WO2010119842A1 - 非発泡成形用加工助剤、樹脂組成物及び成形体 - Google Patents
非発泡成形用加工助剤、樹脂組成物及び成形体 Download PDFInfo
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- WO2010119842A1 WO2010119842A1 PCT/JP2010/056532 JP2010056532W WO2010119842A1 WO 2010119842 A1 WO2010119842 A1 WO 2010119842A1 JP 2010056532 W JP2010056532 W JP 2010056532W WO 2010119842 A1 WO2010119842 A1 WO 2010119842A1
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- Prior art keywords
- vinyl chloride
- chloride resin
- mass
- alkyl
- meth
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Classifications
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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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
Definitions
- the present invention relates to a non-foaming molding processing aid, a non-foaming molding vinyl chloride resin composition containing a vinyl chloride resin and a non-foaming molding processing aid, a vinyl chloride resin and a non-foaming molding processing aid.
- the present invention relates to a vinyl chloride-based resin molded article containing bismuth and a method for producing the same.
- a 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 various physical properties such as chemical resistance, impact resistance and weather resistance and is inexpensive.
- the vinyl chloride resin has a high softening temperature
- the melting temperature at the time of thermoforming must be set to a temperature close to the pyrolysis temperature, until the temperature range in which thermoforming can be performed is narrow and until it becomes a molten state.
- Has a problem related to thermoforming such as a long time.
- the elongation characteristics and the melt strength are insufficient at normal thermoforming temperatures, it is difficult to obtain a satisfactory molded article even if the molding process conditions are adjusted.
- Patent Document 1 proposes a vinyl chloride resin composition in which a polymer mainly containing units based on alkyl methacrylate other than methyl methacrylate is blended.
- Patent Document 2 discloses an alkyl methacrylate polymer obtained by polymerizing a monomer component composed of 40 to 80% by mass of methyl methacrylate and 20 to 60% by mass of alkyl methacrylate having 2 to 8 carbon atoms in the alkyl group.
- a vinyl chloride resin composition in which
- An object of the present invention is to provide a processing aid for improving the gelation characteristics of a vinyl chloride resin composition, improving molding processability, and obtaining a molded article having a good surface appearance.
- 0.1 to 30 parts by mass of the non-foaming processing aid is blended with 100 parts by mass of the vinyl chloride resin (B), and the resulting vinyl chloride resin composition is extruded.
- the processing aid for non-foaming molding of the present invention improves the gelation characteristics of the vinyl chloride resin, improves the molding processability, and enables the production of a molded article having a good surface appearance.
- the vinyl chloride resin composition for non-foaming molding of the present invention has an improved gelling property, is excellent in molding processability, and enables the production of a molded article having a good surface appearance.
- the vinyl chloride resin molded article of the present invention has a good surface appearance.
- the alkyl (meth) acrylate polymer (A) of the present invention contains 65% by mass or more of i-butyl methacrylate (a1) units.
- an alkyl (meth) acrylate type polymer (A) makes all the monomer units to contain 100 mass%. If the content of the i-butyl methacrylate (a1) unit in the alkyl (meth) acrylate polymer (A) is 65% by mass or more, the alkyl (meth) acrylate in the vinyl chloride resin (B) The dispersibility of the polymer (A) becomes good and the gelation property becomes good.
- the content of the i-butyl methacrylate (a1) unit in the alkyl (meth) acrylate polymer (A) is preferably 75% by mass or more, and more preferably 85% by mass or more.
- the alkyl (meth) acrylate polymer (A) of the present invention can be added to other vinyl units as necessary within the range of improving the gelation characteristics of the vinyl chloride resin. You may contain 35 mass% or less of a monomer (a2) unit. If the content of other vinyl monomer (a2) units in the alkyl (meth) acrylate polymer (A) is 35% by mass or less, the alkyl (meth) in the vinyl chloride resin (B) The dispersibility of the acrylate polymer (A) becomes good, and the gelation property becomes good.
- the content of the other vinyl monomer (a2) unit in the alkyl (meth) acrylate polymer (A) is preferably 25% by mass or less, and more preferably 15% by mass or less.
- Examples of the other vinyl monomer (a2) serving as a constituent raw material of the other vinyl monomer (a2) unit include methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, phenyl acrylate and other acrylates; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, phenyl methacrylate, and other methacrylates; styrene, ⁇ -methylstyrene Aromatic vinyl monomers such as vinyl toluene; vinyl cyanide monomers such as (meth) acrylonitrile; fatty acid vinyl esters such as vinyl acetate; unsaturated acids such as maleic
- the mass average molecular weight (Mw) of the alkyl (meth) acrylate polymer (A) of the present invention improves the gelation characteristics of the vinyl chloride resin and the surface appearance of the resulting molded article is good, 20 It is 10,000 to 2,000,000, preferably 400,000 to 2,000,000, more preferably 500,000 to 1,500,000.
- the Mw of the alkyl (meth) acrylate polymer (A) can be set by adjusting the type and amount of the initiator used during polymerization and the type and amount of the chain transfer agent.
- the alkyl (meth) acrylate polymer (A) of the present invention can be obtained by polymerizing the monomer component (a) containing i-butyl methacrylate (a1).
- the monomer component (a) contains 35 masses of other vinyl monomers (a2) as necessary within the range of improving the gelation characteristics of the vinyl chloride resin. % Or less. If the content of the other vinyl monomer (a2) in the monomer component (a) is 35% by mass or less, an alkyl (meth) acrylate polymer (in vinyl chloride resin (B)) The dispersibility of A) becomes good, and the gelation characteristics become good.
- the content of the other vinyl monomer (a2) in the monomer component (a) is preferably 25% by mass or less, and more preferably 15% by mass or less.
- the monomer component (a) can be polymerized by a known polymerization method.
- the polymerization method include an emulsion polymerization method, a suspension polymerization method, and a bulk polymerization method.
- the emulsion polymerization method is preferable because the alkyl (meth) acrylate polymer (A) can be obtained in the form of powder.
- the polymerization temperature of the monomer component (a) is generally 40 to 90 ° C.
- emulsifier used in the emulsion polymerization method examples include anionic emulsifiers such as fatty acid salt compounds, sulfonate compounds, sulfate compounds, phosphate ester compounds, dialkylsulfosuccinate compounds; polyoxyethylene alkyl ethers, polyoxyethylene fatty acids
- anionic emulsifiers such as esters, sorbitan fatty acid esters and glycerin fatty acid esters
- cationic emulsifiers such as alkylamine salts.
- a pH adjuster can be used to suppress hydrolysis of the alkyl (meth) acrylate.
- the pH regulator 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, And disodium hydrogen phosphate-citric acid.
- the initiator examples include persulfates such as potassium persulfate and sodium persulfate; organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide and benzoyl peroxide; azobisisobutyronitrile and the like.
- persulfates such as potassium persulfate and sodium persulfate
- organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide and benzoyl peroxide
- azobisisobutyronitrile An azo compound; the redox initiator which combined the said persulfate or the said organic peroxide, and the reducing agent is mentioned.
- chain transfer agent examples include alkyl mercaptans such as n-octyl mercaptan and t-dodecyl mercaptan.
- the powder recovery method include a coagulation method, a spray drying method, and a freeze drying method.
- the latex of the obtained alkyl (meth) acrylate polymer (A) is cooled and then coagulated.
- the alkyl (meth) acrylate polymer (A) may be coagulated using a depositing agent to precipitate, and further filtered, washed and dried.
- the coagulant examples include inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid; inorganic salts such as aluminum chloride, calcium chloride, magnesium sulfate, aluminum sulfate, and calcium acetate.
- inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid
- inorganic salts such as aluminum chloride, calcium chloride, magnesium sulfate, aluminum sulfate, and calcium acetate.
- the vinyl chloride resin (B) used in the present invention is a known vinyl chloride resin.
- Examples of the vinyl chloride resin (B) include vinyl chloride homopolymers, post-chlorinated vinyl chloride polymers, partially cross-linked vinyl chloride polymers, and copolymers of vinyl chloride and other vinyl monomers. It is done. These may be used alone or in combination of two or more.
- a monomer composition for obtaining a copolymer of vinyl chloride and other vinyl monomers a total of 100 masses of vinyl chloride and other vinyl monomers is used from the viewpoint of maintaining the characteristics of the vinyl chloride resin.
- % Of vinyl chloride is preferably 70% by mass or more and 30% by mass or less of other vinyl monomers.
- Examples of other vinyl monomers include alkyl (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate; aromatic vinyl monomers such as styrene; olefins such as ethylene and propylene; vinyl acetate, Fatty acid vinyl esters such as vinyl propionate; alkyl vinyl ethers such as vinyl methyl ether and vinyl butyl ether; unsaturated carboxylic acids such as (meth) acrylic acid and maleic anhydride, or acid anhydrides thereof. These may be used alone or in combination of two or more.
- the average degree of polymerization of the vinyl chloride resin (B) is preferably 300 to 5,000, more preferably 500 to 3,000. If the average degree of polymerization of the vinyl chloride resin (B) is 300 or more, the resulting molded article has good mechanical properties, and if it is 5,000 or less, the moldability of the vinyl chloride resin composition is good. Become.
- the non-foaming molding vinyl chloride resin composition of the present invention contains 0.1 to 30 parts by mass of the non-foaming molding processing aid of the present invention with respect to 100 parts by mass of the vinyl chloride resin (B). If the content of the processing aid for non-foaming molding is 0.1 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin (B), the gelation characteristics of the vinyl chloride resin composition are improved, and If the surface appearance is good and the amount is 30 parts by mass or less, the surface appearance of the molded body is poor in appearance and coloring.
- the content of the processing aid for non-foaming molding is preferably 0.1 to 20 parts by mass, and more preferably 0.3 to 10 parts by mass.
- the non-foaming vinyl chloride resin composition is a stabilizer, lubricant, filler, impact modifier, flame retardant, mold release agent, and fluidity improvement, as long as the properties are not impaired.
- Additives such as a colorant, a colorant, an antistatic agent, a surfactant, an antifogging agent, and an antibacterial agent can be added.
- the stabilizer examples include lead 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 ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, behenic acid; alkyl groups Organic tin stabilizers having ester groups, fatty acid groups, maleic acid groups, sulfide-containing groups, etc .; Ba—Zn series, Ca—Zn series, Ba—Ca—Sn series, Ca—Mg—Sn series, Ca— Composite metal soap stabilizers such as Zn-Sn, Pb-Sn, and Pb-Ba-
- the lubricant examples include pure hydrocarbon lubricants such as liquid paraffin, natural paraffin, micro wax, synthetic paraffin, and low molecular weight polyethylene; 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; Examples include fatty alcohols; polyhydric alcohols; polyglycols; polyglycerols; partial esters of fatty acids and polyhydric alcohols; fatty acids and polyglycols; partial esters of polyglycerols. These may be used alone or in combination of two or more.
- the filler examples include carbonates such as heavy calcium carbonate, precipitated calcium carbonate, and colloidal calcium carbonate, aluminum hydroxide, magnesium hydroxide, titanium oxide, clay, mica, talc, wollastonite, zeolite, silica, Examples thereof include inorganic materials such as zinc oxide, magnesium oxide, carbon blank, graphite, glass beads, glass fibers, carbon fibers, and metal fibers; and organic materials such as polyamide. These may be used alone or in combination of two or more.
- the impact modifier examples include polybutadiene, polyisoprene, polychloroprene, fluorine rubber, styrene-butadiene copolymer rubber, acrylonitrile-styrene-butadiene copolymer rubber, and styrene-butadiene-styrene block copolymer rubber.
- Styrene-isoprene-styrene block copolymer rubber styrene-ethylene-butylene-styrene block copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber (EPDM), MBS resin, acrylic System strengthening agents.
- Examples of the diene of EPDM include 1,4-hexadiene, dicyclopentadiene, methylene norbornene, ethylidene norbornene, and propenyl norbornene. These may be used alone or in combination of two or more.
- flame retardants include chlorinated paraffin, aluminum hydroxide, antimony dioxide, and halogen compounds. These may be used alone or in combination of two or more.
- the vinyl chloride resin molded product of the present invention contains 0.1 to 30 parts by mass of the non-foaming molding processing aid of the present invention with respect to 100 parts by mass of the vinyl chloride resin (B) and has a density of 1.3 g. / Cm 3 or more non-foamed body. If the content of the processing aid for non-foaming molding is 0.1 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin (B), the surface appearance of the molded article is good, and if it is 30 parts by mass or less, Defects in surface appearance and coloration of the molded body are suppressed. If the density of the molded body is 1.3 g / cm 3 or more, a molded body having a good surface appearance can be obtained.
- the vinyl chloride resin molded product of the present invention is obtained by molding the vinyl chloride resin composition of the present invention.
- a known molding method can be used, and examples thereof include extrusion molding by a kneading extruder such as a single screw extruder and a twin screw extruder, calendar molding, injection molding, and hollow molding.
- the polymerization rate of the alkyl (meth) acrylate polymer (A) is determined by adding an inhibitor (hydroquinone) to the latex of the polymer collected after polymerization and heating it at 180 ° C for 30 minutes. Measured and calculated by comparison with the calculated value from the charged amount.
- Mass average molecular weight (Mw), number average molecular weight (Mn) Mw and Mn of the alkyl (meth) acrylate polymer (A) are gel permeation chromatography (model name “HLC”) using the tetrahydrofuran (THF) soluble content of the alkyl (meth) acrylate polymer (A) as a sample. -8220 ", manufactured by Tosoh Corporation), and a column (trade name” TSK-GEL SUPER HZM-M ", manufactured by Tosoh Corporation) under the conditions of eluent THF and temperature of 40 ° C.
- Mw and Mn in this invention were calculated
- alkyl (meth) acrylate polymer (A1) latex was obtained.
- the resulting latex of the alkyl methacrylate polymer (A1) was dropped into 100 parts of hot water containing 5 parts of calcium acetate for coagulation. The coagulated material was separated and washed, and then dried at 65 ° C. for 16 hours to obtain an alkyl (meth) acrylate polymer (A1) in the form of powder. Mw of the alkyl (meth) acrylate polymer (A1) was 1,000,000.
- Table 1 shows the polymerization rate, Mw, and Mn of the alkyl (meth) acrylate polymers (A) obtained in Production Examples 1 to 10.
- the obtained alkyl (meth) acrylate polymer (A) is used as a processing aid for non-foaming molding.
- Table 1 shows the numbers of the processing aids for non-foaming molding corresponding to the alkyl (meth) acrylate polymer (A).
- Example 1 Using a 20L Henschel mixer (model name “FM20C / I”, manufactured by Nihon Coke Kogyo Co., Ltd.) with the following amounts of non-foaming processing aid, vinyl chloride resin (B), and various additives The mixture was heated up to 115 ° C. and then taken out to obtain a non-foaming vinyl chloride resin composition.
- Examples 2 to 8, Comparative Examples 1 to 7 A vinyl chloride resin molded body was obtained in the same manner as in Example 1 except that the processing aid for non-foaming molding was changed as shown in Table 2. Moreover, in the comparative example 5, what added the following additive to the said compounding composition was used. Other than that was carried out similarly to Example 1, and obtained the vinyl chloride-type resin molding.
- Foaming agent Azodicarbonamide manufactured by Eiwa Kasei Co., Ltd.
- Foaming agent baking soda trade name “Selfon SC-P”, produced by Eiwa Kasei Co., Ltd.
- Table 2 shows the gelation characteristics of the vinyl chloride resin compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 7, and the surface appearance and density of the vinyl chloride resin moldings.
- Comparative Example 4 where an alkyl (meth) acrylate polymer having a content of n-butyl methacrylate (a2) units of 100% was used as a processing aid, the surface appearance of the molded article was good, Compared to Example 1, the gelation time was significantly longer and the gelation characteristics were inferior in that the maximum torque value was also large.
- An alkyl (meth) acrylate polymer having an i-butyl methacrylate (a1) unit content of 65% or more was used as a processing aid. However, since a foaming agent was included, the density of the molded product was 1.3 g / cm 3. In lower Comparative Example 5, the gelation characteristics of the resin composition were good, but the surface appearance of the molded article was poor.
- the processing aid for non-foaming molding of the present invention improves the gelation characteristics of the vinyl chloride resin, improves the molding processability, and enables the production of a molded article having a good surface appearance.
- the vinyl chloride resin molded body of the present invention has a good surface appearance, and is suitably used for coating materials such as irregularly shaped products, plates, sheets, films, pipes, electric wires and the like.
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Abstract
Description
また本発明は、塩化ビニル系樹脂(B)100質量部に対して、前記の非発泡成形用加工助剤を0.1~30質量部含有する非発泡成形用塩化ビニル系樹脂組成物を提供する。
また本発明は、塩化ビニル系樹脂(B)100質量部に対して、前記の非発泡成形用加工助剤を0.1~30質量部含有し、密度が1.3g/cm3以上である、塩化ビニル系樹脂成形体を提供する。
本発明の非発泡成形用塩化ビニル系樹脂組成物は、ゲル化特性が改良され成形加工性に優れ、表面外観の良好な成形体の製造を可能とする。
本発明の塩化ビニル系樹脂成形体は、表面外観が良好である。
尚、「(メタ)アクリレート」は、「アクリレート」又は「メタクリレート」を表す。
アルキル(メタ)アクリレート系重合体(A)中の、i-ブチルメタクリレート(a1)単位の含有率が65質量%以上であれば、塩化ビニル系樹脂(B)中でのアルキル(メタ)アクリレート系重合体(A)の分散性が良好となり、ゲル化特性が良好となる。
アルキル(メタ)アクリレート系重合体(A)中の、i-ブチルメタクリレート(a1)単位の含有率は75質量%以上が好ましく、85質量%以上がより好ましい。
アルキル(メタ)アクリレート系重合体(A)中の、他のビニル単量体(a2)単位の含有率が35質量%以下であれば、塩化ビニル系樹脂(B)中でのアルキル(メタ)アクリレート系重合体(A)の分散性が良好となり、ゲル化特性が良好となる。
アルキル(メタ)アクリレート系重合体(A)中の、他のビニル単量体(a2)単位の含有率は25質量%以下が好ましく、15質量%以下がより好ましい。
これらは単独で使用してもよいし、また2種以上を併用してもよい。
アルキル(メタ)アクリレート系重合体(A)のMwは、重合時に用いる開始剤の種類及び量、連鎖移動剤の種類及び量を調整することによって設定できる。
単量体成分(a)中の、i-ブチルメタクリレート(a1)の含有率が65質量%以上であれば、塩化ビニル系樹脂(B)中でのアルキル(メタ)アクリレート系重合体(A)の分散性が良好となり、ゲル化特性が良好となる。
単量体成分(a)中の、i-ブチルメタクリレート(a1)の含有率は75質量%以上が好ましく、85質量%以上がより好ましい。
単量体成分(a)中の、他のビニル単量体(a2)の含有率が35質量%以下であれば、塩化ビニル系樹脂(B)中でのアルキル(メタ)アクリレート系重合体(A)の分散性が良好となり、ゲル化特性が良好となる。
単量体成分(a)中の、他のビニル単量体(a2)の含有率は25質量%以下が好ましく、15質量%以下がより好ましい。
重合方法としては、例えば、乳化重合法、懸濁重合法、塊状重合法が挙げられる。この中では、アルキル(メタ)アクリレート系重合体(A)を粉体の形態で得られることから、乳化重合法が好ましい。
単量体成分(a)の重合温度は、40~90℃が一般的である。
これらは単独で使用してもよいし、また2種以上を併用してもよい。
pH調節剤としては、例えば、硼酸-塩化カリウム-水酸化カリウム、燐酸二水素カリウム-燐酸水素二ナトリウム、硼酸-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、燐酸二水素カリウム-硼砂、燐酸水素二ナトリウム-クエン酸が挙げられる。
粉体回収方法としては、例えば、凝析法、噴霧乾燥法、凍結乾燥法が挙げられる。
塩化ビニル系樹脂(B)としては、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、塩化ビニルと他のビニル単量体との共重合体が挙げられる。
これらは単独で使用してもよいし、また2種以上を併用してもよい。
これらは単独で使用してもよいし、また2種以上を併用してもよい。
塩化ビニル系樹脂(B)100質量部に対する、非発泡成形用加工助剤の含有量が0.1質量部以上であれば、塩化ビニル系樹脂組成物のゲル化特性が改良されて成形体の表面外観が良好となり、30質量部以下であれば、成形体の表面外観の不良や着色が抑制される。非発泡成形用加工助剤の含有量は0.1~20質量部であることが好ましく、さらに0.3~10質量部であることがより好ましい。
溶融混練方法としては、例えば、ヘンシェルミキサ、バンバリーミキサ、V型ミキサ、リボンブレンダを用いる方法が挙げられる。
これらは単独で使用してもよいし、また2種以上を併用してもよい。
これらは単独で使用してもよいし、また2種以上を併用してもよい。
これらは単独で使用してもよいし、また2種以上を併用してもよい。
EPDMのジエンとしては、例えば、1,4-ヘキサジエン、ジシクロペンタジエン、メチレンノルボルネン、エチリデンノルボルネン、プロペニルノルボルネンが挙げられる。
これらは単独で使用してもよいし、また2種以上を併用してもよい。
塩化ビニル系樹脂(B)100質量部に対する、非発泡成形用加工助剤の含有量が0.1質量部以上であれば、成形体の表面外観が良好となり、30質量部以下であれば、成形体の表面外観の不良や着色が抑制される。
成形体の密度が1.3g/cm3以上であれば、表面外観が良好な成形体が得られる。
尚、実施例中の「部」及び「%」は、それぞれ「質量部」及び「質量%」を表す。
アルキル(メタ)アクリレート系重合体(A)の重合率は、重合後に採取した重合体のラテックスに禁止剤(ハイドロキノン)を投入し、180℃で30分加熱して固形分を測定し、仕込み量からの計算値との比較により算出した。
アルキル(メタ)アクリレート系重合体(A)のMw及びMnは、アルキル(メタ)アクリレート系重合体(A)のテトラヒドロフラン(THF)可溶分を試料として、ゲルパーミエーションクロマトグラフィー(機種名「HLC-8220」、東ソー(株)製)、カラム(商品名「TSK-GEL SUPER HZM-M」、東ソー(株)製)を用いて、溶離液THF、温度40℃の条件で測定した。
尚、本発明におけるMw及びMnは、標準ポリスチレンによる検量線から求めた。
塩化ビニル系樹脂組成物を、ラボプラストミル(機種名「30C-150」、(株)東洋精機製作所製)を用いて、温度190℃、充填量63g、回転数30rpmの条件で、ゲル化特性の評価を行なった。ゲル化特性としては、ゲル化時間、最大トルク、平衡トルクの評価を行なった。
尚、ゲル化時間が短く最大トルク値が小さいほど、塩化ビニル系樹脂組成物の熱履歴が低減し、ゲル化特性に優れることを意味する。
塩化ビニル系樹脂成形体の表面外観を、以下の指標に基づいて評価した。
○:成形体表面に荒れがない
△:成形体表面に部分的に荒れがある
×:成形体表面に荒れがある
塩化ビニル系樹脂成形体の密度を、JIS K7112に準拠して測定した。
i-ブチルメタクリレート(i-BMA)100部(1,000グラム)、n-オクチルメルカプタン0.02部、脱イオン水300部、ドデシルベンゼンスルホン酸ナトリウム1.1部を、ホモミキサーを用いて10,000rpmで6分間攪拌し、乳化混合物を得た。
温度計、窒素導入管、冷却管及び攪拌装置を備えたセパラブルフラスコ(容量5リットル)に、上記乳化混合物を投入し、容器内を窒素で置換した。次いで、内温を60℃まで昇温させて、過硫酸カリウム0.15部を加えた。
その後、加熱攪拌を2時間継続して重合を終了し、アルキル(メタ)アクリレート系重合体(A1)のラテックスを得た。得られたアルキルメタクリレート系重合体(A1)のラテックスを、酢酸カルシウム5部を含む熱水100部中に滴下して凝析を行なった。
凝析物を分離洗浄後、65℃で16時間乾燥して、アルキル(メタ)アクリレート系重合体(A1)を粉体の形態で得た。
アルキル(メタ)アクリレート系重合体(A1)のMwは100万であった。
単量体成分(a)の組成を表1に記載のように変更した以外は、製造例1と同様にしてアルキル(メタ)アクリレート系重合体(A)の製造を行なった。表1中、「n-BMA」はn-ブチルメタクリレートを、「MMA」はメチルメタクリレートを、「n-BA」はn-ブチルアクリレートを、それぞれ表す。
n-オクチルメルカプタンの量を0.05部と変更した以外は、製造例1と同様にしてアルキル(メタ)アクリレート系重合体(A8)の製造を行なった。
n-オクチルメルカプタンの量を0.05部と変更した以外は、製造例5と同様にしてアルキル(メタ)アクリレート系重合体(A9)の製造を行なった。
n-オクチルメルカプタンの量を0.22部と変更した以外は、製造例1と同様にしてアルキル(メタ)アクリレート系重合体(A10)の製造を行なった。
次の工程では、得られたアルキル(メタ)アクリレート系重合体(A)を、非発泡成形用加工助剤として用いる。アルキル(メタ)アクリレート系重合体(A)に対応する非発泡成形用加工助剤の番号を、表1に示す。
非発泡成形用加工助剤、塩化ビニル系樹脂(B)、及び各種添加剤を、以下に記載の量で20Lヘンシェルミキサ(機種名「FM20C/I」、日本コークス工業(株)製)を用いて混合し、115℃まで昇温した後に取り出して、非発泡成形用塩化ビニル系樹脂組成物を得た。
非発泡成形用加工助剤:1部
塩化ビニル系樹脂(B)(商品名「TK-1000」、信越化学工業(株)製、平均重合度1,000):100部(7,000グラム)
二塩基性亜燐酸鉛(商品名「DLP」、堺化学工業(株)製):2.5部
二塩基性ステアリン酸鉛(商品名「DS-2」、品川化工(株)製):0.7部
ステアリン酸鉛(商品名「NF-SP」、日産化学工業(株)製):0.9部
ステアリン酸カルシウム(商品名「NF-SC」、日産化学工業(株)製):0.5部
部分酸化ポリエチレンワックス(商品名「ハイワックス220MP」、三井化学(株)製):0.1部
酸化チタン(商品名「R-830」、石原産業(株)製):5部
軽質炭酸カルシウム(商品名「CC-R」、白石カルシウム(株)製):5部
アクリル系強化剤(商品名「メタブレンW-450A」、三菱レイヨン(株)製):5部
非発泡成形用加工助剤を表2に記載のように変更した以外は、実施例1と同様にして、塩化ビニル系樹脂成形体を得た。
また、比較例5においては、上記の配合組成に、以下に記載の添加剤を加えたものを用いた。それ以外は実施例1と同様にして、塩化ビニル系樹脂成形体を得た。
発泡剤 アゾジカルボンアミド(永和化成(株)製):1部
発泡剤 重曹(商品名「セルボンSC-P」、永和化成(株)製):0.7部
i-ブチルメタクリレート(a1)単位の含有率が65%未満であるアルキル(メタ)アクリレート系重合体を加工助剤として用いた比較例1及び6では、実施例と比べて樹脂組成物のゲル化時間が顕著に長い点でゲル化特性が劣り、成形体の表面外観も不良であった。
i-ブチルメタクリレート(a1)単位を含有しないアルキル(メタ)アクリレート系重合体を加工助剤として用いた比較例2及び3では、実施例と比べて最大トルク値が有意に大きい点でゲル化特性が劣り、成形体の表面外観も不良であった。
i-ブチルメタクリレート(a1)単位の含有率が65%以上であるアルキル(メタ)アクリレート系重合体を加工助剤として用いたが、発泡剤を含めたため成形体の密度が1.3g/cm3より低い比較例5では、樹脂組成物のゲル化特性は良好であったが、成形体の表面外観が不良であった。
i-ブチルメタクリレート(a1)単位の含有率が65%以上であり、Mwが11.4万のアルキル(メタ)アクリレート系重合体を加工助剤として用いた比較例7では、樹脂組成物のゲル化特性は良好であったが、成形体の表面外観が不良であった。
Claims (4)
- i-ブチルメタクリレート(a1)単位を65質量%以上含有し、質量平均分子量が20万~200万であるアルキル(メタ)アクリレート系重合体(A)からなる非発泡成形用加工助剤。
- 塩化ビニル系樹脂(B)100質量部に対して、請求項1記載の非発泡成形用加工助剤を0.1~30質量部含有する非発泡成形用塩化ビニル系樹脂組成物。
- 塩化ビニル系樹脂(B)100質量部に対して、請求項1記載の非発泡成形用加工助剤を0.1~30質量部含有し、
密度が1.3g/cm3以上である、塩化ビニル系樹脂成形体。 - 塩化ビニル系樹脂(B)100質量部に対して、請求項1記載の非発泡成形用加工助剤0.1~30質量部を配合し、
得られた塩化ビニル系樹脂組成物を押出成形する、
密度が1.3g/cm3以上の塩化ビニル系樹脂成形体の製造方法。
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WO2015045928A1 (ja) * | 2013-09-25 | 2015-04-02 | 三菱レイヨン株式会社 | 電線被覆材及び被覆された電線 |
WO2015045930A1 (ja) * | 2013-09-25 | 2015-04-02 | 三菱レイヨン株式会社 | 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 |
JP2015098578A (ja) * | 2013-10-18 | 2015-05-28 | 東亞合成株式会社 | (メタ)アクリル系重合体の製造方法及び(メタ)アクリル系重合体 |
JPWO2015108101A1 (ja) * | 2014-01-17 | 2017-03-23 | 三菱レイヨン株式会社 | 塩化ビニル樹脂組成物、及び塩化ビニル樹脂成形体 |
KR20200060929A (ko) * | 2018-11-23 | 2020-06-02 | 주식회사 엘지화학 | 코어-쉘 공중합체 조성물, 이의 제조방법 및 이를 포함하는 열가소성 수지 조성물 |
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