工助剤なし(比較例12、14)及び、同配合の請求項範囲外の加工助剤添加(比較例13、15)に比べ、成形外観が向上し、可塑化効率も向上している。これは特定量の(b-1)成分の使用により混練・分散が良好となり、また塩化ビニル系樹脂分子鎖間の距離が充分広げられたためと考えられる。
表3の結果より、(b-1)成分を請求項の範囲で含有する実施例11~15は可塑剤種によらず、同配合の加工助剤なし(比較例16、18、20、22、24)及び、同配合の請求項範囲外の加工助剤添加(比較例17、19、21、23、25)に比べ、成形外観が向上し、可塑化効率も向上している。これは特定量の(b-1)成分の使用により、混練・分散が良好となり、また塩化ビニル系樹脂分子鎖間の距離が充分広げられたためと考えられる。
Claims (10)
- 下記(A)100質量部に対して、(B)を0.1~20質量部及び(C)を10~150質量部を含有する、軟質塩化ビニル系樹脂組成物。
(A)塩化ビニル系樹脂、
(B)アルキルエステル部のアルキル基が炭素数3~5の分岐アルキル基からなるメタクリル酸アルキルエステル10~100質量%、メタクリル酸メチル0~90質量%及びその他の共重合し得る単量体0~20質量%を重合して得られるメタクリル酸アルキルエステル系共重合体を含む粉体状の軟質塩化ビニル系樹脂用加工助剤、
(C)可塑剤。 - 塩化ビニル系樹脂(A)100質量部に対して、軟質塩化ビニル系樹脂用加工助剤(B)を0.5~20質量部を含有する、請求項1記載の軟質塩化ビニル系樹脂組成物。
- 前記炭素数3~5の分岐アルキル基が炭素数4の分岐アルキル基である請求項1記載の軟質塩化ビニル系樹脂組成物。
- アルキルエステル部のアルキル基が炭素数3~5の分岐アルキル基からなるメタクリル酸アルキルエステルがメタクリル酸-i-ブチルである、請求項1記載の軟質塩化ビニル系樹脂組成物。
- 可塑剤(C)が、フタル酸系化合物、トリメリット酸系化合物、リン酸系化合物、アジピン酸系化合物、クエン酸系化合物、エーテル系化合物、ポリエステル系化合物、及び大豆油系化合物から選ばれる少なくとも1種である、請求項1記載の軟質塩化ビニル系樹脂組成物。
- 塩化ビニル系樹脂(A)が、平均塩素含有量が56~75質量%である塩化ビニル重合体、塩化ビニル重合体と弾性体及び/又はエラストマーを共重合した塩化ビニル系共重合体から選ばれる少なくとも1種である、請求項1記載の軟質塩化ビニル系樹脂組成物。
- 請求項1記載の軟質塩化ビニル系樹脂組成物から成形された成形体。
- 表面硬度が75以下(デュロメーターD硬度)である、請求項7に記載の成形体。
- 成形体が電線被覆材である、請求項7記載の成形体。
- 請求項9に記載の電線被覆材で被覆された電線。
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KR101829559B1 (ko) | 2018-02-14 |
EP3050922A1 (en) | 2016-08-03 |
TWI624502B (zh) | 2018-05-21 |
JP6315207B2 (ja) | 2018-04-25 |
EP3050922A4 (en) | 2016-09-28 |
US20160237297A1 (en) | 2016-08-18 |
CN105722913A (zh) | 2016-06-29 |
TW201520258A (zh) | 2015-06-01 |
KR20160046867A (ko) | 2016-04-29 |
CN105722913B (zh) | 2018-03-16 |
US10072172B2 (en) | 2018-09-11 |
JPWO2015045930A1 (ja) | 2017-03-09 |
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