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WO2009122681A1 - Particulate powder of hydrotalcite type compound, chlorinated-resin stabilizer comprising the particulate powder of hydrotalcite type compound, and chlorinated-resin composition - Google Patents

Particulate powder of hydrotalcite type compound, chlorinated-resin stabilizer comprising the particulate powder of hydrotalcite type compound, and chlorinated-resin composition Download PDF

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Publication number
WO2009122681A1
WO2009122681A1 PCT/JP2009/001335 JP2009001335W WO2009122681A1 WO 2009122681 A1 WO2009122681 A1 WO 2009122681A1 JP 2009001335 W JP2009001335 W JP 2009001335W WO 2009122681 A1 WO2009122681 A1 WO 2009122681A1
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WIPO (PCT)
Prior art keywords
hydrotalcite
type compound
chlorine
resin composition
particle powder
Prior art date
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PCT/JP2009/001335
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French (fr)
Japanese (ja)
Inventor
山本学武
小林斉也
本名虎之
Original Assignee
戸田工業株式会社
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Application filed by 戸田工業株式会社 filed Critical 戸田工業株式会社
Priority to CN200980111183.1A priority Critical patent/CN101980963B/en
Publication of WO2009122681A1 publication Critical patent/WO2009122681A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
    • C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
    • C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
    • C01F7/785—Hydrotalcite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Definitions

  • the present invention can suppress a decrease in electrical insulation derived from hydrotalcite-type compound particle powder, and has excellent thermal stability of the chlorine-containing resin, and can suppress resin coloring. It is.
  • Hydrotalcite is generally a layered compound represented by Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O, and CO 3 , H 2 O, OH ⁇ are inserted between layers of Mg—Al.
  • Mg 2+ in the structure can be replaced with divalent cations such as Ni 2+ , Zn 2+ , Sr 2+ and Ca 2+
  • Al 3+ can be replaced with Fe 3+ , Cr 3+, etc. It can be replaced with a trivalent cation.
  • CO 3 2 ⁇ can also be exchanged for anions such as SO 4 2+ and Cl ⁇ .
  • the structure can be maintained even when the molar ratio of divalent and trivalent cations is changed, and a layered structure can be formed in a molar ratio of 2 to 4.
  • Layered compounds in which the composition of these constituent elements and the ratio of divalent and trivalent cations are changed are generally called hydrotalcite compounds.
  • stabilizers for wire coating applications are rapidly changing to those containing hydrotalcite type compounds.
  • hydrotalcite-type compounds are used as stabilizers for wire coating applications, the electrical resistance tends to decrease, and it can be used for low-voltage wires.
  • Pb-based stabilizers with high electrical insulation are still used.
  • Hydrotalcite-type compound particles contain trace amounts of impurity ions such as sulfate ions and sodium ions in the structure and in the vicinity of the surface, and are considered to be a cause of lowering electrical insulation. These ions are also a cause of deterioration of resin coloring and thermal stability.
  • the present invention is Mg-Al-based or Mg-Zn-Al-based hydrotalcite-type compound particle powder characterized in that the total value of soluble anions is 70 ppm or less (Invention 1).
  • a chlorine-containing resin stabilizer for stabilizing a chlorine-containing resin composition using the hydrotalcite-type compound particle powder according to the first or second aspect of the invention (Invention 3).
  • the step of washing is the production method according to the fifth aspect of the present invention, wherein the washing is performed with a dilute alkaline aqueous solution and then further washed with water (the seventh aspect of the present invention).
  • the manufacturing method according to the sixth aspect of the present invention wherein the temperature of the dilute alkaline aqueous solution and / or water used in the washing step is 30 to 90 ° C. (the present invention 8).
  • the resin can have high electrical insulation. Moreover, thermal stability and coloring can also be improved.
  • hydrotalcite-type compound particle powder according to the present invention will be described.
  • the hydrotalcite-type compound is composed of Mg, Al, Zn, etc., and is commonly used as Mg-Al type or Mg-Zn-Al. It is written as a system.
  • the composition of the hydrotalcite type compound particle powder according to the present invention is not particularly limited.
  • the generally known Mg / Al molar ratio is preferably 1.0 to 3.5
  • Mg— Zinc in the Al—Zn system is preferably in a molar ratio of 0.0010 to 0.30 with respect to the total number of moles of Mg and Al, and expressed as a Zn / Al molar ratio of about 0.005 to 0.5. preferable.
  • the total value of soluble anions (soluble sulfate ion, soluble nitrate ion and soluble chloride ion) contained in the hydrotalcite-type compound particle powder according to the present invention is 70 ppm or less. If the amount of these soluble anions is large, high electrical insulation cannot be obtained. In particular, bivalent sulfate ions have a greater adverse effect on electrical insulation than monovalent ions.
  • the soluble anion is preferably 60 ppm or less, more preferably 50 ppm or less. The lower limit is usually about 5 ppm.
  • the sodium contained in the hydrotalcite-type compound particle powder according to the present invention is preferably 700 ppm or less. If there is little sodium contained, possibility that the sodium which melt
  • Preferably sodium is 600 ppm or less, and even more preferably 550 ppm or less. In addition, a lower limit is about 20 ppm normally.
  • the specific surface area of the hydrotalcite-type compound particle powder according to the present invention is 5 to 150 m 2 / g. Hydrotalcite-type compound particles of less than 5 m 2 / g are difficult to obtain industrially. Even if it exceeds 150 m 2 / g, it is difficult to obtain industrially. It is preferably 7 to 100 m 2 / g, more preferably 8 to 50 m 2 / g.
  • the hydrotalcite type compound particle powder according to the present invention may contain about 0.01 to 5 wt% of calcium.
  • the hydrotalcite-type compound particle powder according to the present invention may contain about 0.01 to 8 wt% of zinc oxide.
  • the average plate surface diameter of the hydrotalcite-type compound particle powder according to the present invention is preferably 0.05 to 0.8 ⁇ m.
  • the hydrotalcite-type compound particle powder in the present invention is prepared by mixing an alkaline aqueous solution containing anions, a magnesium salt aqueous solution and an aluminum salt aqueous solution to obtain a mixed solution having a pH value in the range of 10 to 14, and then mixing the mixed solution.
  • the magnesium added to the aqueous suspension containing the core particles at the time of forming the core particles by aging in the temperature range of 80 to 105 ° C. to form core particles of Mg—Al hydrotalcite type particles.
  • the pH value is 10 to 14.
  • a core at normal pressure that is aged in the range of 60 to 105 ° C to obtain Mg-Al hydrotalcite-type particle powder Growth and reaction (JP-2002-293535) for the child, it is desirable to use a generated by 105 ⁇ 350 ° C. using an autoclave.
  • raw materials such as sulfate metal, nitrate metal, chloride salt metal, and metal oxide, alkali such as caustic soda and potassium hydroxide, sodium carbonate, basic magnesium carbonate, carbonate What is necessary is just to produce from anion source materials, such as potassium.
  • a slurry after the target hydrotalcite-type compound particles are generated and aged, or
  • the slurry after the treatment such as the hydrophobizing surface treatment is preferably adjusted to pH 9.5 to 12, more preferably 9.8 to 11.5.
  • anions such as sulfate ions are likely to be lowered by washing (water washing). Sodium tends to fall relatively easily with water washing, but soluble anions such as soluble sulfate ions, soluble nitrate ions and soluble chloride ions are difficult to reduce simply by washing.
  • washing with a thin alkaline aqueous solution first to reduce anions such as sulfate ions, and then washing with water further reduces the anions such as sulfate ions.
  • An alkaline aqueous solution such as sodium hydroxide or sodium carbonate may be used as the thin alkaline aqueous solution used for pH adjustment of the slurry containing the hydrotalcite-type particle powder and washing before washing with water.
  • the temperature of the thin alkaline aqueous solution and / or the thin alkaline aqueous solution and / or water used for washing is preferably 30 to 90 ° C.
  • the diffusion rate of ions is improved, and the viscosity of water is further lowered to enhance the washing effect. More preferably, it is 40 to 70 ° C.
  • the hydrotalcite-type compound particle powder obtained as described above is preferably basically dried at 105 to 150 ° C. At a drying temperature of less than 105 ° C., the resulting hydrotalcite-type compound particle powder has a large amount of water, so that foaming is likely to occur in the resin. When the temperature exceeds 150 ° C., the function of suppressing deterioration of the resin tends to decrease as a stabilizer for soft to semi-rigid chlorine-containing resin compositions. In the use of a soft to semi-rigid chlorine-containing resin composition as a stabilizer, the drying temperature is more preferably 105 to 130 ° C. The drying time may be as long as necessary depending on the amount of drying and the drying method. Preferably, it is 3 to 24 h.
  • the hydrotalcite-type compound particle powder of the present invention 1 or 2 can be used as a chlorine-containing resin stabilizer added to a chlorine-containing resin composition.
  • the chlorine-containing resin composition according to the present invention preferably contains 0.01 to 10 parts by weight of the hydrotalcite-type compound particle powder with respect to 100 parts by weight of the resin.
  • the content of the hydrotalcite-type compound particle powder is less than 0.01 parts by weight, the effect as a stabilizer is low.
  • the amount exceeds 10 parts by weight the effect is saturated, so there is no point in adding more than necessary.
  • foaming is likely to occur, which may have adverse effects such as poor appearance and initial coloration.
  • the resin may contain a plasticizer, other stabilizers and additives.
  • plasticizer examples include trioctyl ester plasticizers such as trioctyl trimellitate (TOTM) and tri-n-octyl-n-decyl trimellitate, diirodecyl phthalate (DIDP), diisononyl phthalate (DINP), di- Preferred are phthalate plasticizers such as -2-ethylhexyl phthalate (DOP), and polyester plasticizers such as polypropylene / adipate and polypropylene / sebacate.
  • TOTM trioctyl trimellitate
  • DIDP diirodecyl phthalate
  • DINP diisononyl phthalate
  • di- Preferred are phthalate plasticizers such as -2-ethylhexyl phthalate (DOP), and polyester plasticizers such as polypropylene / adipate and polypropylene / sebacate.
  • stabilizers include zinc compounds such as zinc stearate, zinc laurate, zinc ricinoleate, ⁇ -diketones such as dibenzoylmethane, stearoylbenzoylmethane, dehydroacetic acid, alkylallyl phosphates, trialkyl phosphates, etc. Phosphites, dipentaerythritol, pentaerythritol, polyhydric alcohol compounds such as glycerin, diglycerin, trimethylolpropane, higher fatty acids such as stearic acid, lauric acid, oleic acid, epoxidized linseed oil, epoxidized soybean oil, etc. Of these, epoxy compounds are preferred.
  • additives include phenolic compounds, amine compounds, phosphoric acid compounds and other antioxidants, polyesters with OH-terminated polyester, acrylonitrile-styrene copolymers, and methyl methacrylate styrene copolymers.
  • Accelerator extenders such as calcium carbonate, silica, glass beads, mica, glass fiber, inorganic flame retardants such as antimony trioxide, aluminum hydroxide, zinc borate, bromine-containing organic flame retardants, halogen phosphate ester-based flame retardants Flame retardants such as flame retardants, lubricants such as stearic acid, polyethylene wax, calcium stearate, magnesium stearate, barium stearate, anti-fungal agents such as triclosan, orthoside, sun isol 100, sun isol 300 and the like are used.
  • inorganic flame retardants such as antimony trioxide, aluminum hydroxide, zinc borate, bromine-containing organic flame retardants, halogen phosphate ester-based flame retardants
  • Flame retardants such as flame retardants, lubricants such as stearic acid, polyethylene wax, calcium stearate, magnesium stearate, barium stearate, anti-fungal agents such as triclosan, orthoside, sun is
  • hydrotalcite-type compound according to the present invention When used as a chlorine-containing resin composition, a higher fatty acid, an anionic surfactant, a higher fatty acid phosphate, a coupling agent, and a polyhydric alcohol ester are added to the hydrotalcite-type compound. It is preferable to perform at least one surface treatment selected from By applying the surface treatment, a further stability of the chlorine-containing resin composition can be imparted.
  • Examples of the higher fatty acid include lauric acid, stearic acid, palmitic acid, oleic acid, and linoleic acid.
  • Examples of the higher fatty acid phosphate ester include stearyl ether phosphoric acid, oleyl ether phosphoric acid, and lauryl ether phosphoric acid.
  • Examples of the polyhydric alcohol ester include sorbitan monooleate, sorbitan monolaurate, and stearic acid monoglyceride.
  • anionic surfactant examples include salts such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium stearate, potassium oleate, and potassium castor oil.
  • a silane-based, aluminum-based, titanium-based, zirconium-based coupling agent or the like can be used as the coupling agent.
  • the treatment method of the surface treatment agent is not particularly limited, but may be performed on the surface of the hydrotalcite type compound particles by a wet reaction.
  • the surface of the hydrotalcite compound particles may be subjected to a dry surface treatment using a Henschel mixer or the like.
  • the hydrotalcite type compound particles and the surface treatment agent may be simply mixed.
  • the hydrotalcite according to the present invention is a chlorine-containing resin composition having the following composition:
  • the type compound is used, 0.8 parts by weight of zinc stearate has a level 3 time of 65 minutes or more and a level 5 time of 100 minutes or more at the coloring level described later.
  • Chlorine-containing resin degree of polymerization 1000: Taiyo PVC TH1000 manufactured by Taiyo PVC Co., Ltd. 100 parts by weight Di-2-ethylhexyl phthalate (DOP manufactured by Daihachi Chemical) 0 to 25 parts by weight Hydrotalcite type compound particle powder 3.5 parts by weight Zinc stearate (general reagent) 0.6 to 0.9 parts by weight
  • the level 3 time is 65 minutes at the coloring level described later.
  • the level 5 time is 100 minutes or longer.
  • Chlorine-containing resin degree of polymerization 1000
  • Taiyo PVC TH1000 manufactured by Taiyo PVC Co., Ltd. 100 parts by weight Di-2-ethylhexyl phthalate (DOP manufactured by Daihachi Chemical) 40-80 parts by weight
  • Hydrotalcite compound of the present invention 3.0 parts by weight
  • Zinc stearate (general reagent) 0.6 parts by weight
  • the chlorine-containing resin composition according to the present invention preferably has a volume resistivity value of 2.0 ⁇ 10 14 ⁇ ⁇ cm or more, although it varies depending on the application.
  • the chlorine-containing resin composition according to the present invention can be obtained by an ordinary production method. For example, when obtaining a kneaded sheet, the resin, the hydrotalcite-type compound particle powder and the above various stabilizers and additives are added. It is obtained by mixing a predetermined amount, kneading the mixture with a hot roll to obtain a kneaded sheet, and then pressurizing with a hot press.
  • the kneading temperature of the hot roll varies depending on the resin and resin composition used, but is preferably 140 to 300 ° C.
  • the press temperature of the hot press is preferably 145 to 320 ° C.
  • the hydrotalcite-type compound particle powder according to the present invention was used as a resin stabilizer because it has a low content of soluble anions such as soluble sulfate ions, soluble nitrate ions and soluble chloride ions having electrical conductivity.
  • soluble anions such as soluble sulfate ions, soluble nitrate ions and soluble chloride ions having electrical conductivity.
  • a resin composition having high electrical insulation is obtained.
  • resin burning due to salt can be suppressed, and a resin composition having high thermal stability and suppressed coloring can be obtained.
  • a higher effect will be acquired.
  • a typical embodiment of the present invention is as follows.
  • the content of elements such as sodium, magnesium, aluminum, zinc, and calcium is obtained by dissolving a sample with an acid and analyzing it with a plasma emission spectroscopic analyzer (manufactured by Thermo Electron Co., Ltd., iCAP6500) using yttrium as an internal standard. It was.
  • the method for measuring soluble anions is described below. Disperse 5 g of sample in 40 ml of ethanol, add 100 ml of ultrapure water, shake in a sealed container for 1 minute, leave it at 22 ° C. for 20 hours, filter this slurry, and replenish ultrapure water. The filtrate was boiled for 60 minutes to evaporate ethanol, cooled, and the liquid volume was adjusted to 100 ml with ultrapure water. This was analyzed with an ion chromatograph (Toa DKK, ICA-2000) to measure sulfate ion, nitrate ion, and chloride ion, respectively.
  • ion chromatograph Toa DKK, ICA-2000
  • Specific surface area value is B. using nitrogen.
  • Resin roll kneading was carried out by adjusting the temperature to 140 to 190 ° C. according to the resin composition using a 6-inch two-piece type. The kneading time was 5 minutes.
  • the roll-kneaded sheet was formed into a compression molded body of 200 ⁇ 200 ⁇ 1 to 1.5 mm.
  • the heating press was a 70-ton automatic press (ram area 210 cm 2 )
  • the cooling press was a 30-ton manual press (ram area 180 cm 2 ).
  • the compression molding conditions were 140-190 ° C., preheating (no pressure) for 3 minutes, pressurizing (6.3 MPa) for 2 minutes, and cooling (3.1 MPa) for 3 minutes.
  • the thermal stability test was performed with a gear aging type tester (manufactured by Yasuda Seiki Seisakusho, 102-SHF-77S).
  • the pressed sheet was cut into 30 ⁇ 30 mm squares, placed on a glass plate, tested at 190 ° C. for 200 minutes, and taken out every 2 minutes / sample for 10 minutes. Pasted on paper.
  • the coloring levels of the press sheet and the thermal stability test piece are defined as 1 to 7 as follows.
  • Example 1 (Preparation of hydrotalcite-type compound particle powder) A slurry in which 26.9 g of magnesium oxide was dispersed in pure water and an aqueous solution of 81.0 g of aluminum sulfate octahydrate crystals were mixed with stirring. Separately, 35.7 g of sodium carbonate crystals were dissolved in pure water, and 58.3 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into a slurry obtained by mixing the above magnesium oxide and aluminum sulfate octahydrate, heated to 80 ° C., and stirred at 80 ° C. for 5 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 175 ° C. for 4 hours.
  • reaction slurry was stirred and brought to 67 ° C., and the pH was adjusted to 10.3.
  • a solution prepared by dissolving 2.3 g of sodium palmitate in hot water (80 ° C.) was added. This was aged for 0.7 hours. After filtration, it was washed with 2 L of a thin caustic soda solution having a pH of 11.5 at 40 ° C., then washed with 15 L of 40 ° C. pure water, and dried at 125 ° C. for 8 hours.
  • the specific surface area of the obtained sample was 11.0 m 2 / g.
  • Chlorine-containing resin composition 100phr DOP 55 phr Zinc stearate 0.6 phr Sample above 3.0 phr
  • Example 2 (Preparation of hydrotalcite-type compound particle powder) 141.0 g of magnesium sulfate heptahydrate crystals, 41.5 g of zinc sulfate heptahydrate crystals and 69.4 g of aluminum sulfate octahydrate crystals were dissolved in pure water. Separately, 30.6 g of sodium carbonate crystals were dissolved in pure water, and 152.4 ml of caustic soda (12N) and pure water were further added.
  • This alkaline solution was put into an aqueous solution in which the magnesium sulfate heptahydrate crystals, zinc sulfate heptahydrate crystals and aluminum sulfate octahydrate were mixed, heated to 85 ° C., and stirred at 85 ° C. for 6 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 185 ° C. for 6 hours.
  • reaction slurry was stirred and brought to 65 ° C. to adjust the pH to 10.1.
  • a solution prepared by dissolving 2.5 g of sodium stearate in hot water (80 ° C.) was added. This was aged for 0.6 hours. After filtration, it was washed with 2 L of a thin aqueous solution of caustic soda having a pH of 11 at 50 ° C., then washed with 15 L of pure water at 50 ° C., and dried at 125 ° C. for 8 hours.
  • the specific surface area of the obtained sample was 10.0 m 2 / g.
  • Chlorine-containing resin composition 100phr DOP 55 phr Zinc stearate 0.6 phr Sample above 3.0 phr
  • Example 3 (Preparation of hydrotalcite-type compound particle powder) 176.3 g of magnesium sulfate heptahydrate crystals and 69.4 g of aluminum sulfate octahydrate crystals were dissolved in pure water. Separately, 30.6 g of sodium carbonate crystals were dissolved in pure water, and 152.4 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into an aqueous solution in which the magnesium sulfate heptahydrate crystal and aluminum sulfate octahydrate were mixed, heated to 90 ° C., and stirred at 90 ° C. for 10 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 145 ° C. for 6 hours.
  • reaction slurry was stirred and brought to 65 ° C., and the pH was adjusted to 11.2.
  • a solution prepared by dissolving 1.9 g of sodium laurate in hot water (80 ° C.) was added. This was aged for 0.8 hours. After filtration, it was washed with 2 L of a thin caustic soda solution having a pH of 12.5 at 45 ° C., then washed with 15 L of pure water at 45 ° C., and dried at 125 ° C. for 8 hours.
  • the specific surface area of the obtained sample was 9.0 m 2 / g.
  • Chlorine-containing resin composition 100phr DOP 20 phr Zinc stearate 0.8 phr Sample above 3.5phr
  • Example 4 (Preparation of hydrotalcite-type compound particle powder) Magnesium chloride hexahydrate crystal 101.9 g, zinc chloride monohydrate crystal 26.0 g crystal and aluminum chloride hexahydrate crystal 80.5 g were dissolved in pure water. Separately, 35.7 g of sodium carbonate crystals were dissolved in pure water, and 136.1 ml of caustic soda (12N) and pure water were added. This alkaline solution was put into an aqueous solution obtained by mixing the above magnesium chloride hexahydrate crystal, zinc chloride monohydrate crystal and aluminum chloride hexahydrate, heated to 95 ° C., and stirred at 95 ° C. for 8 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 165 ° C. for 7 hours.
  • reaction slurry was stirred and brought to 70 ° C., and the pH was adjusted to 9.9.
  • a solution prepared by dissolving 2.5 g of sodium palmitate in hot water (80 ° C.) was added. This was aged for 0.7 hours. After filtration, it was washed with 2 L of an aqueous solution of thin caustic soda having a pH of 11 at 45 ° C., then washed with 16 L of pure water at 45 ° C., and dried at 125 ° C. for 8 hours.
  • the specific surface area of the obtained sample was 10.2 m 2 / g.
  • Chlorine-containing resin composition 100phr DOP 55 phr Zinc stearate 0.6 phr Sample above 3.0 phr
  • Example 5 (Preparation of hydrotalcite-type compound particle powder) Magnesium chloride hexahydrate crystals 141.0 g and aluminum chloride hexahydrate crystals 74.3 g were dissolved in pure water. Separately, 32.9 g of sodium carbonate crystals were dissolved in pure water, and 163.5 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into an aqueous solution in which the magnesium chloride hexahydrate crystals and aluminum chloride hexahydrate were mixed, heated to 75 ° C., and stirred at 75 ° C. for 15 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 170 ° C. for 9 hours.
  • reaction slurry was stirred and brought to 70 ° C., and the pH was adjusted to 10.9.
  • a solution prepared by dissolving 2.0 g of sodium laurate in hot water (80 ° C.) was added. This was aged for 0.9 hours. After filtration, it was washed with 2 L of an aqueous solution of thin caustic soda having a pH of 12 at 40 ° C., then washed with 15 L of pure water at 40 ° C., and dried at 125 ° C. for 8 hours.
  • the specific surface area of the obtained sample was 10.4 m 2 / g.
  • Chlorine-containing resin composition 100phr DOP 55 phr Zinc stearate 0.6 phr Sample above 3.0 phr
  • Example 6 (Preparation of hydrotalcite-type compound particle powder) 149.8 g of magnesium nitrate hexahydrate crystals, 25.0 g of zinc nitrate hexahydrate crystals and 125.0 g of aluminum nitrate 9 hydrate crystals were dissolved in pure water. Separately, 35.7 g of sodium carbonate crystals were dissolved in pure water, and 126.4 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into an aqueous solution obtained by mixing the above magnesium nitrate hexahydrate crystal, zinc nitrate hexahydrate crystal and aluminum nitrate nonahydrate, heated to 90 ° C., and stirred at 90 ° C. for 10 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 175 ° C. for 8 hours.
  • reaction slurry was stirred and brought to 62 ° C., and the pH was adjusted to 10.0.
  • a solution prepared by dissolving 2.5 g of sodium stearate in hot water (80 ° C.) was added. This was aged for 0.6 hours. After filtration, it was washed with 2 L of a thin caustic soda solution having a pH of 11.5 at 45 ° C., then washed with 15 L of pure water at 45 ° C., and dried at 125 ° C. for 8 hours.
  • the specific surface area of the obtained sample was 9.8 m 2 / g.
  • Chlorine-containing resin composition 100phr TOTM 60phr Zinc stearate 0.7 phr Sample above 3.3 phr
  • Example 7 (Preparation of hydrotalcite-type compound particle powder) 171.2 g of magnesium nitrate hexahydrate crystals and 125.0 g of aluminum nitrate 9 hydrate crystals were dissolved in pure water. Separately, 35.7 g of sodium carbonate crystals were dissolved in pure water, and 126.4 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into an aqueous solution in which the magnesium nitrate hexahydrate crystal and the aluminum nitrate nonahydrate were mixed, heated to 90 ° C., and stirred at 90 ° C. for 10 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 130 ° C. for 5 hours.
  • reaction slurry was stirred and brought to 62 ° C., and the pH was adjusted to 10.0.
  • a solution prepared by dissolving 2.5 g of sodium stearate in hot water (80 ° C.) was added. This was aged for 0.6 hours. After filtration, it was washed with 3 L of a thin caustic soda solution having a pH of 11 at 60 ° C., then washed with 25 L of pure water at 60 ° C., and dried at 125 ° C. for 8 hours.
  • the specific surface area of the obtained sample was 19.2 m 2 / g.
  • Chlorine-containing resin composition 100phr DOP 55 phr Zinc stearate 0.6 phr Sample above 3.0 phr
  • Example 8 (Preparation of hydrotalcite-type compound particle powder) 176.3 g of magnesium sulfate heptahydrate crystals and 69.4 g of aluminum sulfate octahydrate crystals were dissolved in pure water. Separately, 30.6 g of sodium carbonate crystals were dissolved in pure water, and 152.4 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into an aqueous solution in which the magnesium sulfate heptahydrate crystal and aluminum sulfate octahydrate were mixed, heated to 90 ° C., and stirred at 90 ° C. for 10 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 145 ° C. for 6 hours.
  • reaction slurry was stirred and brought to 65 ° C., and the pH was adjusted to 11.9.
  • a solution prepared by dissolving 1.9 g of sodium laurate in hot water (80 ° C.) was added. This was aged for 0.8 hours. After filtration, it was washed with 2 L of a thin caustic soda solution having a pH of 13 at 40 ° C., then washed with 15 L of pure water at 45 ° C., and dried at 125 ° C. for 8 hours.
  • the specific surface area of the obtained sample was 9.3 m 2 / g.
  • Chlorine-containing resin composition 100phr DOP 20 phr Zinc stearate 0.8 phr Sample above 3.5phr
  • Example 9 (Preparation of hydrotalcite-type compound particle powder) Magnesium chloride hexahydrate crystal 101.9 g, zinc chloride monohydrate crystal 26.0 g crystal and aluminum chloride hexahydrate crystal 80.5 g were dissolved in pure water. Separately, 35.7 g of sodium carbonate crystals were dissolved in pure water, and 136.1 ml of caustic soda (12N) and pure water were added. This alkaline solution was put into an aqueous solution obtained by mixing the above magnesium chloride hexahydrate crystal, zinc chloride monohydrate crystal and aluminum chloride hexahydrate, heated to 95 ° C., and stirred at 95 ° C. for 8 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 165 ° C. for 7 hours.
  • reaction slurry was stirred and brought to 70 ° C., and the pH was adjusted to 11.7.
  • a solution prepared by dissolving 2.5 g of sodium palmitate in hot water (80 ° C.) was added. This was aged for 0.7 hours. After filtration, it was washed with 2 L of a thin caustic soda solution having a pH of 13 at 55 ° C., then washed with 16 L of pure water at 45 ° C., and dried at 125 ° C. for 8 hours.
  • the specific surface area of the obtained sample was 10.1 m 2 / g.
  • Chlorine-containing resin composition 100phr DOP 55 phr Zinc stearate 0.6 phr Sample above 3.0 phr
  • Example 10 (Preparation of hydrotalcite-type compound particle powder) Magnesium chloride hexahydrate crystals 141.0 g and aluminum chloride hexahydrate crystals 74.3 g were dissolved in pure water. Separately, 32.9 g of sodium carbonate crystals were dissolved in pure water, and 203.5 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into an aqueous solution in which magnesium chloride hexahydrate crystals and aluminum chloride hexahydrate were mixed, and then an aqueous solution in which 4.50 g of calcium chloride dihydrate crystals were dissolved was added, and the temperature was raised to 75 ° C. did. Stir at 75 ° C. for 15 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 170 ° C. for 9 hours.
  • reaction slurry was stirred and brought to 70 ° C., and the pH was adjusted to 10.9.
  • a solution prepared by dissolving 2.0 g of sodium laurate in hot water (80 ° C.) was added. This was aged for 0.9 hours. After filtration, it was washed with 2 L of an aqueous solution of thin caustic soda having a pH of 12 at 40 ° C., then washed with 15 L of pure water at 40 ° C., and dried at 125 ° C. for 8 hours.
  • the specific surface area of the obtained sample was 10.0 m 2 / g.
  • the molar ratio of Mg / Ca / Al was 2.40 / 0.10 / 1.00.
  • Chlorine-containing resin composition 100phr DOP 55 phr Zinc stearate 0.6 phr Sample above 3.0 phr
  • Example 11 (Preparation of hydrotalcite-type compound particle powder) 101.9 g of magnesium chloride hexahydrate crystals, 23.4 g of zinc chloride monohydrate crystals and 80.5 g of aluminum chloride hexahydrate crystals were dissolved in pure water. Separately, 35.7 g of sodium carbonate crystals were dissolved in pure water, and 136.1 ml of caustic soda (12N) and pure water were added. This alkaline solution was put into an aqueous solution obtained by mixing the above magnesium chloride hexahydrate crystal, zinc chloride monohydrate crystal and aluminum chloride hexahydrate, heated to 95 ° C., and stirred at 95 ° C. for 8 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 165 ° C. for 7 hours. Thereafter, 1.4 g of zinc oxide was added and mixed.
  • reaction slurry was stirred and brought to 70 ° C., and the pH was adjusted to 11.7.
  • a solution prepared by dissolving 2.5 g of sodium palmitate in hot water (80 ° C.) was added. This was aged for 0.7 hours. After filtration, it was washed with 2 L of a thin aqueous solution of caustic soda having a pH of 12.5 at 45 ° C., then washed with 16 L of pure water at 45 ° C., and dried at 125 ° C. for 8 hours.
  • the specific surface area of the obtained sample was 10.7 m 2 / g.
  • Chlorine-containing resin composition 100phr DOP 55 phr Zinc stearate 0.6 phr Sample above 3.0 phr
  • Comparative Example 1 (Preparation of hydrotalcite-type compound particle powder) A slurry in which 26.9 g of magnesium oxide was dispersed in pure water and an aqueous solution of 81.0 g of aluminum sulfate octahydrate crystals were mixed with stirring. Separately, 35.7 g of sodium carbonate crystals were dissolved in pure water, and 58.3 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into a slurry obtained by mixing the above magnesium oxide and aluminum sulfate octahydrate, heated to 80 ° C., and stirred at 80 ° C. for 5 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 175 ° C. for 4 hours.
  • reaction slurry was stirred and brought to 72 ° C., and the pH was adjusted to 8.9.
  • a solution prepared by dissolving 2.3 g of sodium palmitate in hot water (80 ° C.) was added. This was aged for 0.7 hours. After filtration, it was washed with 15 L of 40 ° C. pure water and dried at 125 ° C. for 8 hours.
  • the specific surface area of the obtained sample was 11.3 m 2 / g.
  • Chlorine-containing resin composition 100phr DOP 55 phr Zinc stearate 0.6 phr Sample above 3.0 phr
  • Comparative Example 2 (Preparation of hydrotalcite-type compound particle powder) 176.3 g of magnesium sulfate heptahydrate crystals and 69.4 g of aluminum sulfate octahydrate crystals were dissolved in pure water. Separately, 30.6 g of sodium carbonate crystals were dissolved in pure water, and 152.4 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into an aqueous solution in which the magnesium sulfate heptahydrate crystal and aluminum sulfate octahydrate were mixed, heated to 90 ° C., and stirred at 90 ° C. for 10 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 145 ° C. for 6 hours.
  • reaction slurry was stirred and brought to 65 ° C., and the pH was adjusted to 9.0.
  • a solution prepared by dissolving 1.9 g of sodium laurate in hot water (80 ° C.) was added. This was aged for 0.8 hours. After filtration, it was washed with 15 L of pure water at 45 ° C. and dried at 125 ° C. for 8 hours.
  • the specific surface area of the obtained sample was 9.5 m 2 / g.
  • Chlorine-containing resin composition 100phr DOP 20 phr Zinc stearate 0.8 phr Sample above 3.5phr
  • Comparative Example 3 (Preparation of hydrotalcite-type compound particle powder) Magnesium chloride hexahydrate crystal 101.9 g, zinc chloride monohydrate crystal 26.0 g crystal and aluminum chloride hexahydrate crystal 80.5 g were dissolved in pure water. Separately, 35.7 g of sodium carbonate crystals were dissolved in pure water, and 136.1 ml of caustic soda (12N) and pure water were added. This alkaline solution was put into an aqueous solution obtained by mixing the above magnesium chloride hexahydrate crystal, zinc chloride monohydrate crystal and aluminum chloride hexahydrate, heated to 95 ° C., and stirred at 95 ° C. for 8 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 165 ° C. for 7 hours.
  • reaction slurry was stirred and brought to 70 ° C., and the pH was adjusted to 9.1.
  • a solution prepared by dissolving 2.5 g of sodium palmitate in hot water (80 ° C.) was added. This was aged for 0.7 hours. After filtration, it was washed with 16 L of pure water at 45 ° C. and dried at 125 ° C. for 8 hours.
  • the specific surface area of the obtained sample was 9.5 m 2 / g.
  • Chlorine-containing resin composition 100phr DOP 55 phr Zinc stearate 0.6 phr Sample above 3.0 phr
  • Comparative Example 4 (Preparation of hydrotalcite-type compound particle powder) 171.2 g of magnesium nitrate hexahydrate crystals and 125.0 g of aluminum nitrate 9 hydrate crystals were dissolved in pure water. Separately, 35.7 g of sodium carbonate crystals were dissolved in pure water, and 126.4 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into an aqueous solution in which the magnesium nitrate hexahydrate crystal and the aluminum nitrate nonahydrate were mixed, heated to 90 ° C., and stirred at 90 ° C. for 10 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 130 ° C. for 5 hours.
  • reaction slurry was stirred and brought to 62 ° C., and the pH was adjusted to 8.6.
  • a solution prepared by dissolving 2.5 g of sodium stearate in hot water (80 ° C.) was added. This was aged for 0.6 hours. After filtration, it was washed with 25 L of pure water at 60 ° C. and dried at 125 ° C. for 8 hours.
  • the specific surface area of the obtained sample was 18.9 m 2 / g.
  • Chlorine-containing resin composition 100phr DOP 55 phr Zinc stearate 0.6 phr Sample above 3.0 phr
  • Comparative Example 5 (Preparation of hydrotalcite-type compound particle powder) 176.3 g of magnesium sulfate heptahydrate crystals and 69.4 g of aluminum sulfate octahydrate crystals were dissolved in pure water. Separately, 30.6 g of sodium carbonate crystals were dissolved in pure water, and 122.4 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into an aqueous solution in which the magnesium sulfate heptahydrate crystal and aluminum sulfate octahydrate were mixed, heated to 90 ° C., and stirred at 90 ° C. for 10 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 145 ° C. for 6 hours.
  • reaction slurry was stirred and brought to 65 ° C., and the pH was adjusted to 7.4.
  • a solution prepared by dissolving 1.9 g of sodium laurate in hot water (80 ° C.) was added. This was aged for 0.8 hours. After filtration, it was washed with 15 L of pure water at 45 ° C. and dried at 125 ° C. for 8 hours.
  • the specific surface area of the obtained sample was 9.7 m 2 / g.
  • Chlorine-containing resin composition 100phr DOP 20 phr Zinc stearate 0.8 phr Sample above 3.5phr
  • the electrical insulation, coloring and thermal stability of the resin composition can be improved by using the hydrotalcite particle powder according to the present invention. For this reason, the expansion to more applications becomes possible.

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Abstract

A particulate powder of an Mg-Al or Mg-Zn-Al hydrotalcite type compound, characterized by having a total content of soluble anions of 70 ppm or lower; a chlorinated-resin stabilizer for stabilizing a chlorinated-resin composition, the stabilizer comprising the particulate powder; and a chlorinated-resin composition comprising a chlorinated resin and the particulate powder contained therein. The particulate powder can be produced by yielding and aging hydrotalcite type compound particles, regulating the pH of the resultant slurry to 9.5-12, and then cleaning and drying the particles.

Description

ハイドロタルサイト型化合物粒子粉末、該ハイドロタルサイト型化合物粒子粉末を用いた含塩素樹脂安定剤及び含塩素樹脂組成物Hydrotalcite-type compound particle powder, chlorine-containing resin stabilizer and chlorine-containing resin composition using the hydrotalcite-type compound particle powder
　本発明は、含塩素樹脂組成物においてハイドロタルサイト型化合物粒子粉末由来の電気絶縁性の低下を抑制でき、且つ、優れた含塩素樹脂の熱安定性を有し、樹脂の着色を抑制できるものである。 In the chlorine-containing resin composition, the present invention can suppress a decrease in electrical insulation derived from hydrotalcite-type compound particle powder, and has excellent thermal stability of the chlorine-containing resin, and can suppress resin coloring. It is.
　近年、含塩素樹脂の安定化剤としてＰｂやＳｎから、無毒な金属石鹸類とハイドロタルサイト型化合物の組合せに変わりつつあり、含塩素樹脂を用いた材料は、電線被覆、フィルム、建材やパイプなど様々な用途で利用されている。 In recent years, as a stabilizer for chlorine-containing resins, Pb and Sn are changing to a combination of non-toxic metal soaps and hydrotalcite-type compounds, and materials using chlorine-containing resins include wire coatings, films, building materials and pipes. It is used for various purposes.
　ハイドロタルサイトは一般的に、Ｍｇ６Ａｌ２（ＯＨ）１６ＣＯ３・４Ｈ２Ｏで示される層状の化合物で、Ｍｇ－Ａｌからなる層の層間にＣＯ３、Ｈ２Ｏ、ＯＨ－が挿入されている。構造中のＭｇ２＋の一部もしくは全部をＮｉ２＋、Ｚｎ２＋、Ｓｒ２＋やＣａ２＋等の２価カチオンと置き換えることができ、同様にＡｌ３＋の一部もしくは全部をＦｅ３＋やＣｒ３＋等の３価カチオンと置き換えることができる。さらに、ＣＯ３ ２－もＳＯ４ ２＋やＣｌ－等のアニオンと交換することができる。また、一般的に２価と３価のカチオンのモル比を変えても構造を保持し、モル比が２～４の範囲で層状構造をとることができる。これら構成元素の組成や２価と３価のカチオンの比率を変えた層状の化合物を一般的にハイドロタルサイト型化合物と呼ぶ。 Hydrotalcite is generally a layered compound represented by Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O, and CO 3 , H 2 O, OH − are inserted between layers of Mg—Al. Has been. Part or all of Mg 2+ in the structure can be replaced with divalent cations such as Ni 2+ , Zn 2+ , Sr 2+ and Ca 2+ , and part or all of Al 3+ can be replaced with Fe 3+ , Cr 3+, etc. It can be replaced with a trivalent cation. Furthermore, CO 3 2− can also be exchanged for anions such as SO 4 2+ and Cl − . In general, the structure can be maintained even when the molar ratio of divalent and trivalent cations is changed, and a layered structure can be formed in a molar ratio of 2 to 4. Layered compounds in which the composition of these constituent elements and the ratio of divalent and trivalent cations are changed are generally called hydrotalcite compounds.
　特に電線被覆用途の安定剤では急激にハイドロタルサイト型化合物を含むものに変わりつつある。しかし、電線被覆用途の安定剤にハイドロタルサイト型化合物を用いると電気抵抗が低下する傾向があり、低電圧電線では、なんとか使用できるレベルであるが、高電圧電線では漏電しやすくなるので使用することが出来ず、依然として電気絶縁性の高いＰｂ系の安定剤が使用されている。 Especially, stabilizers for wire coating applications are rapidly changing to those containing hydrotalcite type compounds. However, if hydrotalcite-type compounds are used as stabilizers for wire coating applications, the electrical resistance tends to decrease, and it can be used for low-voltage wires. Pb-based stabilizers with high electrical insulation are still used.
　しかし、環境への配慮から高電圧電線でも脱Ｐｂが求められており、高い電気絶縁性を保持できるハイドロタルサイト型化合物が渇望されている。 However, in consideration of the environment, Pb removal is required even for high-voltage electric wires, and hydrotalcite-type compounds that can maintain high electrical insulation are desired.
　一般的に水溶液等では溶解したイオンを多く含むほど導電性は高くなり、樹脂中でも同様に導電性のイオンが多いほど樹脂の導電性が高くなる。言い換えれば導電性イオンが多いほど樹脂の電気絶縁性は低下する。 In general, in an aqueous solution or the like, the more the dissolved ions are contained, the higher the conductivity, and the more conductive ions in the resin, the higher the conductivity of the resin. In other words, the more conductive ions, the lower the electrical insulation of the resin.
　ハイドロタルサイト型化合物粒子はその構造中及び表面付近に硫酸イオンやナトリウムイオンの様な微量の不純物イオンを含んでおり、電気絶縁性を低下させる原因となっていると考えられる。また、これらのイオンは樹脂の着色や熱安定性を悪化させる原因ともなっている。 Hydrotalcite-type compound particles contain trace amounts of impurity ions such as sulfate ions and sodium ions in the structure and in the vicinity of the surface, and are considered to be a cause of lowering electrical insulation. These ions are also a cause of deterioration of resin coloring and thermal stability.
　これまで塩素含有樹脂の安定剤としてハイドロタルサイト型化合物を用いることが知られており（特許文献１～３）、ハイドロタルサイト型化合物粒子が含有するナトリウム量が少ないと電気抵抗が向上する傾向があることも知られている（特許文献２、３）。 It has been known that hydrotalcite-type compounds are used as stabilizers for chlorine-containing resins (Patent Documents 1 to 3), and electrical resistance tends to improve when the amount of sodium contained in hydrotalcite-type compound particles is small. It is also known that there are (Patent Documents 2 and 3).
特開２０００－２９０４５１号公報JP 2000-290451 A 特開２００７－１０６６２０号公報JP 2007-106620 A 国際公開第２００６／０４３３５２号パンフレットInternational Publication No. 2006/043352 Pamphlet
　前記特許文献１～３に記載されたハイドロタルサイト型化合物では、樹脂の電気絶縁性が十分とは言い難く、含塩素樹脂組成物の安定剤として優れた機能を有するとは言い難いものであった。 The hydrotalcite-type compounds described in Patent Documents 1 to 3 cannot be said to have an excellent function as a stabilizer for a chlorine-containing resin composition because the electrical insulation of the resin is not sufficient. It was.
　そこで、本発明は、溶出する導電性イオンが少ないハイドロタルサイト型化合物を提供し、該ハイドロタルサイト型化合物を含む高い電気絶縁性を持った樹脂を提供することを技術的課題とする。 Therefore, it is a technical object of the present invention to provide a hydrotalcite-type compound with a small amount of conductive ions to be eluted, and to provide a resin having high electrical insulation containing the hydrotalcite-type compound.
　前記技術的課題は、次の通りの本発明によって達成できる。 The technical problem can be achieved by the present invention as follows.
　即ち、本発明は、可溶性アニオンの合計値が７０ｐｐｍ以下であることを特徴とするＭｇ－Ａｌ系又はＭｇ－Ｚｎ－Ａｌ系ハイドロタルサイト型化合物粒子粉末である（本発明１）。 That is, the present invention is Mg-Al-based or Mg-Zn-Al-based hydrotalcite-type compound particle powder characterized in that the total value of soluble anions is 70 ppm or less (Invention 1).
　本発明１記載のハイドロタルサイト型化合物のうち含有するナトリウムが７００ｐｐｍ以下であることを特徴とするＭｇ－Ａｌ系又はＭｇ－Ｚｎ－Ａｌ系ハイドロタルサイト型化合物粒子粉末である（本発明２）。 Mg-Al-based or Mg-Zn-Al-based hydrotalcite-type compound particle powder characterized in that sodium contained in the hydrotalcite-type compound according to the present invention 1 is 700 ppm or less (Invention 2) .
　本発明１又は２に記載のハイドロタルサイト型化合物粒子粉末を用いた含塩素樹脂組成物を安定化させるための含塩素樹脂安定剤である（本発明３）。 A chlorine-containing resin stabilizer for stabilizing a chlorine-containing resin composition using the hydrotalcite-type compound particle powder according to the first or second aspect of the invention (Invention 3).
　本発明１又は２に記載のハイドロタルサイト型化合物粒子粉末を塩素含有樹脂中に含有することを特徴とする含塩素樹脂組成物である（本発明４）。 A chlorine-containing resin composition characterized in that the hydrotalcite-type compound particle powder described in the present invention 1 or 2 is contained in a chlorine-containing resin (invention 4).
　本発明１又は２に記載のハイドロタルサイト型化合物粒子粉末を塩素含有樹脂中に含有することを特徴とする含塩素樹脂組成物である（本発明５）。 A chlorine-containing resin composition characterized in that the hydrotalcite-type compound particle powder described in the present invention 1 or 2 is contained in a chlorine-containing resin (invention 5).
　本発明１又は２に記載のハイドロタルサイト型化合物粒子粉末の製造方法であって、ハイドロタルサイト型化合物粒子を生成および熟成させた後のスラリーを、ｐＨ９．５～１２に調節した後、洗浄し、乾燥することを特徴とするハイドロタルサイト型化合物粒子粉末の製造方法である（本発明６）。 The method for producing hydrotalcite-type compound particle powder according to the present invention 1 or 2, wherein the slurry after the hydrotalcite-type compound particles are generated and aged is adjusted to pH 9.5 to 12, and then washed. And drying the hydrotalcite-type compound particle powder (Invention 6).
　洗浄する工程が、希アルカリ水溶液で洗浄した後、さらに水洗する本発明５に記載の製造方法である（本発明７）。 The step of washing is the production method according to the fifth aspect of the present invention, wherein the washing is performed with a dilute alkaline aqueous solution and then further washed with water (the seventh aspect of the present invention).
　洗浄工程で使用する希アルカリ水溶液および／または水の温度が３０～９０℃である本発明６に記載の製造方法である（本発明８）。 The manufacturing method according to the sixth aspect of the present invention, wherein the temperature of the dilute alkaline aqueous solution and / or water used in the washing step is 30 to 90 ° C. (the present invention 8).
　本発明に係る溶出する導電性イオンが少ないハイドロタルサイト型化合物粒子粉末を用いることにより、樹脂に高い電気絶縁性を持たせることが出来る。また、熱安定性及び着色も改善することが出来る。 By using the hydrotalcite-type compound particle powder with less conductive ions to be eluted according to the present invention, the resin can have high electrical insulation. Moreover, thermal stability and coloring can also be improved.
　先ず、本発明に係るハイドロタルサイト型化合物粒子粉末について述べる。 First, the hydrotalcite-type compound particle powder according to the present invention will be described.
　本発明に係る溶出する導電性イオンが少ないハイドロタルサイト型化合物粒子粉末において、ハイドロタルサイト型化合物はＭｇ，Ａｌ，Ｚｎなどから構成されており、俗にＭｇ－Ａｌ系やＭｇ－Ｚｎ－Ａｌ系と表記されるものである。 In the hydrotalcite-type compound particle powder with less conductive ions to be eluted according to the present invention, the hydrotalcite-type compound is composed of Mg, Al, Zn, etc., and is commonly used as Mg-Al type or Mg-Zn-Al. It is written as a system.
　本発明に係るハイドロタルサイト型化合物粒子粉末の組成は特に限定されるものではないが、例えば、一般に知られているようなＭｇ／Ａｌモル比は１．０～３．５が好ましく、Ｍｇ－Ａｌ－Ｚｎ系での亜鉛はＭｇ及びＡｌの合計モル数に対してモル比で０．００１０～０．３０が好ましく、Ｚｎ／Ａｌのモル比で表すと、０．００５～０．５程度が好ましい。 The composition of the hydrotalcite type compound particle powder according to the present invention is not particularly limited. For example, the generally known Mg / Al molar ratio is preferably 1.0 to 3.5, and Mg— Zinc in the Al—Zn system is preferably in a molar ratio of 0.0010 to 0.30 with respect to the total number of moles of Mg and Al, and expressed as a Zn / Al molar ratio of about 0.005 to 0.5. preferable.
　本発明に係るハイドロタルサイト型化合物粒子粉末が含む可溶性アニオン（可溶性硫酸イオン、可溶性硝酸イオン及び可溶性塩化物イオン）の合計値は７０ｐｐｍ以下である。これらの可溶性アニオン量が多いと高い電気絶縁性が得られない。特に、価数が２価の硫酸イオンは１価のイオンに比べて電気絶縁性に対する悪影響が大きい。可溶性アニオンは好ましくは６０ｐｐｍ以下、より好ましくは５０ｐｐｍ以下である。なお、下限値は、通常５ｐｐｍ程度である。 The total value of soluble anions (soluble sulfate ion, soluble nitrate ion and soluble chloride ion) contained in the hydrotalcite-type compound particle powder according to the present invention is 70 ppm or less. If the amount of these soluble anions is large, high electrical insulation cannot be obtained. In particular, bivalent sulfate ions have a greater adverse effect on electrical insulation than monovalent ions. The soluble anion is preferably 60 ppm or less, more preferably 50 ppm or less. The lower limit is usually about 5 ppm.
　本発明に係るハイドロタルサイト型化合物粒子粉末が含むナトリウムは７００ｐｐｍ以下が好ましい。含有するナトリウムが少なければ溶解するナトリウムが少なくなる可能性が高くなる。ナトリウムイオンは可溶性アニオンよりも影響が少ないものの、ナトリウムが少ない方がより高い電気絶縁性が得られる。好ましくはナトリウムが６００ｐｐｍ以下であり、更により好ましくは５５０ｐｐｍ以下である。なお、下限値は、通常２０ｐｐｍ程度である。 The sodium contained in the hydrotalcite-type compound particle powder according to the present invention is preferably 700 ppm or less. If there is little sodium contained, possibility that the sodium which melt | dissolves will decrease will become high. Although sodium ions have less influence than soluble anions, higher electrical insulation is obtained with less sodium. Preferably sodium is 600 ppm or less, and even more preferably 550 ppm or less. In addition, a lower limit is about 20 ppm normally.
　本発明に係るハイドロタルサイト型化合物粒子粉末の比表面積は５～１５０ｍ２／ｇである。５ｍ２／ｇ未満のハイドロタルサイト型化合物粒子は工業的に得られにくい。１５０ｍ２／ｇを超えても工業的に得られにくい。好ましくは７～１００ｍ２／ｇ、より好ましくは８～５０ｍ２／ｇである。 The specific surface area of the hydrotalcite-type compound particle powder according to the present invention is 5 to 150 m 2 / g. Hydrotalcite-type compound particles of less than 5 m 2 / g are difficult to obtain industrially. Even if it exceeds 150 m 2 / g, it is difficult to obtain industrially. It is preferably 7 to 100 m 2 / g, more preferably 8 to 50 m 2 / g.
　本発明に係るハイドロタルサイト型化合物粒子粉末は、０．０１～５ｗｔ％程度のカルシウムを含有しても良い。 The hydrotalcite type compound particle powder according to the present invention may contain about 0.01 to 5 wt% of calcium.
　本発明に係るハイドロタルサイト型化合物粒子粉末は、０．０１～８ｗｔ％程度の酸化亜鉛を含有しても良い。 The hydrotalcite-type compound particle powder according to the present invention may contain about 0.01 to 8 wt% of zinc oxide.
　本発明に係るハイドロタルサイト型化合物粒子粉末の平均板面径は０．０５～０．８μｍが好ましい。 The average plate surface diameter of the hydrotalcite-type compound particle powder according to the present invention is preferably 0.05 to 0.8 μm.
　次に、本発明に係るハイドロタルサイト型化合物粒子粉末の製造法について述べる。 Next, a method for producing hydrotalcite-type compound particle powder according to the present invention will be described.
　本発明におけるハイドロタルサイト型化合物粒子粉末は、アニオンを含有したアルカリ性水溶液とマグネシウム塩水溶液とアルミニウム塩水溶液とを混合し、ｐＨ値が１０～１４の範囲の混合溶液とした後、該混合溶液を８０～１０５℃の温度範囲で熟成してＭｇ－Ａｌ系ハイドロタルサイト型粒子の芯粒子を生成させ、次いで、該芯粒子を含む水性懸濁液に、該芯粒子の生成時に添加した前記マグネシウムと前記アルミニウムとの合計モル数に対して、合計モル数が０．３５以下となる割合でマグネシウム及びアルミニウムを含有するマグネシウム塩水溶液とアルミニウム塩水溶液とを添加した後、ｐＨ値が１０～１４の範囲、温度が６０～１０５℃の範囲で熟成してＭｇ－Ａｌ系ハイドロタルサイト型粒子粉末を得るような常圧での芯粒子に対する成長反応（特開２００２－２９３５３５号公報）や、オートクレーブを用いて１０５～３５０℃にて生成されたものを用いることが望ましい。これらは、例えば、Ｍｇ，Ａｌ，Ｚｎについては硫酸塩金属、硝酸塩金属、塩化物塩金属、金属酸化物などの原料と、苛性ソーダや水酸化カリウムなどのアルカリ、炭酸ソーダや塩基性炭酸マグネシウム、炭酸カリウムなどのアニオン源原料から作製すればよい。 The hydrotalcite-type compound particle powder in the present invention is prepared by mixing an alkaline aqueous solution containing anions, a magnesium salt aqueous solution and an aluminum salt aqueous solution to obtain a mixed solution having a pH value in the range of 10 to 14, and then mixing the mixed solution. The magnesium added to the aqueous suspension containing the core particles at the time of forming the core particles by aging in the temperature range of 80 to 105 ° C. to form core particles of Mg—Al hydrotalcite type particles. After adding a magnesium salt aqueous solution containing magnesium and aluminum and an aluminum salt aqueous solution in a ratio such that the total number of moles is 0.35 or less with respect to the total number of moles of aluminum and aluminum, the pH value is 10 to 14. A core at normal pressure that is aged in the range of 60 to 105 ° C to obtain Mg-Al hydrotalcite-type particle powder Growth and reaction (JP-2002-293535) for the child, it is desirable to use a generated by 105 ~ 350 ° C. using an autoclave. For example, for Mg, Al, and Zn, raw materials such as sulfate metal, nitrate metal, chloride salt metal, and metal oxide, alkali such as caustic soda and potassium hydroxide, sodium carbonate, basic magnesium carbonate, carbonate What is necessary is just to produce from anion source materials, such as potassium.
　可溶性アニオン（可溶性硫酸イオン、可溶性硝酸イオン及び可溶性塩化物イオン）の少ないハイドロタルサイト型化合物粒子を作製するには、目標とするハイドロタルサイト型化合物粒子を生成及び熟成させた後のスラリー、又は疎水化表面処理などの処理を行った後のスラリーを、ｐＨ９．５～１２に調節することが好ましく、より好ましいｐＨは９．８～１１．５である。前記ｐHの範囲に調整することで硫酸イオン等のアニオンが洗浄（水洗）で低下しやすくなる。ナトリウムは水洗で比較的容易に落ちやすいが、可溶性硫酸イオン、可溶性硝酸イオン及び可溶性塩化物イオンのような可溶性アニオンは単に水洗では低減することが困難である。そこで、水洗時に、まず薄いアルカリ水溶液で洗浄して硫酸イオン等のアニオンを低減させてから、さらに水で水洗することで、より硫酸イオン等のアニオンが低下しやすくなる。前記ハイドロタルサイト型粒子粉末を含有するスラリーのｐＨ調節及び水洗前の洗浄で用いる薄いアルカリ水溶液には、水酸化ナトリウム、炭酸ナトリウムなどのアルカリ水溶液を用いればよい。 In order to produce hydrotalcite-type compound particles with less soluble anions (soluble sulfate ions, soluble nitrate ions and soluble chloride ions), a slurry after the target hydrotalcite-type compound particles are generated and aged, or The slurry after the treatment such as the hydrophobizing surface treatment is preferably adjusted to pH 9.5 to 12, more preferably 9.8 to 11.5. By adjusting to the pH range, anions such as sulfate ions are likely to be lowered by washing (water washing). Sodium tends to fall relatively easily with water washing, but soluble anions such as soluble sulfate ions, soluble nitrate ions and soluble chloride ions are difficult to reduce simply by washing. Therefore, at the time of washing with water, washing with a thin alkaline aqueous solution first to reduce anions such as sulfate ions, and then washing with water further reduces the anions such as sulfate ions. An alkaline aqueous solution such as sodium hydroxide or sodium carbonate may be used as the thin alkaline aqueous solution used for pH adjustment of the slurry containing the hydrotalcite-type particle powder and washing before washing with water.
　さらに、薄いアルカリ水溶液および／または水洗に用いる薄いアルカリ水溶液および／または水の温度は、３０～９０℃であることが好ましい。この範囲の温度の薄いアルカリ水溶液および／または水を用いるとイオンの拡散速度が向上し、さらに水の粘度が低下して水洗効果が高まる。より好ましくは４０～７０℃である。 Furthermore, the temperature of the thin alkaline aqueous solution and / or the thin alkaline aqueous solution and / or water used for washing is preferably 30 to 90 ° C. When an alkaline aqueous solution and / or water having a thin temperature in this range is used, the diffusion rate of ions is improved, and the viscosity of water is further lowered to enhance the washing effect. More preferably, it is 40 to 70 ° C.
　上記のようにして得られたハイドロタルサイト型化合物粒子粉末は、基本的には１０５～１５０℃にて乾燥を行うことが好ましい。１０５℃未満の乾燥温度では得られるハイドロタルサイト型化合物粒子粉末の水分が多いので樹脂中で発泡が起きやすく、また乾燥させるために長時間必要となり経済的ではない。１５０℃を超える場合は、軟質～半硬質含塩素樹脂組成物の安定剤用途として樹脂に対する劣化抑制の働きが低下する傾向にある。軟質～半硬質含塩素樹脂組成物の安定剤用途では、乾燥温度は１０５～１３０℃がより好ましい。乾燥時間は乾燥量や乾燥方法によって必要な時間行えばよい。好ましくは３～２４ｈである。 The hydrotalcite-type compound particle powder obtained as described above is preferably basically dried at 105 to 150 ° C. At a drying temperature of less than 105 ° C., the resulting hydrotalcite-type compound particle powder has a large amount of water, so that foaming is likely to occur in the resin. When the temperature exceeds 150 ° C., the function of suppressing deterioration of the resin tends to decrease as a stabilizer for soft to semi-rigid chlorine-containing resin compositions. In the use of a soft to semi-rigid chlorine-containing resin composition as a stabilizer, the drying temperature is more preferably 105 to 130 ° C. The drying time may be as long as necessary depending on the amount of drying and the drying method. Preferably, it is 3 to 24 h.
　次に、本発明に係る含塩素樹脂安定剤及び含塩素樹脂組成物について述べる。 Next, the chlorine-containing resin stabilizer and chlorine-containing resin composition according to the present invention will be described.
　本発明１又は２のハイドロタルサイト型化合物粒子粉末を含塩素樹脂安定剤として含塩素樹脂組成物に添加して用いることができる。 The hydrotalcite-type compound particle powder of the present invention 1 or 2 can be used as a chlorine-containing resin stabilizer added to a chlorine-containing resin composition.
　本発明に係る含塩素樹脂組成物は、樹脂１００重量部に対して、前記ハイドロタルサイト型化合物粒子粉末を０．０１～１０重量部含有することが好ましい。ハイドロタルサイト型化合物粒子粉末の含有量が０．０１重量部未満の場合には、安定剤としての効果が低い。１０重量部を超える場合には、効果が飽和するため必要以上に添加する意味がない。また、ハイドロタルサイト型粒子粉末を必要以上に多量に添加すると、発泡が起こりやすく、外観不良や初期着色等の悪影響を及ぼす場合がある。 The chlorine-containing resin composition according to the present invention preferably contains 0.01 to 10 parts by weight of the hydrotalcite-type compound particle powder with respect to 100 parts by weight of the resin. When the content of the hydrotalcite-type compound particle powder is less than 0.01 parts by weight, the effect as a stabilizer is low. When the amount exceeds 10 parts by weight, the effect is saturated, so there is no point in adding more than necessary. Moreover, when hydrotalcite-type particle powder is added in a larger amount than necessary, foaming is likely to occur, which may have adverse effects such as poor appearance and initial coloration.
　また、必要に応じて、樹脂中に可塑剤、その他安定剤及び添加剤を含有してもよい。 Further, if necessary, the resin may contain a plasticizer, other stabilizers and additives.
　可塑剤としては、トリオクチルトリメリテート（ＴＯＴＭ）、トリ－ｎ－オクチル－ｎ－デシルトリメリテート等のトリメトリット酸エステル系可塑剤、フタル酸ジイロデシル（ＤＩＤＰ）、ジイソノニル・フタレート（ＤＩＮＰ）、ジ－２－エチルヘキシル・フタレート（ＤＯＰ）等のフタル酸エステル系可塑剤、ポリプロピレン・アジペート、ポリプロピレン・セバケート等のポリエステル系可塑剤等が好ましい。 Examples of the plasticizer include trioctyl ester plasticizers such as trioctyl trimellitate (TOTM) and tri-n-octyl-n-decyl trimellitate, diirodecyl phthalate (DIDP), diisononyl phthalate (DINP), di- Preferred are phthalate plasticizers such as -2-ethylhexyl phthalate (DOP), and polyester plasticizers such as polypropylene / adipate and polypropylene / sebacate.
　その他安定剤としては、ステアリン酸亜鉛、ラウリン酸亜鉛、リシノール酸亜鉛等の亜鉛化合物、ジベンゾイルメタン、ステアロイルベンゾイルメタン、デヒドロ酢酸等のβ－ジケトン類、アルキルアリルフォスフェート、トリアルキルフォスフェート等のフォスファイト類、ジペンタエリスリトール、ペンタエリスリトール、グリセリン、ジグリセリン、トリメチロールプロパン等の多価アルコール系化合物、ステアリン酸、ラウリン酸、オレイン酸等の高級脂肪酸、エポキシ化アマニ油、エポキシ化大豆油等のエポキシ系化合物等が好ましい。 Other stabilizers include zinc compounds such as zinc stearate, zinc laurate, zinc ricinoleate, β-diketones such as dibenzoylmethane, stearoylbenzoylmethane, dehydroacetic acid, alkylallyl phosphates, trialkyl phosphates, etc. Phosphites, dipentaerythritol, pentaerythritol, polyhydric alcohol compounds such as glycerin, diglycerin, trimethylolpropane, higher fatty acids such as stearic acid, lauric acid, oleic acid, epoxidized linseed oil, epoxidized soybean oil, etc. Of these, epoxy compounds are preferred.
　その他の添加剤としては、フェノール系化合物、アミン系化合物、りん酸系化合物等の酸化防止剤、ポリエステルの末端をＯＨ基に変えたもの、アクリロニトリル－スチレンコポリマー、メタクリル酸メチルスチレンコポリマー等のゲル化促進剤、炭酸カルシウム、シリカ、ガラスビーズ、マイカ、ガラス繊維等の増量剤、三酸化アンチモン、水酸化アルミニウム、ほう酸亜鉛等の無機難燃剤、含臭素有機系難燃剤、含ハロゲンリン酸エステル系難燃剤等の難燃剤、ステアリン酸、ポリエチレンワックス、ステアリン酸カルシウム、ステアリン酸マグネシウム、ステアリン酸バリウム等の滑剤、トリクロサン、オーソサイド、サンアイゾール１００、サンアイゾール３００等防カビ剤等が使用される。 Other additives include phenolic compounds, amine compounds, phosphoric acid compounds and other antioxidants, polyesters with OH-terminated polyester, acrylonitrile-styrene copolymers, and methyl methacrylate styrene copolymers. Accelerator, extenders such as calcium carbonate, silica, glass beads, mica, glass fiber, inorganic flame retardants such as antimony trioxide, aluminum hydroxide, zinc borate, bromine-containing organic flame retardants, halogen phosphate ester-based flame retardants Flame retardants such as flame retardants, lubricants such as stearic acid, polyethylene wax, calcium stearate, magnesium stearate, barium stearate, anti-fungal agents such as triclosan, orthoside, sun isol 100, sun isol 300 and the like are used.
　本発明に係るハイドロタルサイト型化合物を含塩素樹脂組成物として用いる場合、該ハイドロタルサイト型化合物に高級脂肪酸やアニオン系界面活性剤、高級脂肪酸リン酸エステル、カップリング剤及び多価アルコールエステル類から選ばれる少なくとも一種の表面処理を施すことが好ましい。表面処理を施すことでより一層の含塩素樹脂組成物の安定性を付与することができる。 When the hydrotalcite-type compound according to the present invention is used as a chlorine-containing resin composition, a higher fatty acid, an anionic surfactant, a higher fatty acid phosphate, a coupling agent, and a polyhydric alcohol ester are added to the hydrotalcite-type compound. It is preferable to perform at least one surface treatment selected from By applying the surface treatment, a further stability of the chlorine-containing resin composition can be imparted.
　高級脂肪酸としては、例えば、ラウリル酸、ステアリン酸、パルミチン酸、オレイン酸、リノール酸などであり、高級脂肪酸リン酸エステルとしては、例えば、ステアリルエーテルリン酸、オレイルエーテルリン酸、ラウリルエーテルリン酸などであり、多価アルコールエステルとしては、ソルビタンモノオレエート、ソルビタンモノラウレート、ステアリン酸モノグリセライドなどが挙げられる。 Examples of the higher fatty acid include lauric acid, stearic acid, palmitic acid, oleic acid, and linoleic acid. Examples of the higher fatty acid phosphate ester include stearyl ether phosphoric acid, oleyl ether phosphoric acid, and lauryl ether phosphoric acid. Examples of the polyhydric alcohol ester include sorbitan monooleate, sorbitan monolaurate, and stearic acid monoglyceride.
　アニオン系界面活性剤としては、例えば、ラウリル硫酸ナトリウム、ドデシルベンゼンスルフォン酸ナトリウム、ステアリン酸ナトリウム、オレイン酸カリウム、ひまし油カリウムなどの塩類などが挙げられる。 Examples of the anionic surfactant include salts such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium stearate, potassium oleate, and potassium castor oil.
　カップリング剤としては、シラン系、アルミニウム系、チタン系、ジルコニウム系カップリング剤などを使用できる。 As the coupling agent, a silane-based, aluminum-based, titanium-based, zirconium-based coupling agent or the like can be used.
　表面処理剤の処理方法は、特に限定されないが、ハイドロタルサイト型化合物粒子表面に湿式反応によって行ってもよい。あるいは、ハイドロタルサイト型化合物粒子表面に、ヘンシェルミキサー等によって乾式表面処理してもよい。または、単純に該ハイドロタルサイト型化合物粒子と表面処理剤を混合するだけでもよい。 The treatment method of the surface treatment agent is not particularly limited, but may be performed on the surface of the hydrotalcite type compound particles by a wet reaction. Alternatively, the surface of the hydrotalcite compound particles may be subjected to a dry surface treatment using a Henschel mixer or the like. Alternatively, the hydrotalcite type compound particles and the surface treatment agent may be simply mixed.
　本発明に係る含塩素樹脂組成物は、可塑剤が全く含まれない若しくは少量しか含まれない硬質若しくは半硬質材料の場合、下記組成からなる含塩素樹脂組成物において、本発明に係るハイドロタルサイト型化合物を用いれば、ステアリン酸亜鉛０．８重量部では、後述する着色レベルにおいて、レベル３の時間が６５分以上、レベル５の時間が１００分以上である。 When the chlorine-containing resin composition according to the present invention is a hard or semi-rigid material that contains no plasticizer or only a small amount, the hydrotalcite according to the present invention is a chlorine-containing resin composition having the following composition: When the type compound is used, 0.8 parts by weight of zinc stearate has a level 3 time of 65 minutes or more and a level 5 time of 100 minutes or more at the coloring level described later.
　含塩素樹脂（重合度１０００）：
　　大洋塩ビ株式会社製　大洋ＰＶＣ　ＴＨ１０００
　　　　　　　　　　　　　　　　　　　　　　　　　　　　１００重量部
　　フタル酸ジ－２－エチルヘキシル（大八化学製　ＤＯＰ）
　　　　　　　　　　　　　　　　　　　　　　　　　　　０～２５重量部
　　ハイドロタルサイト型化合物粒子粉末
　　　　　　　　　　　　　　　　　　　　　　　　　　　　３．５重量部
　　ステアリン酸亜鉛（一般試薬）
　　　　　　　　　　　　　　　　　　　　　　　　０．６～０．９重量部 Chlorine-containing resin (degree of polymerization 1000):
Taiyo PVC TH1000 manufactured by Taiyo PVC Co., Ltd.
100 parts by weight Di-2-ethylhexyl phthalate (DOP manufactured by Daihachi Chemical)
0 to 25 parts by weight Hydrotalcite type compound particle powder 3.5 parts by weight Zinc stearate (general reagent)
0.6 to 0.9 parts by weight
　また、可塑剤が多く含まれる軟質材料の場合、下記組成からなる含塩素樹脂組成物において、本発明に係るハイドロタルサイト型化合物を用いれば、後述する着色レベルにおいて、レベル３の時間が６５分以上で、レベル５の時間が１００分以上である。 In the case of a soft material containing a large amount of plasticizer, in a chlorine-containing resin composition having the following composition, if the hydrotalcite-type compound according to the present invention is used, the level 3 time is 65 minutes at the coloring level described later. The level 5 time is 100 minutes or longer.
　含塩素樹脂（重合度１０００）
　　大洋塩ビ株式会社製　大洋ＰＶＣ　ＴＨ１０００
　　　　　　　　　　　　　　　　　　　　　　　　　　　　１００重量部
　　フタル酸ジ－２－エチルヘキシル（大八化学製　ＤＯＰ）
　　　　　　　　　　　　　　　　　　　　　　　　　　４０～８０重量部
　　本発明ハイドロタルサイト型化合物
　　　　　　　　　　　　　　　　　　　　　　　　　　　　３．０重量部
　　ステアリン酸亜鉛（一般試薬）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　０．６重量部 Chlorine-containing resin (degree of polymerization 1000)
Taiyo PVC TH1000 manufactured by Taiyo PVC Co., Ltd.
100 parts by weight Di-2-ethylhexyl phthalate (DOP manufactured by Daihachi Chemical)
40-80 parts by weight Hydrotalcite compound of the present invention 3.0 parts by weight Zinc stearate (general reagent)
0.6 parts by weight
　本発明に係る含塩素樹脂組成物は、用途によっても異なるが、体積固有抵抗値が２．０×１０１４Ω・ｃｍ以上であることが好ましい。 The chlorine-containing resin composition according to the present invention preferably has a volume resistivity value of 2.0 × 10 14 Ω · cm or more, although it varies depending on the application.
　次に、本発明に係る含塩素樹脂組成物の製造法について述べる。 Next, a method for producing the chlorine-containing resin composition according to the present invention will be described.
　本発明に係る含塩素樹脂組成物は通常の製造法によって得ることができるが、例えば、練り込みシートを得る場合には、樹脂、ハイドロタルサイト型化合物粒子粉末及び上記各種安定剤、添加剤を所定量混合し、該混合物を熱間ロールで練り込み、練り込みシートを得た後、熱間プレスで加圧処理することによって得られる。熱間ロールの練り込み温度は用いる樹脂や樹脂組成物によって異なるが、１４０～３００℃が好ましい。熱間プレスのプレス温度は１４５～３２０℃が好ましい。 The chlorine-containing resin composition according to the present invention can be obtained by an ordinary production method. For example, when obtaining a kneaded sheet, the resin, the hydrotalcite-type compound particle powder and the above various stabilizers and additives are added. It is obtained by mixing a predetermined amount, kneading the mixture with a hot roll to obtain a kneaded sheet, and then pressurizing with a hot press. The kneading temperature of the hot roll varies depending on the resin and resin composition used, but is preferably 140 to 300 ° C. The press temperature of the hot press is preferably 145 to 320 ° C.
＜作用＞
　本発明に係るハイドロタルサイト型化合物粒子粉末を用いることにより、樹脂の電気絶縁性を低下することが抑制でき、しかも、熱安定性の向上及び着色の抑制をもたらすことができる。 <Action>
By using the hydrotalcite-type compound particle powder according to the present invention, it is possible to suppress a decrease in the electrical insulation of the resin, and it is possible to improve the thermal stability and suppress the coloring.
　即ち、本発明に係るハイドロタルサイト型化合物粒子粉末は、電気伝導性のある可溶性硫酸イオン、可溶性硝酸イオン及び可溶性塩化物イオン等の可溶性アニオンの含有量が少ないため、樹脂の安定剤として用いた場合に、高い電気絶縁性を有する樹脂組成物が得られる。しかも、塩による樹脂焼けも抑えることができ、高い熱安定性を有し、着色の抑制された樹脂組成物を得ることができる。また、含有するナトリウムが少ないとより高い効果が得られる。 That is, the hydrotalcite-type compound particle powder according to the present invention was used as a resin stabilizer because it has a low content of soluble anions such as soluble sulfate ions, soluble nitrate ions and soluble chloride ions having electrical conductivity. In some cases, a resin composition having high electrical insulation is obtained. In addition, resin burning due to salt can be suppressed, and a resin composition having high thermal stability and suppressed coloring can be obtained. Moreover, when there is little sodium contained, a higher effect will be acquired.
　本発明の代表的な実施の形態は次の通りである。 A typical embodiment of the present invention is as follows.
　ナトリウム、マグネシウム、アルミニウム、亜鉛、カルシウム等の元素の含有量は、試料を酸で溶解し、プラズマ発光分光分析装置（サーモエレクトロン株式会社製、ｉＣＡＰ６５００）でイットリウムを内部標準として用いて分析して求めた。 The content of elements such as sodium, magnesium, aluminum, zinc, and calcium is obtained by dissolving a sample with an acid and analyzing it with a plasma emission spectroscopic analyzer (manufactured by Thermo Electron Co., Ltd., iCAP6500) using yttrium as an internal standard. It was.
　可溶性アニオンの測定法について以下に述べる。試料５ｇをエタノール４０ｍｌに馴染ませて分散させ、超純水１００ｍｌを追加して密封容器で１分間振り混ぜ、そのまま２２℃で２０時間放置した後、このスラリーを濾過し、超純水を補給しながら濾液を６０分間煮沸させてエタノールを蒸発させ、冷却して超純水で液量を１００ｍｌに調節した。これをイオンクロマト分析装置（東亜ディーケーケー、ＩＣＡ－２０００）で分析し硫酸イオン、硝酸イオン、塩化物イオンの測定をそれぞれ行った。 The method for measuring soluble anions is described below. Disperse 5 g of sample in 40 ml of ethanol, add 100 ml of ultrapure water, shake in a sealed container for 1 minute, leave it at 22 ° C. for 20 hours, filter this slurry, and replenish ultrapure water. The filtrate was boiled for 60 minutes to evaporate ethanol, cooled, and the liquid volume was adjusted to 100 ml with ultrapure water. This was analyzed with an ion chromatograph (Toa DKK, ICA-2000) to measure sulfate ion, nitrate ion, and chloride ion, respectively.
　比表面積値は、窒素を用いたＢ．Ｅ．Ｔ．法により測定した。 Specific surface area value is B. using nitrogen. E. T.A. Measured by the method.
　樹脂のロール混練は、６インチ２本タイプを用いて、樹脂組成物に合わせて温度を１４０～１９０℃に調整した。混練時間は５分にて行った。 Resin roll kneading was carried out by adjusting the temperature to 140 to 190 ° C. according to the resin composition using a 6-inch two-piece type. The kneading time was 5 minutes.
　上記ロール混練したシートを、２００×２００×１～１．５ｍｍの圧縮成型体にした。圧縮成形体を作製する装置は加熱プレスが７０トン自動プレス（ラム面積２１０ｃｍ２）、冷却プレスが３０トン手動プレス（ラム面積１８０ｃｍ２）とした。圧縮成型条件は、１４０～１９０℃にて、予熱（無圧）にて３分、加圧（６．３ＭＰａ）にて２分、冷却（３．１ＭＰａ）にて３分の手順で行った。 The roll-kneaded sheet was formed into a compression molded body of 200 × 200 × 1 to 1.5 mm. As the apparatus for producing the compression molded body, the heating press was a 70-ton automatic press (ram area 210 cm 2 ), and the cooling press was a 30-ton manual press (ram area 180 cm 2 ). The compression molding conditions were 140-190 ° C., preheating (no pressure) for 3 minutes, pressurizing (6.3 MPa) for 2 minutes, and cooling (3.1 MPa) for 3 minutes.
　得られたシートを用いて電気抵抗（電気絶縁性）を測定した。厚さ１．０ｍｍの樹脂プレスシートを作成し、３０℃－６０％のデシケーターに１日保管し、ＪＩＳ　Ｋ６７２３に準じて、体積固有抵抗値（Ω・ｃｍ）を測定した。 Electrical resistance (electrical insulation) was measured using the obtained sheet. A 1.0 mm thick resin press sheet was prepared, stored in a desiccator at 30 ° C.-60% for 1 day, and the volume resistivity (Ω · cm) was measured according to JIS K6723.
　熱安定性試験はギヤー老化式試験機（株式会社安田精機製作所製、１０２－ＳＨＦ－７７Ｓ）にて行った。上記プレスしたシートを３０×３０ｍｍ角に切り出し、ガラス板上にこの試験片を置いて、１９０℃で２００分間試験をしながら、１０分毎に試験片を２枚／１サンプルずつ取り出して、記録紙に貼り付けた。 The thermal stability test was performed with a gear aging type tester (manufactured by Yasuda Seiki Seisakusho, 102-SHF-77S). The pressed sheet was cut into 30 × 30 mm squares, placed on a glass plate, tested at 190 ° C. for 200 minutes, and taken out every 2 minutes / sample for 10 minutes. Pasted on paper.
　プレスシート及び熱安定性試験片の着色レベルは次のような１～７のレベルに定義した。 The coloring levels of the press sheet and the thermal stability test piece are defined as 1 to 7 as follows.
　　レベル１　ほとんど着色がない
　　レベル２　淡い褐色
　　レベル３　褐色
　　レベル４　一部が炭化・黒化
　　レベル５　全体が炭化・黒化 Level 1 Almost no color Level 2 Light brown Level 3 Brown Level 4 Partial carbonization / blackening Level 5 Whole carbonization / blackening
　次に実施の形態を述べる。 Next, an embodiment will be described.
　実施例１：
（ハイドロタルサイト型化合物粒子粉末の作製）
　酸化マグネシウム２６．９ｇを純水に分散させたスラリーと硫酸アルミニウム８水塩結晶８１．０ｇの水溶液を攪拌しながら混合した。別に、炭酸ソーダ結晶３５．７ｇを純水で溶解し、さらに苛性ソーダ（１２Ｎ）５８．３ｍｌと純水を加えた。このアルカリ溶液を先の酸化マグネシウムと硫酸アルミニウム８水塩を混合したスラリーに投入して８０℃に昇温し、８０℃にて５時間撹拌した。全量を１Ｌとし、これをオートクレーブに移して１７５℃にて４時間撹拌しながらエージングした。 Example 1:
(Preparation of hydrotalcite-type compound particle powder)
A slurry in which 26.9 g of magnesium oxide was dispersed in pure water and an aqueous solution of 81.0 g of aluminum sulfate octahydrate crystals were mixed with stirring. Separately, 35.7 g of sodium carbonate crystals were dissolved in pure water, and 58.3 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into a slurry obtained by mixing the above magnesium oxide and aluminum sulfate octahydrate, heated to 80 ° C., and stirred at 80 ° C. for 5 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 175 ° C. for 4 hours.
　続いて、この反応スラリーを撹拌しながら６７℃にして、ｐＨを１０．３に調整した。この状態に２．３ｇのパルミチン酸ソーダを熱湯（８０℃）に溶解した溶液を投入した。これを０．７時間エージングした。濾過後、４０℃のｐＨ１１．５の薄い苛性ソーダの水溶液２Ｌで水洗し、その後４０℃の純水１５Ｌで水洗し、１２５℃で８ｈ乾燥を行った。得られた試料の比表面積は１１．０ｍ２／ｇであった。 Subsequently, the reaction slurry was stirred and brought to 67 ° C., and the pH was adjusted to 10.3. In this state, a solution prepared by dissolving 2.3 g of sodium palmitate in hot water (80 ° C.) was added. This was aged for 0.7 hours. After filtration, it was washed with 2 L of a thin caustic soda solution having a pH of 11.5 at 40 ° C., then washed with 15 L of 40 ° C. pure water, and dried at 125 ° C. for 8 hours. The specific surface area of the obtained sample was 11.0 m 2 / g.
（含塩素樹脂組成物の作製及び評価）
　上記ハイドロタルサイト型化合物粒子粉末を用いて以下の含塩素樹脂組成物とした（軟質組成）。 (Production and evaluation of chlorine-containing resin composition)
The following hydrotalcite-type compound particle powder was used to prepare the following chlorine-containing resin composition (soft composition).
　　　含塩素樹脂組成物　　　　　　　　　　　　１００ｐｈｒ
　　　ＤＯＰ　　　　　　　　　　　　　　　　　　５５ｐｈｒ
　　　ステアリン酸亜鉛　　　　　　　　　　　　０．６ｐｈｒ
　　　上記試料　　　　　　　　　　　　　　　　３．０ｐｈｒ Chlorine-containing resin composition 100phr
DOP 55 phr
Zinc stearate 0.6 phr
Sample above 3.0 phr
１５８℃にて５分ロール混練し、１５８℃にて圧縮成形プレス処理を行った。得られたシートのレベル３の時間は８０ｍｉｎ、レベル５の時間は１２０ｍｉｎであった。 Roll kneading was performed at 158 ° C. for 5 minutes, and compression molding press processing was performed at 158 ° C. The level 3 time of the obtained sheet was 80 min, and the level 5 time was 120 min.
　　実施例２：
（ハイドロタルサイト型化合物粒子粉末の作製）
　硫酸マグネシウム７水塩結晶１４１．０ｇ、硫酸亜鉛７水塩結晶４１．５ｇ結晶及び硫酸アルミニウム８水塩結晶６９．４ｇを純水に溶解した。別に、炭酸ソーダ結晶３０．６ｇを純水で溶解し、さらに苛性ソーダ（１２Ｎ）１５２．４ｍｌと純水を加えた。このアルカリ溶液を先の硫酸マグネシウム７水塩結晶、硫酸亜鉛７水塩結晶及び硫酸アルミニウム８水塩を混合した水溶液に投入して８５℃に昇温し、８５℃にて６時間撹拌した。全量を１Ｌとし、これをオートクレーブに移して１８５℃にて６時間撹拌しながらエージングした。 Example 2:
(Preparation of hydrotalcite-type compound particle powder)
141.0 g of magnesium sulfate heptahydrate crystals, 41.5 g of zinc sulfate heptahydrate crystals and 69.4 g of aluminum sulfate octahydrate crystals were dissolved in pure water. Separately, 30.6 g of sodium carbonate crystals were dissolved in pure water, and 152.4 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into an aqueous solution in which the magnesium sulfate heptahydrate crystals, zinc sulfate heptahydrate crystals and aluminum sulfate octahydrate were mixed, heated to 85 ° C., and stirred at 85 ° C. for 6 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 185 ° C. for 6 hours.
　続いて、この反応スラリーを撹拌しながら６５℃にして、ｐＨを１０．１に調整した。この状態に２．５ｇのステアリン酸ソーダを熱湯（８０℃）に溶解した溶液を投入した。これを０．６時間エージングした。濾過後、５０℃のｐＨ１１の薄い苛性ソーダの水溶液２Ｌで水洗し、その後５０℃の純水１５Ｌで水洗し、１２５℃で８ｈ乾燥を行った。得られた試料の比表面積は１０．０ｍ２／ｇであった。 Subsequently, the reaction slurry was stirred and brought to 65 ° C. to adjust the pH to 10.1. In this state, a solution prepared by dissolving 2.5 g of sodium stearate in hot water (80 ° C.) was added. This was aged for 0.6 hours. After filtration, it was washed with 2 L of a thin aqueous solution of caustic soda having a pH of 11 at 50 ° C., then washed with 15 L of pure water at 50 ° C., and dried at 125 ° C. for 8 hours. The specific surface area of the obtained sample was 10.0 m 2 / g.
（含塩素樹脂組成物の作製及び評価）
　上記ハイドロタルサイト型化合物粒子粉末を用いて以下の含塩素樹脂組成物とした（軟質組成）。 (Production and evaluation of chlorine-containing resin composition)
The following hydrotalcite-type compound particle powder was used to prepare the following chlorine-containing resin composition (soft composition).
　　　含塩素樹脂組成物　　　　　　　　　　　　１００ｐｈｒ
　　　ＤＯＰ　　　　　　　　　　　　　　　　　　５５ｐｈｒ
　　　ステアリン酸亜鉛　　　　　　　　　　　　０．６ｐｈｒ
　　　上記試料　　　　　　　　　　　　　　　　３．０ｐｈｒ Chlorine-containing resin composition 100phr
DOP 55 phr
Zinc stearate 0.6 phr
Sample above 3.0 phr
１５８℃にて５分ロール混練し、１５８℃にて圧縮成形プレス処理を行った。得られたシートのレベル３の時間は７５ｍｉｎ、レベル５の時間は１１５ｍｉｎであった。 Roll kneading was performed at 158 ° C. for 5 minutes, and compression molding press processing was performed at 158 ° C. The level 3 time of the obtained sheet was 75 min, and the level 5 time was 115 min.
　実施例３：
（ハイドロタルサイト型化合物粒子粉末の作製）
　硫酸マグネシウム７水塩結晶１７６．３ｇ及び硫酸アルミニウム８水塩結晶６９．４ｇを純水に溶解した。別に、炭酸ソーダ結晶３０．６ｇを純水で溶解し、さらに苛性ソーダ（１２Ｎ）１５２．４ｍｌと純水を加えた。このアルカリ溶液を先の硫酸マグネシウム７水塩結晶及び硫酸アルミニウム８水塩を混合した水溶液に投入して９０℃に昇温し、９０℃にて１０時間撹拌した。全量を１Ｌとし、これをオートクレーブに移して１４５℃にて６時間撹拌しながらエージングした。 Example 3:
(Preparation of hydrotalcite-type compound particle powder)
176.3 g of magnesium sulfate heptahydrate crystals and 69.4 g of aluminum sulfate octahydrate crystals were dissolved in pure water. Separately, 30.6 g of sodium carbonate crystals were dissolved in pure water, and 152.4 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into an aqueous solution in which the magnesium sulfate heptahydrate crystal and aluminum sulfate octahydrate were mixed, heated to 90 ° C., and stirred at 90 ° C. for 10 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 145 ° C. for 6 hours.
　続いて、この反応スラリーを撹拌しながら６５℃にして、ｐＨを１１．２に調整した。この状態に１．９ｇのラウリン酸ソーダを熱湯（８０℃）に溶解した溶液を投入した。これを０．８時間エージングした。濾過後、４５℃のｐＨ１２．５の薄い苛性ソーダの水溶液２Ｌで水洗し、その後４５℃の純水１５Ｌで水洗し、１２５℃で８ｈ乾燥を行った。得られた試料の比表面積は９．０ｍ２／ｇであった。 Subsequently, the reaction slurry was stirred and brought to 65 ° C., and the pH was adjusted to 11.2. In this state, a solution prepared by dissolving 1.9 g of sodium laurate in hot water (80 ° C.) was added. This was aged for 0.8 hours. After filtration, it was washed with 2 L of a thin caustic soda solution having a pH of 12.5 at 45 ° C., then washed with 15 L of pure water at 45 ° C., and dried at 125 ° C. for 8 hours. The specific surface area of the obtained sample was 9.0 m 2 / g.
（含塩素樹脂組成物の作製及び評価）
　上記ハイドロタルサイト型化合物粒子粉末を用いて以下の含塩素樹脂組成物とした（半硬質組成）。 (Production and evaluation of chlorine-containing resin composition)
The following hydrotalcite-type compound particle powder was used to prepare the following chlorine-containing resin composition (semi-hard composition).
　　　含塩素樹脂組成物　　　　　　　　　　　　１００ｐｈｒ
　　　ＤＯＰ　　　　　　　　　　　　　　　　　　２０ｐｈｒ
　　　ステアリン酸亜鉛　　　　　　　　　　　　０．８ｐｈｒ
　　　上記試料　　　　　　　　　　　　　　　　３．５ｐｈｒ Chlorine-containing resin composition 100phr
DOP 20 phr
Zinc stearate 0.8 phr
Sample above 3.5phr
１７８℃にて５分ロール混練し、１７８℃にて圧縮成形プレス処理を行った。得られたシートのレベル３の時間は７５ｍｉｎ、レベル５の時間は１１５ｍｉｎであった。 Roll kneading was performed at 178 ° C. for 5 minutes, and compression molding press processing was performed at 178 ° C. The level 3 time of the obtained sheet was 75 min, and the level 5 time was 115 min.
　実施例４：
（ハイドロタルサイト型化合物粒子粉末の作製）
　塩化マグネシウム６水塩結晶１０１．９ｇ、塩化亜鉛１水塩結晶２６．０ｇ結晶及び塩化アルミニウム６水塩結晶８０．５ｇを純水に溶解した。別に、炭酸ソーダ結晶３５．７ｇを純水で溶解し、さらに苛性ソーダ（１２Ｎ）１３６．１ｍｌと純水を加えた。このアルカリ溶液を先の塩化マグネシウム６水塩結晶、塩化亜鉛１水塩結晶及び塩化アルミニウム６水塩を混合した水溶液に投入して９５℃に昇温し、９５℃にて８時間撹拌した。全量を１Ｌとし、これをオートクレーブに移して１６５℃にて７時間撹拌しながらエージングした。 Example 4:
(Preparation of hydrotalcite-type compound particle powder)
Magnesium chloride hexahydrate crystal 101.9 g, zinc chloride monohydrate crystal 26.0 g crystal and aluminum chloride hexahydrate crystal 80.5 g were dissolved in pure water. Separately, 35.7 g of sodium carbonate crystals were dissolved in pure water, and 136.1 ml of caustic soda (12N) and pure water were added. This alkaline solution was put into an aqueous solution obtained by mixing the above magnesium chloride hexahydrate crystal, zinc chloride monohydrate crystal and aluminum chloride hexahydrate, heated to 95 ° C., and stirred at 95 ° C. for 8 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 165 ° C. for 7 hours.
　続いて、この反応スラリーを撹拌しながら７０℃にして、ｐＨを９．９に調整した。この状態に２．５ｇのパルミチン酸ソーダを熱湯（８０℃）に溶解した溶液を投入した。これを０．７時間エージングした。濾過後、４５℃のｐＨ１１の薄い苛性ソーダの水溶液２Ｌで水洗し、その後４５℃の純水１６Ｌで水洗し、１２５℃で８ｈ乾燥を行った。得られた試料の比表面積は１０．２ｍ２／ｇであった。 Subsequently, the reaction slurry was stirred and brought to 70 ° C., and the pH was adjusted to 9.9. In this state, a solution prepared by dissolving 2.5 g of sodium palmitate in hot water (80 ° C.) was added. This was aged for 0.7 hours. After filtration, it was washed with 2 L of an aqueous solution of thin caustic soda having a pH of 11 at 45 ° C., then washed with 16 L of pure water at 45 ° C., and dried at 125 ° C. for 8 hours. The specific surface area of the obtained sample was 10.2 m 2 / g.
（含塩素樹脂組成物の作製及び評価）
　上記ハイドロタルサイト型化合物粒子粉末を用いて以下の含塩素樹脂組成物とした（軟質組成）。 (Production and evaluation of chlorine-containing resin composition)
The following hydrotalcite-type compound particle powder was used to prepare the following chlorine-containing resin composition (soft composition).
　　　含塩素樹脂組成物　　　　　　　　　　　　１００ｐｈｒ
　　　ＤＯＰ　　　　　　　　　　　　　　　　　　５５ｐｈｒ
　　　ステアリン酸亜鉛　　　　　　　　　　　　０．６ｐｈｒ
　　　上記試料　　　　　　　　　　　　　　　　３．０ｐｈｒ Chlorine-containing resin composition 100phr
DOP 55 phr
Zinc stearate 0.6 phr
Sample above 3.0 phr
１５８℃にて５分ロール混練し、１５８℃にて圧縮成形プレス処理を行った。得られたシートのレベル３の時間は７５ｍｉｎ、レベル５の時間は１２０ｍｉｎであった。 Roll kneading was performed at 158 ° C. for 5 minutes, and compression molding press processing was performed at 158 ° C. The level 3 time of the obtained sheet was 75 min, and the level 5 time was 120 min.
　実施例５：
（ハイドロタルサイト型化合物粒子粉末の作製）
　塩化マグネシウム６水塩結晶１４１．０ｇ及び塩化アルミニウム６水塩結晶７４．３ｇを純水に溶解した。別に、炭酸ソーダ結晶３２．９ｇを純水で溶解し、さらに苛性ソーダ（１２Ｎ）１６３．５ｍｌと純水を加えた。このアルカリ溶液を先の塩化マグネシウム６水塩結晶及び塩化アルミニウム６水塩を混合した水溶液に投入して７５℃に昇温し、７５℃にて１５時間撹拌した。全量を１Ｌとし、これをオートクレーブに移して１７０℃にて９時間撹拌しながらエージングした。 Example 5:
(Preparation of hydrotalcite-type compound particle powder)
Magnesium chloride hexahydrate crystals 141.0 g and aluminum chloride hexahydrate crystals 74.3 g were dissolved in pure water. Separately, 32.9 g of sodium carbonate crystals were dissolved in pure water, and 163.5 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into an aqueous solution in which the magnesium chloride hexahydrate crystals and aluminum chloride hexahydrate were mixed, heated to 75 ° C., and stirred at 75 ° C. for 15 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 170 ° C. for 9 hours.
　続いて、この反応スラリーを撹拌しながら７０℃にして、ｐＨを１０．９に調整した。この状態に２．０ｇのラウリン酸ソーダを熱湯（８０℃）に溶解した溶液を投入した。これを０．９時間エージングした。濾過後、４０℃のｐＨ１２の薄い苛性ソーダの水溶液２Ｌで水洗し、その後４０℃の純水１５Ｌで水洗し、１２５℃で８ｈ乾燥を行った。得られた試料の比表面積は１０．４ｍ２／ｇであった。 Subsequently, the reaction slurry was stirred and brought to 70 ° C., and the pH was adjusted to 10.9. In this state, a solution prepared by dissolving 2.0 g of sodium laurate in hot water (80 ° C.) was added. This was aged for 0.9 hours. After filtration, it was washed with 2 L of an aqueous solution of thin caustic soda having a pH of 12 at 40 ° C., then washed with 15 L of pure water at 40 ° C., and dried at 125 ° C. for 8 hours. The specific surface area of the obtained sample was 10.4 m 2 / g.
（含塩素樹脂組成物の作製及び評価）
　上記ハイドロタルサイト型化合物粒子粉末を用いて以下の含塩素樹脂組成物とした（軟質組成）。 (Production and evaluation of chlorine-containing resin composition)
The following hydrotalcite-type compound particle powder was used to prepare the following chlorine-containing resin composition (soft composition).
　　　含塩素樹脂組成物　　　　　　　　　　　　１００ｐｈｒ
　　　ＤＯＰ　　　　　　　　　　　　　　　　　　５５ｐｈｒ
　　　ステアリン酸亜鉛　　　　　　　　　　　　０．６ｐｈｒ
　　　上記試料　　　　　　　　　　　　　　　　３．０ｐｈｒ Chlorine-containing resin composition 100phr
DOP 55 phr
Zinc stearate 0.6 phr
Sample above 3.0 phr
１５８℃にて５分ロール混練し、１５８℃にて圧縮成形プレス処理を行った。得られたシートのレベル３の時間は９０ｍｉｎ、レベル５の時間は１１０ｍｉｎであった。 Roll kneading was performed at 158 ° C. for 5 minutes, and compression molding press processing was performed at 158 ° C. The level 3 time of the obtained sheet was 90 min, and the level 5 time was 110 min.
　実施例６：
（ハイドロタルサイト型化合物粒子粉末の作製）
　硝酸マグネシウム６水塩結晶１４９．８ｇ、硝酸亜鉛６水塩結晶２５．０ｇ結晶及び硝酸アルミニウム９水塩結晶１２５．０ｇを純水に溶解した。別に、炭酸ソーダ結晶３５．７ｇを純水で溶解し、さらに苛性ソーダ（１２Ｎ）１２６．４ｍｌと純水を加えた。このアルカリ溶液を先の硝酸マグネシウム６水塩結晶、硝酸亜鉛６水塩結晶及び硝酸アルミニウム９水塩を混合した水溶液に投入して９０℃に昇温し、９０℃にて１０時間撹拌した。全量を１Ｌとし、これをオートクレーブに移して１７５℃にて８時間撹拌しながらエージングした。 Example 6:
(Preparation of hydrotalcite-type compound particle powder)
149.8 g of magnesium nitrate hexahydrate crystals, 25.0 g of zinc nitrate hexahydrate crystals and 125.0 g of aluminum nitrate 9 hydrate crystals were dissolved in pure water. Separately, 35.7 g of sodium carbonate crystals were dissolved in pure water, and 126.4 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into an aqueous solution obtained by mixing the above magnesium nitrate hexahydrate crystal, zinc nitrate hexahydrate crystal and aluminum nitrate nonahydrate, heated to 90 ° C., and stirred at 90 ° C. for 10 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 175 ° C. for 8 hours.
　続いて、この反応スラリーを撹拌しながら６２℃にして、ｐＨを１０．０に調整した。この状態に２．５ｇのステアリン酸ソーダを熱湯（８０℃）に溶解した溶液を投入した。これを０．６時間エージングした。濾過後、４５℃のｐＨ１１．５の薄い苛性ソーダの水溶液２Ｌで水洗し、その後４５℃の純水１５Ｌで水洗し、１２５℃で８ｈ乾燥を行った。得られた試料の比表面積は９．８ｍ２／ｇであった。 Subsequently, the reaction slurry was stirred and brought to 62 ° C., and the pH was adjusted to 10.0. In this state, a solution prepared by dissolving 2.5 g of sodium stearate in hot water (80 ° C.) was added. This was aged for 0.6 hours. After filtration, it was washed with 2 L of a thin caustic soda solution having a pH of 11.5 at 45 ° C., then washed with 15 L of pure water at 45 ° C., and dried at 125 ° C. for 8 hours. The specific surface area of the obtained sample was 9.8 m 2 / g.
（含塩素樹脂組成物の作製及び評価）
　上記ハイドロタルサイト型化合物粒子粉末を用いて以下の含塩素樹脂組成物とした（軟質組成）。 (Production and evaluation of chlorine-containing resin composition)
The following hydrotalcite-type compound particle powder was used to prepare the following chlorine-containing resin composition (soft composition).
　　　含塩素樹脂組成物　　　　　　　　　　　　１００ｐｈｒ
　　　ＴＯＴＭ　　　　　　　　　　　　　　　　　６０ｐｈｒ
　　　ステアリン酸亜鉛　　　　　　　　　　　　０．７ｐｈｒ
　　　上記試料　　　　　　　　　　　　　　　　３．３ｐｈｒ Chlorine-containing resin composition 100phr
TOTM 60phr
Zinc stearate 0.7 phr
Sample above 3.3 phr
１６２℃にて５分ロール混練し、１６２℃にて圧縮成形プレス処理を行った。得られたシートのレベル３の時間は８０ｍｉｎ、レベル５の時間は１１０ｍｉｎであった。 Roll kneading was performed at 162 ° C. for 5 minutes, and compression molding press processing was performed at 162 ° C. The level 3 time of the obtained sheet was 80 min, and the level 5 time was 110 min.
　実施例７：
（ハイドロタルサイト型化合物粒子粉末の作製）
　硝酸マグネシウム６水塩結晶１７１．２ｇ及び硝酸アルミニウム９水塩結晶１２５．０ｇを純水に溶解した。別に、炭酸ソーダ結晶３５．７ｇを純水で溶解し、さらに苛性ソーダ（１２Ｎ）１２６．４ｍｌと純水を加えた。このアルカリ溶液を先の硝酸マグネシウム６水塩結晶及び硝酸アルミニウム９水塩を混合した水溶液に投入して９０℃に昇温し、９０℃にて１０時間撹拌した。全量を１Ｌとし、これをオートクレーブに移して１３０℃にて５時間撹拌しながらエージングした。 Example 7:
(Preparation of hydrotalcite-type compound particle powder)
171.2 g of magnesium nitrate hexahydrate crystals and 125.0 g of aluminum nitrate 9 hydrate crystals were dissolved in pure water. Separately, 35.7 g of sodium carbonate crystals were dissolved in pure water, and 126.4 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into an aqueous solution in which the magnesium nitrate hexahydrate crystal and the aluminum nitrate nonahydrate were mixed, heated to 90 ° C., and stirred at 90 ° C. for 10 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 130 ° C. for 5 hours.
　続いて、この反応スラリーを撹拌しながら６２℃にして、ｐＨを１０．０に調整した。この状態に２．５ｇのステアリン酸ソーダを熱湯（８０℃）に溶解した溶液を投入した。これを０．６時間エージングした。濾過後、６０℃のｐＨ１１の薄い苛性ソーダの水溶液３Ｌで水洗し、その後６０℃の純水２５Ｌで水洗し、１２５℃で８ｈ乾燥を行った。得られた試料の比表面積は１９．２ｍ２／ｇであった。 Subsequently, the reaction slurry was stirred and brought to 62 ° C., and the pH was adjusted to 10.0. In this state, a solution prepared by dissolving 2.5 g of sodium stearate in hot water (80 ° C.) was added. This was aged for 0.6 hours. After filtration, it was washed with 3 L of a thin caustic soda solution having a pH of 11 at 60 ° C., then washed with 25 L of pure water at 60 ° C., and dried at 125 ° C. for 8 hours. The specific surface area of the obtained sample was 19.2 m 2 / g.
（含塩素樹脂組成物の作製及び評価）
　上記ハイドロタルサイト型化合物粒子粉末を用いて以下の含塩素樹脂組成物とした（軟質組成）。 (Production and evaluation of chlorine-containing resin composition)
The following hydrotalcite-type compound particle powder was used to prepare the following chlorine-containing resin composition (soft composition).
　　　含塩素樹脂組成物　　　　　　　　　　　　１００ｐｈｒ
　　　ＤＯＰ　　　　　　　　　　　　　　　　　５５ｐｈｒ
　　　ステアリン酸亜鉛　　　　　　　　　　　　０．６ｐｈｒ
　　　上記試料　　　　　　　　　　　　　　　　３．０ｐｈｒ Chlorine-containing resin composition 100phr
DOP 55 phr
Zinc stearate 0.6 phr
Sample above 3.0 phr
１５８℃にて５分ロール混練し、１５８℃にて圧縮成形プレス処理を行った。得られたシートのレベル３の時間は８０ｍｉｎ、レベル５の時間は１１５ｍｉｎであった。 Roll kneading was performed at 158 ° C. for 5 minutes, and compression molding press processing was performed at 158 ° C. The level 3 time of the obtained sheet was 80 min, and the level 5 time was 115 min.
　実施例８：
（ハイドロタルサイト型化合物粒子粉末の作製）
　硫酸マグネシウム７水塩結晶１７６．３ｇ及び硫酸アルミニウム８水塩結晶６９．４ｇを純水に溶解した。別に、炭酸ソーダ結晶３０．６ｇを純水で溶解し、さらに苛性ソーダ（１２Ｎ）１５２．４ｍｌと純水を加えた。このアルカリ溶液を先の硫酸マグネシウム７水塩結晶及び硫酸アルミニウム８水塩を混合した水溶液に投入して９０℃に昇温し、９０℃にて１０時間撹拌した。全量を１Ｌとし、これをオートクレーブに移して１４５℃にて６時間撹拌しながらエージングした。 Example 8:
(Preparation of hydrotalcite-type compound particle powder)
176.3 g of magnesium sulfate heptahydrate crystals and 69.4 g of aluminum sulfate octahydrate crystals were dissolved in pure water. Separately, 30.6 g of sodium carbonate crystals were dissolved in pure water, and 152.4 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into an aqueous solution in which the magnesium sulfate heptahydrate crystal and aluminum sulfate octahydrate were mixed, heated to 90 ° C., and stirred at 90 ° C. for 10 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 145 ° C. for 6 hours.
　続いて、この反応スラリーを撹拌しながら６５℃にして、ｐＨを１１．９に調整した。この状態に１．９ｇのラウリン酸ソーダを熱湯（８０℃）に溶解した溶液を投入した。これを０．８時間エージングした。濾過後、４０℃のｐＨ１３の薄い苛性ソーダの水溶液２Ｌで水洗し、その後４５℃の純水１５Ｌで水洗し、１２５℃で８ｈ乾燥を行った。得られた試料の比表面積は９．３ｍ２／ｇであった。 Subsequently, the reaction slurry was stirred and brought to 65 ° C., and the pH was adjusted to 11.9. In this state, a solution prepared by dissolving 1.9 g of sodium laurate in hot water (80 ° C.) was added. This was aged for 0.8 hours. After filtration, it was washed with 2 L of a thin caustic soda solution having a pH of 13 at 40 ° C., then washed with 15 L of pure water at 45 ° C., and dried at 125 ° C. for 8 hours. The specific surface area of the obtained sample was 9.3 m 2 / g.
（含塩素樹脂組成物の作製及び評価）
　上記ハイドロタルサイト型化合物粒子粉末を用いて以下の含塩素樹脂組成物とした（半硬質組成）。 (Production and evaluation of chlorine-containing resin composition)
The following hydrotalcite-type compound particle powder was used to prepare the following chlorine-containing resin composition (semi-hard composition).
　　　含塩素樹脂組成物　　　　　　　　　　　　１００ｐｈｒ
　　　ＤＯＰ　　　　　　　　　　　　　　　　　　２０ｐｈｒ
　　　ステアリン酸亜鉛　　　　　　　　　　　　０．８ｐｈｒ
　　　上記試料　　　　　　　　　　　　　　　　３．５ｐｈｒ Chlorine-containing resin composition 100phr
DOP 20 phr
Zinc stearate 0.8 phr
Sample above 3.5phr
１７８℃にて５分ロール混練し、１７８℃にて圧縮成形プレス処理を行った。得られたシートのレベル３の時間は７５ｍｉｎ、レベル５の時間は１１０ｍｉｎであった。 Roll kneading was performed at 178 ° C. for 5 minutes, and compression molding press processing was performed at 178 ° C. The level 3 time of the obtained sheet was 75 min, and the level 5 time was 110 min.
　実施例９：
（ハイドロタルサイト型化合物粒子粉末の作製）
　塩化マグネシウム６水塩結晶１０１．９ｇ、塩化亜鉛１水塩結晶２６．０ｇ結晶及び塩化アルミニウム６水塩結晶８０．５ｇを純水に溶解した。別に、炭酸ソーダ結晶３５．７ｇを純水で溶解し、さらに苛性ソーダ（１２Ｎ）１３６．１ｍｌと純水を加えた。このアルカリ溶液を先の塩化マグネシウム６水塩結晶、塩化亜鉛１水塩結晶及び塩化アルミニウム６水塩を混合した水溶液に投入して９５℃に昇温し、９５℃にて８時間撹拌した。全量を１Ｌとし、これをオートクレーブに移して１６５℃にて７時間撹拌しながらエージングした。 Example 9:
(Preparation of hydrotalcite-type compound particle powder)
Magnesium chloride hexahydrate crystal 101.9 g, zinc chloride monohydrate crystal 26.0 g crystal and aluminum chloride hexahydrate crystal 80.5 g were dissolved in pure water. Separately, 35.7 g of sodium carbonate crystals were dissolved in pure water, and 136.1 ml of caustic soda (12N) and pure water were added. This alkaline solution was put into an aqueous solution obtained by mixing the above magnesium chloride hexahydrate crystal, zinc chloride monohydrate crystal and aluminum chloride hexahydrate, heated to 95 ° C., and stirred at 95 ° C. for 8 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 165 ° C. for 7 hours.
　続いて、この反応スラリーを撹拌しながら７０℃にして、ｐＨを１１．７に調整した。この状態に２．５ｇのパルミチン酸ソーダを熱湯（８０℃）に溶解した溶液を投入した。これを０．７時間エージングした。濾過後、５５℃のｐＨ１３の薄い苛性ソーダの水溶液２Ｌで水洗し、その後４５℃の純水１６Ｌで水洗し、１２５℃で８ｈ乾燥を行った。得られた試料の比表面積は１０．１ｍ２／ｇであった。 Subsequently, the reaction slurry was stirred and brought to 70 ° C., and the pH was adjusted to 11.7. In this state, a solution prepared by dissolving 2.5 g of sodium palmitate in hot water (80 ° C.) was added. This was aged for 0.7 hours. After filtration, it was washed with 2 L of a thin caustic soda solution having a pH of 13 at 55 ° C., then washed with 16 L of pure water at 45 ° C., and dried at 125 ° C. for 8 hours. The specific surface area of the obtained sample was 10.1 m 2 / g.
（含塩素樹脂組成物の作製及び評価）
　上記ハイドロタルサイト型化合物粒子粉末を用いて以下の含塩素樹脂組成物とした（軟質組成）。 (Production and evaluation of chlorine-containing resin composition)
The following hydrotalcite-type compound particle powder was used to prepare the following chlorine-containing resin composition (soft composition).
　　　含塩素樹脂組成物　　　　　　　　　　　　１００ｐｈｒ
　　　ＤＯＰ　　　　　　　　　　　　　　　　　　５５ｐｈｒ
　　　ステアリン酸亜鉛　　　　　　　　　　　　０．６ｐｈｒ
　　　上記試料　　　　　　　　　　　　　　　　３．０ｐｈｒ Chlorine-containing resin composition 100phr
DOP 55 phr
Zinc stearate 0.6 phr
Sample above 3.0 phr
１５８℃にて５分ロール混練し、１５８℃にて圧縮成形プレス処理を行った。得られたシートのレベル３の時間は７５ｍｉｎ、レベル５の時間は１１０ｍｉｎであった。 Roll kneading was performed at 158 ° C. for 5 minutes, and compression molding press processing was performed at 158 ° C. The level 3 time of the obtained sheet was 75 min, and the level 5 time was 110 min.
　実施例１０：
（ハイドロタルサイト型化合物粒子粉末の作製）
　塩化マグネシウム６水塩結晶１４１．０ｇ及び塩化アルミニウム６水塩結晶７４．３ｇを純水に溶解した。別に、炭酸ソーダ結晶３２．９ｇを純水で溶解し、さらに苛性ソーダ（１２Ｎ）２０３．５ｍｌと純水を加えた。このアルカリ溶液を先の塩化マグネシウム６水塩結晶及び塩化アルミニウム６水塩を混合した水溶液に投入し、その後、塩化カルシウム２水塩結晶４．５０ｇを溶解した水溶液を投入し、７５℃に昇温した。７５℃にて１５時間撹拌した。全量を１Ｌとし、これをオートクレーブに移して１７０℃にて９時間撹拌しながらエージングした。 Example 10:
(Preparation of hydrotalcite-type compound particle powder)
Magnesium chloride hexahydrate crystals 141.0 g and aluminum chloride hexahydrate crystals 74.3 g were dissolved in pure water. Separately, 32.9 g of sodium carbonate crystals were dissolved in pure water, and 203.5 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into an aqueous solution in which magnesium chloride hexahydrate crystals and aluminum chloride hexahydrate were mixed, and then an aqueous solution in which 4.50 g of calcium chloride dihydrate crystals were dissolved was added, and the temperature was raised to 75 ° C. did. Stir at 75 ° C. for 15 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 170 ° C. for 9 hours.
　続いて、この反応スラリーを撹拌しながら７０℃にして、ｐＨを１０．９に調整した。この状態に２．０ｇのラウリン酸ソーダを熱湯（８０℃）に溶解した溶液を投入した。これを０．９時間エージングした。濾過後、４０℃のｐＨ１２の薄い苛性ソーダの水溶液２Ｌで水洗し、その後４０℃の純水１５Ｌで水洗し、１２５℃で８ｈ乾燥を行った。得られた試料の比表面積は１０．０ｍ２／ｇであった。Ｍｇ／Ｃａ／Ａｌのモル比は２．４０／０．１０／１．００であった。 Subsequently, the reaction slurry was stirred and brought to 70 ° C., and the pH was adjusted to 10.9. In this state, a solution prepared by dissolving 2.0 g of sodium laurate in hot water (80 ° C.) was added. This was aged for 0.9 hours. After filtration, it was washed with 2 L of an aqueous solution of thin caustic soda having a pH of 12 at 40 ° C., then washed with 15 L of pure water at 40 ° C., and dried at 125 ° C. for 8 hours. The specific surface area of the obtained sample was 10.0 m 2 / g. The molar ratio of Mg / Ca / Al was 2.40 / 0.10 / 1.00.
（含塩素樹脂組成物の作製及び評価）
　上記ハイドロタルサイト型化合物粒子粉末を用いて以下の含塩素樹脂組成物とした（軟質組成）。 (Production and evaluation of chlorine-containing resin composition)
The following hydrotalcite-type compound particle powder was used to prepare the following chlorine-containing resin composition (soft composition).
　　　含塩素樹脂組成物　　　　　　　　　　　　１００ｐｈｒ
　　　ＤＯＰ　　　　　　　　　　　　　　　　　　５５ｐｈｒ
　　　ステアリン酸亜鉛　　　　　　　　　　　　０．６ｐｈｒ
　　　上記試料　　　　　　　　　　　　　　　　３．０ｐｈｒ Chlorine-containing resin composition 100phr
DOP 55 phr
Zinc stearate 0.6 phr
Sample above 3.0 phr
１５８℃にて５分ロール混練し、１５８℃にて圧縮成形プレス処理を行った。得られたシートのレベル３の時間は９０ｍｉｎ、レベル５の時間は１１０ｍｉｎであった。 Roll kneading was performed at 158 ° C. for 5 minutes, and compression molding press processing was performed at 158 ° C. The level 3 time of the obtained sheet was 90 min, and the level 5 time was 110 min.
　実施例１１：
（ハイドロタルサイト型化合物粒子粉末の作製）
　塩化マグネシウム６水塩結晶１０１．９ｇ、塩化亜鉛１水塩結晶２３．４ｇ結晶及び塩化アルミニウム６水塩結晶８０．５ｇを純水に溶解した。別に、炭酸ソーダ結晶３５．７ｇを純水で溶解し、さらに苛性ソーダ（１２Ｎ）１３６．１ｍｌと純水を加えた。このアルカリ溶液を先の塩化マグネシウム６水塩結晶、塩化亜鉛１水塩結晶及び塩化アルミニウム６水塩を混合した水溶液に投入して９５℃に昇温し、９５℃にて８時間撹拌した。全量を１Ｌとし、これをオートクレーブに移して１６５℃にて７時間撹拌しながらエージングした。この後、酸化亜鉛を１．４ｇ添加し、混合した。 Example 11:
(Preparation of hydrotalcite-type compound particle powder)
101.9 g of magnesium chloride hexahydrate crystals, 23.4 g of zinc chloride monohydrate crystals and 80.5 g of aluminum chloride hexahydrate crystals were dissolved in pure water. Separately, 35.7 g of sodium carbonate crystals were dissolved in pure water, and 136.1 ml of caustic soda (12N) and pure water were added. This alkaline solution was put into an aqueous solution obtained by mixing the above magnesium chloride hexahydrate crystal, zinc chloride monohydrate crystal and aluminum chloride hexahydrate, heated to 95 ° C., and stirred at 95 ° C. for 8 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 165 ° C. for 7 hours. Thereafter, 1.4 g of zinc oxide was added and mixed.
　続いて、この反応スラリーを撹拌しながら７０℃にして、ｐＨを１１．７に調整した。この状態に２．５ｇのパルミチン酸ソーダを熱湯（８０℃）に溶解した溶液を投入した。これを０．７時間エージングした。濾過後、４５℃のｐＨ１２．５の薄い苛性ソーダの水溶液２Ｌで水洗し、その後４５℃の純水１６Ｌで水洗し、１２５℃で８ｈ乾燥を行った。得られた試料の比表面積は１０．７ｍ２／ｇであった。 Subsequently, the reaction slurry was stirred and brought to 70 ° C., and the pH was adjusted to 11.7. In this state, a solution prepared by dissolving 2.5 g of sodium palmitate in hot water (80 ° C.) was added. This was aged for 0.7 hours. After filtration, it was washed with 2 L of a thin aqueous solution of caustic soda having a pH of 12.5 at 45 ° C., then washed with 16 L of pure water at 45 ° C., and dried at 125 ° C. for 8 hours. The specific surface area of the obtained sample was 10.7 m 2 / g.
（含塩素樹脂組成物の作製及び評価）
　上記ハイドロタルサイト型化合物粒子粉末を用いて以下の含塩素樹脂組成物とした（軟質組成）。 (Production and evaluation of chlorine-containing resin composition)
The following hydrotalcite-type compound particle powder was used to prepare the following chlorine-containing resin composition (soft composition).
　　　含塩素樹脂組成物　　　　　　　　　　　　１００ｐｈｒ
　　　ＤＯＰ　　　　　　　　　　　　　　　　　　５５ｐｈｒ
　　　ステアリン酸亜鉛　　　　　　　　　　　　０．６ｐｈｒ
　　　上記試料　　　　　　　　　　　　　　　　３．０ｐｈｒ Chlorine-containing resin composition 100phr
DOP 55 phr
Zinc stearate 0.6 phr
Sample above 3.0 phr
　１５８℃にて５分ロール混練し、１５８℃にて圧縮成形プレス処理を行った。得られたシートのレベル３の時間は８０ｍｉｎ、レベル５の時間は１１０ｍｉｎであった。 Roll kneading at 158 ° C. for 5 minutes and compression molding press treatment at 158 ° C. were performed. The level 3 time of the obtained sheet was 80 min, and the level 5 time was 110 min.
　比較例１：
　（ハイドロタルサイト型化合物粒子粉末の作製）
　酸化マグネシウム２６．９ｇを純水に分散させたスラリーと硫酸アルミニウム８水塩結晶８１．０ｇの水溶液を攪拌しながら混合した。別に、炭酸ソーダ結晶３５．７ｇを純水で溶解し、さらに苛性ソーダ（１２Ｎ）５８．３ｍｌと純水を加えた。このアルカリ溶液を先の酸化マグネシウムと硫酸アルミニウム８水塩を混合したスラリーに投入して８０℃に昇温し、８０℃にて５時間撹拌した。全量を１Ｌとし、これをオートクレーブに移して１７５℃にて４時間撹拌しながらエージングした。 Comparative Example 1:
(Preparation of hydrotalcite-type compound particle powder)
A slurry in which 26.9 g of magnesium oxide was dispersed in pure water and an aqueous solution of 81.0 g of aluminum sulfate octahydrate crystals were mixed with stirring. Separately, 35.7 g of sodium carbonate crystals were dissolved in pure water, and 58.3 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into a slurry obtained by mixing the above magnesium oxide and aluminum sulfate octahydrate, heated to 80 ° C., and stirred at 80 ° C. for 5 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 175 ° C. for 4 hours.
　続いて、この反応スラリーを撹拌しながら７２℃にして、ｐＨを８．９に調整した。この状態に２．３ｇのパルミチン酸ソーダを熱湯（８０℃）に溶解した溶液を投入した。これを０．７時間エージングした。濾過後、４０℃の純水１５Ｌで水洗し、１２５℃で８ｈ乾燥を行った。得られた試料の比表面積は１１．３ｍ２／ｇであった。 Subsequently, the reaction slurry was stirred and brought to 72 ° C., and the pH was adjusted to 8.9. In this state, a solution prepared by dissolving 2.3 g of sodium palmitate in hot water (80 ° C.) was added. This was aged for 0.7 hours. After filtration, it was washed with 15 L of 40 ° C. pure water and dried at 125 ° C. for 8 hours. The specific surface area of the obtained sample was 11.3 m 2 / g.
（含塩素樹脂組成物の作製及び評価）
　上記ハイドロタルサイト型化合物粒子粉末を用いて以下の含塩素樹脂組成物とした（軟質組成）。 (Production and evaluation of chlorine-containing resin composition)
The following hydrotalcite-type compound particle powder was used to prepare the following chlorine-containing resin composition (soft composition).
　　　含塩素樹脂組成物　　　　　　　　　　　　１００ｐｈｒ
　　　ＤＯＰ　　　　　　　　　　　　　　　　　　５５ｐｈｒ
　　　ステアリン酸亜鉛　　　　　　　　　　　　０．６ｐｈｒ
　　　上記試料　　　　　　　　　　　　　　　　３．０ｐｈｒ Chlorine-containing resin composition 100phr
DOP 55 phr
Zinc stearate 0.6 phr
Sample above 3.0 phr
　１５８℃にて５分ロール混練し、１５８℃にて圧縮成形プレス処理を行った。得られたシートのレベル３の時間は５０ｍｉｎ、レベル５の時間は９０ｍｉｎであった。 Roll kneading at 158 ° C. for 5 minutes and compression molding press treatment at 158 ° C. were performed. The level 3 time of the obtained sheet was 50 min, and the level 5 time was 90 min.
　比較例２：
（ハイドロタルサイト型化合物粒子粉末の作製）
　硫酸マグネシウム７水塩結晶１７６．３ｇ及び硫酸アルミニウム８水塩結晶６９．４ｇを純水に溶解した。別に、炭酸ソーダ結晶３０．６ｇを純水で溶解し、さらに苛性ソーダ（１２Ｎ）１５２．４ｍｌと純水を加えた。このアルカリ溶液を先の硫酸マグネシウム７水塩結晶及び硫酸アルミニウム８水塩を混合した水溶液に投入して９０℃に昇温し、９０℃にて１０時間撹拌した。全量を１Ｌとし、これをオートクレーブに移して１４５℃にて６時間撹拌しながらエージングした。 Comparative Example 2:
(Preparation of hydrotalcite-type compound particle powder)
176.3 g of magnesium sulfate heptahydrate crystals and 69.4 g of aluminum sulfate octahydrate crystals were dissolved in pure water. Separately, 30.6 g of sodium carbonate crystals were dissolved in pure water, and 152.4 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into an aqueous solution in which the magnesium sulfate heptahydrate crystal and aluminum sulfate octahydrate were mixed, heated to 90 ° C., and stirred at 90 ° C. for 10 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 145 ° C. for 6 hours.
　続いて、この反応スラリーを撹拌しながら６５℃にして、ｐＨを９．０に調整した。この状態に１．９ｇのラウリン酸ソーダを熱湯（８０℃）に溶解した溶液を投入した。これを０．８時間エージングした。濾過後、４５℃の純水１５Ｌで水洗し、１２５℃で８ｈ乾燥を行った。得られた試料の比表面積は９．５ｍ２／ｇであった。 Subsequently, the reaction slurry was stirred and brought to 65 ° C., and the pH was adjusted to 9.0. In this state, a solution prepared by dissolving 1.9 g of sodium laurate in hot water (80 ° C.) was added. This was aged for 0.8 hours. After filtration, it was washed with 15 L of pure water at 45 ° C. and dried at 125 ° C. for 8 hours. The specific surface area of the obtained sample was 9.5 m 2 / g.
（含塩素樹脂組成物の作製及び評価）
　上記ハイドロタルサイト型化合物粒子粉末を用いて以下の含塩素樹脂組成物とした（半硬質組成）。 (Production and evaluation of chlorine-containing resin composition)
The following hydrotalcite-type compound particle powder was used to prepare the following chlorine-containing resin composition (semi-hard composition).
　　　含塩素樹脂組成物　　　　　　　　　　　　１００ｐｈｒ
　　　ＤＯＰ　　　　　　　　　　　　　　　　　　２０ｐｈｒ
　　　ステアリン酸亜鉛　　　　　　　　　　　　０．８ｐｈｒ
　　　上記試料　　　　　　　　　　　　　　　　３．５ｐｈｒ Chlorine-containing resin composition 100phr
DOP 20 phr
Zinc stearate 0.8 phr
Sample above 3.5phr
１７８℃にて５分ロール混練し、１７８℃にて圧縮成形プレス処理を行った。得られたシートのレベル３の時間は５５ｍｉｎ、レベル５の時間は９５ｍｉｎであった。 Roll kneading was performed at 178 ° C. for 5 minutes, and compression molding press processing was performed at 178 ° C. The level 3 time of the obtained sheet was 55 min, and the level 5 time was 95 min.
　比較例３：
（ハイドロタルサイト型化合物粒子粉末の作製）
　塩化マグネシウム６水塩結晶１０１．９ｇ、塩化亜鉛１水塩結晶２６．０ｇ結晶及び塩化アルミニウム６水塩結晶８０．５ｇを純水に溶解した。別に、炭酸ソーダ結晶３５．７ｇを純水で溶解し、さらに苛性ソーダ（１２Ｎ）１３６．１ｍｌと純水を加えた。このアルカリ溶液を先の塩化マグネシウム６水塩結晶、塩化亜鉛１水塩結晶及び塩化アルミニウム６水塩を混合した水溶液に投入して９５℃に昇温し、９５℃にて８時間撹拌した。全量を１Ｌとし、これをオートクレーブに移して１６５℃にて７時間撹拌しながらエージングした。 Comparative Example 3:
(Preparation of hydrotalcite-type compound particle powder)
Magnesium chloride hexahydrate crystal 101.9 g, zinc chloride monohydrate crystal 26.0 g crystal and aluminum chloride hexahydrate crystal 80.5 g were dissolved in pure water. Separately, 35.7 g of sodium carbonate crystals were dissolved in pure water, and 136.1 ml of caustic soda (12N) and pure water were added. This alkaline solution was put into an aqueous solution obtained by mixing the above magnesium chloride hexahydrate crystal, zinc chloride monohydrate crystal and aluminum chloride hexahydrate, heated to 95 ° C., and stirred at 95 ° C. for 8 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 165 ° C. for 7 hours.
　続いて、この反応スラリーを撹拌しながら７０℃にして、ｐＨを９．１に調整した。この状態に２．５ｇのパルミチン酸ソーダを熱湯（８０℃）に溶解した溶液を投入した。これを０．７時間エージングした。濾過後、４５℃の純水１６Ｌで水洗し、１２５℃で８ｈ乾燥を行った。得られた試料の比表面積は９．５ｍ２／ｇであった。 Subsequently, the reaction slurry was stirred and brought to 70 ° C., and the pH was adjusted to 9.1. In this state, a solution prepared by dissolving 2.5 g of sodium palmitate in hot water (80 ° C.) was added. This was aged for 0.7 hours. After filtration, it was washed with 16 L of pure water at 45 ° C. and dried at 125 ° C. for 8 hours. The specific surface area of the obtained sample was 9.5 m 2 / g.
（含塩素樹脂組成物の作製及び評価）
　上記ハイドロタルサイト型化合物粒子粉末を用いて以下の含塩素樹脂組成物とした（軟質組成）。 (Production and evaluation of chlorine-containing resin composition)
The following hydrotalcite-type compound particle powder was used to prepare the following chlorine-containing resin composition (soft composition).
　　　含塩素樹脂組成物　　　　　　　　　　　　１００ｐｈｒ
　　　ＤＯＰ　　　　　　　　　　　　　　　　　　５５ｐｈｒ
　　　ステアリン酸亜鉛　　　　　　　　　　　　０．６ｐｈｒ
　　　上記試料　　　　　　　　　　　　　　　　３．０ｐｈｒ Chlorine-containing resin composition 100phr
DOP 55 phr
Zinc stearate 0.6 phr
Sample above 3.0 phr
　１５８℃にて５分ロール混練し、１５８℃にて圧縮成形プレス処理を行った。得られたシートのレベル３の時間は６０ｍｉｎ、レベル５の時間は９５ｍｉｎであった。 Roll kneading at 158 ° C. for 5 minutes and compression molding press treatment at 158 ° C. were performed. The level 3 time of the obtained sheet was 60 min, and the level 5 time was 95 min.
　比較例４：
（ハイドロタルサイト型化合物粒子粉末の作製）
　硝酸マグネシウム６水塩結晶１７１．２ｇ及び硝酸アルミニウム９水塩結晶１２５．０ｇを純水に溶解した。別に、炭酸ソーダ結晶３５．７ｇを純水で溶解し、さらに苛性ソーダ（１２Ｎ）１２６．４ｍｌと純水を加えた。このアルカリ溶液を先の硝酸マグネシウム６水塩結晶及び硝酸アルミニウム９水塩を混合した水溶液に投入して９０℃に昇温し、９０℃にて１０時間撹拌した。全量を１Ｌとし、これをオートクレーブに移して１３０℃にて５時間撹拌しながらエージングした。 Comparative Example 4:
(Preparation of hydrotalcite-type compound particle powder)
171.2 g of magnesium nitrate hexahydrate crystals and 125.0 g of aluminum nitrate 9 hydrate crystals were dissolved in pure water. Separately, 35.7 g of sodium carbonate crystals were dissolved in pure water, and 126.4 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into an aqueous solution in which the magnesium nitrate hexahydrate crystal and the aluminum nitrate nonahydrate were mixed, heated to 90 ° C., and stirred at 90 ° C. for 10 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 130 ° C. for 5 hours.
　続いて、この反応スラリーを撹拌しながら６２℃にして、ｐＨを８．６に調整した。この状態に２．５ｇのステアリン酸ソーダを熱湯（８０℃）に溶解した溶液を投入した。これを０．６時間エージングした。濾過後、６０℃の純水２５Ｌで水洗し、１２５℃で８ｈ乾燥を行った。得られた試料の比表面積は１８．９ｍ２／ｇであった。 Subsequently, the reaction slurry was stirred and brought to 62 ° C., and the pH was adjusted to 8.6. In this state, a solution prepared by dissolving 2.5 g of sodium stearate in hot water (80 ° C.) was added. This was aged for 0.6 hours. After filtration, it was washed with 25 L of pure water at 60 ° C. and dried at 125 ° C. for 8 hours. The specific surface area of the obtained sample was 18.9 m 2 / g.
（含塩素樹脂組成物の作製及び評価）
　上記ハイドロタルサイト型化合物粒子粉末を用いて以下の含塩素樹脂組成物とした（軟質組成）。 (Production and evaluation of chlorine-containing resin composition)
The following hydrotalcite-type compound particle powder was used to prepare the following chlorine-containing resin composition (soft composition).
　　　含塩素樹脂組成物　　　　　　　　　　　　１００ｐｈｒ
　　　ＤＯＰ　　　　　　　　　　　　　　　　　５５ｐｈｒ
　　　ステアリン酸亜鉛　　　　　　　　　　　　０．６ｐｈｒ
　　　上記試料　　　　　　　　　　　　　　　　３．０ｐｈｒ Chlorine-containing resin composition 100phr
DOP 55 phr
Zinc stearate 0.6 phr
Sample above 3.0 phr
　１５８℃にて５分ロール混練し、１５８℃にて圧縮成形プレス処理を行った。得られたシートのレベル３の時間は６０ｍｉｎ、レベル５の時間は８５ｍｉｎであった。 Roll kneading at 158 ° C. for 5 minutes and compression molding press treatment at 158 ° C. were performed. The level 3 time of the obtained sheet was 60 min, and the level 5 time was 85 min.
　比較例５：
（ハイドロタルサイト型化合物粒子粉末の作製）
　硫酸マグネシウム７水塩結晶１７６．３ｇ及び硫酸アルミニウム８水塩結晶６９．４ｇを純水に溶解した。別に、炭酸ソーダ結晶３０．６ｇを純水で溶解し、さらに苛性ソーダ（１２Ｎ）１２２．４ｍｌと純水を加えた。このアルカリ溶液を先の硫酸マグネシウム７水塩結晶及び硫酸アルミニウム８水塩を混合した水溶液に投入して９０℃に昇温し、９０℃にて１０時間撹拌した。全量を１Ｌとし、これをオートクレーブに移して１４５℃にて６時間撹拌しながらエージングした。 Comparative Example 5:
(Preparation of hydrotalcite-type compound particle powder)
176.3 g of magnesium sulfate heptahydrate crystals and 69.4 g of aluminum sulfate octahydrate crystals were dissolved in pure water. Separately, 30.6 g of sodium carbonate crystals were dissolved in pure water, and 122.4 ml of caustic soda (12N) and pure water were further added. This alkaline solution was put into an aqueous solution in which the magnesium sulfate heptahydrate crystal and aluminum sulfate octahydrate were mixed, heated to 90 ° C., and stirred at 90 ° C. for 10 hours. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 145 ° C. for 6 hours.
　続いて、この反応スラリーを撹拌しながら６５℃にして、ｐＨを７．４に調整した。この状態に１．９ｇのラウリン酸ソーダを熱湯（８０℃）に溶解した溶液を投入した。これを０．８時間エージングした。濾過後、４５℃の純水１５Ｌで水洗し、１２５℃で８ｈ乾燥を行った。得られた試料の比表面積は９．７ｍ２／ｇであった。 Subsequently, the reaction slurry was stirred and brought to 65 ° C., and the pH was adjusted to 7.4. In this state, a solution prepared by dissolving 1.9 g of sodium laurate in hot water (80 ° C.) was added. This was aged for 0.8 hours. After filtration, it was washed with 15 L of pure water at 45 ° C. and dried at 125 ° C. for 8 hours. The specific surface area of the obtained sample was 9.7 m 2 / g.
（含塩素樹脂組成物の作製及び評価）
　上記ハイドロタルサイト型化合物粒子粉末を用いて以下の含塩素樹脂組成物とした（半硬質組成）。 (Production and evaluation of chlorine-containing resin composition)
The following hydrotalcite-type compound particle powder was used to prepare the following chlorine-containing resin composition (semi-hard composition).
　　　含塩素樹脂組成物　　　　　　　　　　　　１００ｐｈｒ
　　　ＤＯＰ　　　　　　　　　　　　　　　　　　２０ｐｈｒ
　　　ステアリン酸亜鉛　　　　　　　　　　　　０．８ｐｈｒ
　　　上記試料　　　　　　　　　　　　　　　　３．５ｐｈｒ Chlorine-containing resin composition 100phr
DOP 20 phr
Zinc stearate 0.8 phr
Sample above 3.5phr
　１７８℃にて５分ロール混練し、１７８℃にて圧縮成形プレス処理を行った。得られたシートのレベル３の時間は６０ｍｉｎ、レベル５の時間は９５ｍｉｎであった。 Roll kneading at 178 ° C. for 5 minutes and compression molding press treatment at 178 ° C. were performed. The level 3 time of the obtained sheet was 60 min, and the level 5 time was 95 min.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　本発明に係るハイドロタルサイト粒子粉末を用いることで含塩素樹脂組成物材料において、樹脂組成物の電気絶縁性、着色及び熱安定性を改善させることができる。このため、より多くのアプリケーションへの展開が可能となる。 In the chlorine-containing resin composition material, the electrical insulation, coloring and thermal stability of the resin composition can be improved by using the hydrotalcite particle powder according to the present invention. For this reason, the expansion to more applications becomes possible.

Claims (7)

  1. 　可溶性アニオンの合計値が７０ｐｐｍ以下であることを特徴とするＭｇ－Ａｌ系又はＭｇ－Ｚｎ－Ａｌ系ハイドロタルサイト型化合物粒子粉末。 Mg-Al-based or Mg-Zn-Al-based hydrotalcite-type compound particle powder characterized in that the total value of soluble anions is 70 ppm or less.
  2. 　請求項１記載のハイドロタルサイト型化合物粒子粉末において、含有するナトリウムが７００ｐｐｍ以下であることを特徴とするＭｇ－Ａｌ系又はＭｇ－Ｚｎ－Ａｌ系ハイドロタルサイト型化合物粒子粉末。 The hydrotalcite-type compound particle powder according to claim 1, wherein the sodium-containing Mg-Al-based or Mg-Zn-Al-based hydrotalcite-type compound particle powder contains 700 ppm or less.
  3. 　請求項１又は２に記載のハイドロタルサイト型化合物粒子粉末を用いた含塩素樹脂組成物を安定化させるための含塩素樹脂安定剤。 A chlorine-containing resin stabilizer for stabilizing a chlorine-containing resin composition using the hydrotalcite-type compound particle powder according to claim 1 or 2.
  4. 　請求項１又は２に記載のハイドロタルサイト型化合物粒子粉末を塩素含有樹脂中に含有することを特徴とする含塩素樹脂組成物。 A chlorine-containing resin composition comprising the hydrotalcite-type compound particle powder according to claim 1 or 2 in a chlorine-containing resin.
  5. 　請求項１又は２に記載のハイドロタルサイト型化合物粒子粉末の製造方法であって、ハイドロタルサイト型化合物粒子を生成および熟成させた後のスラリーを、ｐＨ９．５～１２に調節した後、洗浄し、乾燥することを特徴とするハイドロタルサイト型化合物粒子粉末の製造方法。 The method for producing hydrotalcite-type compound particle powder according to claim 1 or 2, wherein the slurry after the hydrotalcite-type compound particles are generated and aged is adjusted to pH 9.5 to 12, and then washed. And drying the hydrotalcite-type compound particle powder, which is characterized by being dried.
  6. 　洗浄する工程が、希アルカリ水溶液で洗浄した後、さらに水洗する請求項５に記載の製造方法。 The manufacturing method according to claim 5, wherein the step of cleaning is performed with a dilute alkaline aqueous solution and then with water.
  7. 　洗浄工程で使用する希アルカリ水溶液および／または水の温度が３０～９０℃である請求項６に記載の製造方法。 The method according to claim 6, wherein the temperature of the dilute alkaline aqueous solution and / or water used in the washing step is 30 to 90 ° C.
PCT/JP2009/001335 2008-03-31 2009-03-25 Particulate powder of hydrotalcite type compound, chlorinated-resin stabilizer comprising the particulate powder of hydrotalcite type compound, and chlorinated-resin composition WO2009122681A1 (en)

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