KR20100138966A - Particulate powder of hydrotalcite type compound, chlorinated-resin stabilizer comprising the particulate powder of hydrotalcite type compound, and chlorinated-resin composition - Google Patents

Abstract

Mg-Al- or Mg-Zn-Al-based hydrotalcite-type compound particle powder, characterized in that the total value of soluble anions is 70 ppm or less, chlorine-containing resin for stabilizing chlorine-containing resin composition using the particle powder It relates to a chlorine-containing resin composition containing a resin stabilizer and the particle powder in a chlorine-containing resin. The particle molecule can be produced by adjusting the slurry after the generation and aging of the hydrotalcite compound particles to pH 9.5 to 12, followed by washing and drying.

Description

HYDRROTALCITE POWDER OF HYDROTALCITE TYPE COMPOUND, AND CHLORINATED -RESIN COMPOSITION}

The present invention is derived from the hydrotalcite-type compound particle powder in the chlorine-containing resin composition, which can suppress the deterioration of electrical insulating properties, provide excellent thermal stability of the chlorine-containing resin, and suppress the coloring of the resin.

In recent years, as a stabilizer of chlorine-containing resins, Pb and Sn have been changed into a combination of nontoxic metal soaps and hydrotalcite compounds, and materials using chlorine-containing resins have various uses such as wire coating, films, building materials, and pipes. It is used.

Hydrotalcite is a layered compound generally represented by Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O, in which CO ₃ , H ₂ O, and OH ⁻ are intercalated between layers of Mg-Al. . In the structure, part or all of Mg ²⁺ may be substituted with divalent cations such as Ni ²⁺ , Zn ²⁺ , Sr ²⁺ or Ca ²⁺ , and similarly, part or all of Al ³⁺ may be replaced with Fe ³⁺ or Cr. ^Trivalent cations, such as ³⁺ , can be substituted. CO ₃ ^2- can also be exchanged with anions such as SO ₄ ²⁺ or Cl ⁻ . Moreover, generally, even if the molar ratio of divalent and trivalent cations is changed, a structure can be maintained and a layered structure can be taken in the range whose molar ratio is 2-4. The layered compound which changed the composition of these constituent elements and the ratio of divalent and trivalent cations is generally called a hydrotalcite compound.

In particular, stabilizers for wire coating applications have been rapidly changed to include hydrotalcite compounds. However, when the hydrotalcite-type compound is used as a stabilizer for wire coating, the electrical resistance tends to be lowered, and it can be used in low voltage wires in some way. Pb-based stabilizers with high insulation are used.

However, de-Pb is required in high-voltage wires from environmentally friendly movements, and hydrotalcite-type compounds capable of maintaining high electrical insulation are desired.

In general, in an aqueous solution or the like, the higher the amount of dissolved ions, the higher the conductivity. Similarly, the higher the number of conductive ions in the resin, the higher the conductivity of the resin. In other words, the more electrically conductive ions, the lower the electrical insulation of the resin.

Hydrotalcite-type compound particles contain a small amount of impurity ions such as sulfate ions and sodium ions in the structure and near the surface thereof, which is considered to be a cause of lowering the electrical insulation. In addition, these ions are accompanied by the cause of deterioration of coloring of the resin and thermal stability.

It is known to use a hydrotalcite-type compound as a stabilizer of chlorine-containing resin until now (patent document 1-3), and it is also known that there exists a tendency for electric resistance to improve when there is little amount of sodium contained in hydrotalcite-type compound particle | grains. (Patent Documents 2 and 3).

Japanese Patent Laid-Open No. 2000-290451 Japanese Patent Publication No. 2007-106620 International Publication No. 2006/043352

In the hydrotalcite-type compounds described in the above Patent Documents 1 to 3, it is difficult to say that the electrical insulating property of the resin is sufficient, and that the hydrotalcite compound is excellent in function as a stabilizer of the chlorine-containing resin composition.

Therefore, it is a technical subject of this invention to provide the hydrotalcite type compound with few electroconductive ions eluted, and to provide resin with high electrical insulation containing the said hydrotalcite type compound.

The technical problem can be achieved by the present invention as follows.

That is, this invention is Mg-Al type | system | group or Mg-Zn-Al type | system | group hydrotalcite-type compound particle powder characterized by the sum total of soluble anion being 70 ppm or less (this invention 1).

Sodium contained in the hydrotalcite-type compound according to the present invention is 700 ppm or less, Mg-Al- or Mg-Zn-Al-based hydrotalcite-type compound particle powder (Invention 2).

It is a chlorine-containing resin stabilizer for stabilizing the chlorine-containing resin composition using the hydrotalcite type compound particle powder of this invention 1 or 2 (this invention 3).

It is a chlorine-containing resin composition characterized by containing the hydrotalcite-type compound particle powder of this invention 1 or 2 in chlorine-containing resin (this invention 4).

It is a chlorine-containing resin composition characterized by containing the hydrotalcite-type compound particle powder of this invention 1 or 2 in chlorine-containing resin (this invention 5).

It is a manufacturing method of the hydrotalcite type compound particle of this invention 1 or 2, Comprising: The slurry after producing | generating and ripening hydrotalcite type | mold particle | grains is adjusted to pH 9.5-12, wash | cleaned and dried, It is characterized by the above-mentioned. It is a manufacturing method of the hydrotalcite type compound particle | grains which are mentioned (this invention 6).

It is a manufacturing method as described in this invention 5 which washes further, after wash | cleaning with a pale aqueous alkali solution (this invention 7).

It is the manufacturing method as described in this invention 6 whose temperature of the pale aqueous alkali solution and / or water used at a washing process is 30-90 degreeC (this invention 8).

By using the hydrotalcite-type compound particle powder with little electroconductive ion eluted which concerns on this invention, high electrical insulation can be made to resin. In addition, thermal stability and coloring can also be improved.

First, the hydrotalcite compound particle powder which concerns on this invention is described.

In the hydrotalcite-type compound particle powder having little conductive ions eluted according to the present invention, the hydrotalcite-type compound is composed of Mg, Al, Zn, and the like, and is commonly represented by Mg-Al or Mg-Zn-Al will be.

The composition of the hydrotalcite compound particle powder according to the present invention is not particularly limited. For example, the Mg / Al molar ratio generally known is preferably 1.0 to 3.5, and zinc in the Mg-Al-Zn system is Mg. And 0.0010 to 0.30 in molar ratio with respect to the total moles of Al, and about 0.005 to 0.5 in terms of molar ratio of Zn / Al.

The total value of the soluble anions (soluble sulfate ion, soluble nitrate ion and soluble chloride ion) contained in the hydrotalcite compound particle powder according to the present invention is 70 ppm or less. When these amount of soluble anions is large, high electrical insulation is not 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. In addition, a lower limit is about 5 ppm normally.

The sodium contained in the hydrotalcite compound particle powder according to the present invention is preferably 700 ppm or less. When there is little sodium containing, there is a high possibility that there will be little sodium dissolved. Sodium ions have less effect than soluble anions, but less sodium results in higher electrical insulation. Preferably it is 600 ppm or less sodium, More preferably, it is 550 ppm or less. In addition, a lower limit is about 20 ppm normally.

The specific surface area of the hydrotalcite 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 hardly obtained industrially. It is difficult to obtain industrially even if it exceeds 150 m <2> / g. Preferably it is 7-100 m <2> / g, More preferably, it is 8-50 m <2> / g.

The hydrotalcite compound particle powder according to the present invention may contain about 0.01 to 5% by weight of calcium.

The hydrotalcite compound particle powder according to the present invention may contain about 0.01 to 8% by weight of zinc oxide.

As for the average plate surface diameter of the hydrotalcite type compound particle powder which concerns on this invention, 0.05-0.8 micrometer is preferable.

Next, the manufacturing method of the hydrotalcite-type compound particle powder which concerns on this invention is described.

Hydrotalcite-type compound particle powder in this invention mixes the alkaline aqueous solution containing anion, the magnesium salt aqueous solution, and the aluminum salt aqueous solution, makes it the mixed solution of the pH value 10-14, and then makes the said mixed solution The magnesium was aged at a temperature in the range of 80 to 105 ° C. to produce core particles of Mg-Al-based hydrotalcite-type particles, and then added to the aqueous suspension containing the core particles when the core particles were produced. And a magnesium salt aqueous solution containing magnesium and aluminum and an aqueous aluminum salt solution at a rate such that the total mole number is 0.35 or less with respect to the total number of moles of the aluminum, and the pH value is in the range of 10 to 14, and the temperature is 60 to 105 Growth reaction on core particles at normal pressure, such as Mg-Al-based hydrotalcite-type particle powder, aged in the range of Huh-Open No. 2002-293535 gazette), or it is preferable to use the generated at 105 to 350 ℃ using an autoclave. These materials include, for example, raw materials such as sulfate metals, nitrate metals, chloride metals, and metal oxides for Mg, Al, and Zn, and alkalis such as caustic soda and potassium hydroxide, anions such as sodium carbonate, basic magnesium carbonate, and potassium carbonate. It can produce from a raw material.

In order to produce hydrotalcite-type compound particles having a small amount of soluble anions (soluble sulfate ions, soluble nitrate ions and soluble chloride ions), a slurry or a hydrophobized surface treatment after producing and maturing the target hydrotalcite-type compound particles It is preferable to adjust the slurry after performing the process to pH 9.5-12, and more preferable pH is 9.8-11.5. By adjusting to the said pH range, anions, such as a sulfate ion, fall easily by washing | cleaning (washing water). Sodium tends to fall relatively easily with water, but soluble anions such as soluble sulfate ions, soluble nitrate ions and soluble chloride ions are difficult to simply reduce with water. Therefore, at the time of washing with water, an anion such as sulfate ion is more easily lowered by first washing with a light alkali aqueous solution to reduce anions such as sulfate ions and further washing with water. Alkali aqueous solutions, such as sodium hydroxide and sodium carbonate, can be used for pH adjustment of the slurry containing the said hydrotalcite type particle powder, and the pale aqueous alkali solution used for washing | cleaning before washing with water.

Moreover, it is preferable that the temperature of the pale alkali aqueous solution and / or water used for pale aqueous alkali solution and / or water washing is 30-90 degreeC. When the alkali aqueous solution and / or water of this range are light, the diffusion rate of an ion improves, the viscosity of water falls further, and the water washing effect becomes high. More preferably, it is 40-70 degreeC.

It is preferable to fundamentally dry the hydrotalcite type compound particle powder obtained as mentioned above at 105-150 degreeC. At a drying temperature of less than 105 ° C., since the water of the hydrotalcite-type compound particle powder obtained is large, foaming is likely to occur in the resin, and it is necessary for a long time to dry, which is not economical. When it exceeds 150 degreeC, there exists a tendency for the deterioration suppression function with respect to resin to fall as a stabilizer use of a soft to semi-rigid chlorine containing resin composition. As a stabilizer use of a soft to semi-rigid chlorine containing resin composition, 105-130 degreeC of drying temperature is more preferable. What is necessary is just to perform drying time for the required time by drying amount or a drying method. Preferably it is 3 to 24 hours.

Next, the chlorine-containing resin stabilizer and the chlorine-containing resin composition according to the present invention will be described.

The hydrotalcite compound particle powder of the present invention 1 or 2 can be used by being added to a chlorine-containing resin composition as a chlorine-containing resin stabilizer.

It is preferable that the chlorine-containing resin composition which concerns on this invention contains 0.01-10 weight part of said hydrotalcite type compound particle powders with respect to 100 weight part of resin. When the content of the hydrotalcite compound particle powder is less than 0.01 part by weight, the effect as a stabilizer is low. If it exceeds 10 parts by weight, the effect is saturated, so it is not meant to be added more than necessary. In addition, when the hydrotalcite-type particle powder is added in a large amount more than necessary, foaming is likely to occur, which may adversely affect appearance defects and initial coloring.

Moreover, you may contain a plasticizer, another stabilizer, and an additive in resin as needed.

Examples of the plasticizer include trimellitic acid ester plasticizers such as trioctyl trimellitate (TOTM) and tri-n-octyl-n-decyl trimellitate, diisodecyl phthalate (DIDP), and diisononyl phthalate (DINP). And phthalic acid ester plasticizers such as di-2-ethylhexyl phthalate (DOP), polyester plasticizers such as polypropylene adipate and polypropylene sebacate.

Other stabilizers include zinc compounds such as zinc stearate, zinc laurate, and zinc ricinoleate, β-diketones such as dibenzoylmethane, stearoylbenzoylmethane, dihydroacetic acid, alkyl allyl phosphate, trialkyl phosphate, and the like. Polyhydric alcohol compounds such as phosphites, dipentaerythritol, pentaerythritol, glycerin, diglycerin, trimethylolpropane, higher fatty acids such as stearic acid, lauric acid and oleic acid, epoxidized linseed oil, epoxidized soybean oil, etc. Epoxy compounds and the like are preferable.

As other additives, antioxidants, such as a phenolic compound, an amine compound, and a phosphoric acid type compound, the thing which changed the terminal of polyester into OH group, gelation, such as an acrylonitrile-styrene copolymer, methyl methacrylate copolymer, etc. Extenders such as accelerators, calcium carbonate, silica, glass beads, mica, glass fibers, inorganic flame retardants such as antimony trioxide, aluminum hydroxide, zinc borate, organic flame retardants containing bromine, halogen-containing phosphate ester flame retardants, such as stearic acid, polyethylene Lubricating agents, such as wax, calcium stearate, magnesium stearate, and barium stearate, antifungal agents, such as triclosan, orthoside, acid azole 100, and acid azole 300, etc. are used.

When using the hydrotalcite-type compound which concerns on this invention as a chlorine-containing resin composition, at least 1 selected from a higher fatty acid, an anionic surfactant, a higher fatty acid phosphate ester, a coupling agent, and a polyhydric alcohol ester for the hydrotalcite-type compound is used. It is preferable to perform surface treatment of the species. The surface treatment can further impart stability of the chlorine-containing resin composition.

As the higher fatty acid, for example, lauric acid, stearic acid, palmitic acid, oleic acid, linoleic acid, and the like, and the higher fatty acid phosphate esters are, for example, stearyl ether phosphoric acid, oleyl ether phosphoric acid, lauryl ether phosphoric acid, Examples of the polyhydric alcohol esters include sorbitan monooleate, sorbitan monolaurate, and stearic acid monoglyceride.

Examples of the anionic surfactants include salts such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium stearate, potassium oleate, and potassium castor oil.

As the coupling agent, a silane-based, aluminum-based, titanium-based, zirconium-based coupling agent or the like can be used.

Although the processing method of a surface treating agent is not specifically limited, It can also carry out by a wet reaction on the surface of a hydrotalcite type compound particle | grain. Alternatively, the surface of the hydrotalcite compound particles may be subjected to dry surface treatment by a Henschel mixer or the like. Alternatively, simply mixing the hydrotalcite compound particles and the surface treating agent may be performed.

The chlorine-containing resin composition according to the present invention is a hydrotalcite-type compound according to the present invention in the chlorine-containing resin composition comprising the following composition, in the case of a hard or semi-hard material containing no plasticizer or only a small amount thereof. When 0.8 parts by weight of zinc stearate is used, the time of level 3 is 65 minutes or more and the time of level 5 is 100 minutes or more at the coloring level described later.

Chlorine-containing resin (polymerization degree 1000):

Taiyoenbi Kabuki Kaisha Co., Ltd. Ocean PVC TH1000 100 parts by weight

0-25 parts by weight of di-2-ethylhexyl phthalate (DOP manufactured by Daihachi Chemical Industries, Ltd.)

3.5 parts by weight of hydrotalcite compound particle powder

Zinc stearate (general reagent) 0.6 to 0.9 parts by weight

In addition, in the case of the soft material containing many plasticizers, when the hydrotalcite-type compound which concerns on this invention is used in the chlorine containing resin composition containing the following composition, the time of level 3 is 65 minutes or more at the below-mentioned coloring level. , The level 5 time is more than 100 minutes.

Chlorine-containing resin (polymerization degree 1000)

Taiyoenbi Kabuki Kaisha Co., Ltd. Ocean PVC TH1000 100 parts by weight

40 to 80 parts by weight of di-2-ethylhexyl phthalate (DOP manufactured by Daihachi Chemical Industries, Ltd.)

3.0 parts by weight of the hydrotalcite compound of the present invention

0.6 parts by weight of zinc stearate (general reagent)

Although the chlorine-containing resin composition which concerns on this invention differs also according to a use, it is preferable that volume specific resistance is 2.0x10 <^{14> (} ohm) * cm or more.

Next, the manufacturing method of the chlorine-containing resin composition which concerns on this invention is described.

Although the chlorine-containing resin composition which concerns on this invention can be obtained by a conventional manufacturing method, for example, when obtaining a kneading | mixing sheet, resin, a hydrotalcite-type compound particle powder, the said various stabilizers, additives are mixed, predetermined amount, The mixture is kneaded with a hot roll to obtain a kneading sheet and then obtained by pressurizing with a hot press. Although the kneading temperature of a hot roll changes with resin and resin composition to be used, 140-300 degreeC is preferable. As for the press temperature of a hot press, 145-320 degreeC is preferable.

<Action>

By using the hydrotalcite-type compound particle powder which concerns on this invention, the fall of the electrical insulation of resin can be suppressed, and also the improvement of thermal stability and suppression of coloring can be brought about.

That is, the hydrotalcite-type compound particle powder according to the present invention has a high electric content when used as a stabilizer of resin because the content of soluble anions such as soluble sulfate ions, soluble nitrate ions, and soluble chloride ions with electrical conductivity is small. The resin composition which has insulation is obtained. Moreover, resin baking by a salt can also be suppressed, the resin composition which has high thermal stability, and coloring was suppressed can be obtained. Moreover, when there is little sodium containing, a higher effect is acquired.

<Examples>

Representative embodiments of the present invention are as follows.

The contents of elements such as sodium, magnesium, aluminum, zinc, calcium, and the like were dissolved by acid, and analyzed and determined using yttrium as an internal standard in a plasma emission spectroscopic analyzer (iCAP6500, manufactured by Samo Electron Co., Ltd.). .

The measuring method of soluble anion is described below. 5 g of the sample was dispersed in 40 ml of ethanol, 100 ml of ultrapure water was added, shaken and mixed in a sealed container for 1 minute, and the mixture was left at 22 DEG C for 20 hours, after which the slurry was filtered and the filtrate was supplied while supplying ultrapure water. The mixture was boiled with pearl 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 chromatography analyzer (Dong-A DKK, ICA-2000) to measure sulfate ions, nitrate ions, and chloride ions, respectively.

The specific surface area value was measured by B.E.T.method using nitrogen.

The roll kneading | mixing of resin used the 6-inch two type, and combined with the resin composition, and adjusted the temperature to 140-190 degreeC. Kneading time was performed for 5 minutes.

The roll kneaded sheet was a compression molded article of 200 × 200 × 1 to 1.5 mm. The apparatus for manufacturing the compression molded body was a 70 ton automatic press (ram area 210 cm 2) and a 30 ton manual press (ram area 180 cm 2) as a hot press. Compression molding conditions were carried out in a procedure of 140 minutes to 140 ° C., 3 minutes by preheating (no pressure), 2 minutes by pressurization (6.3 MPa), and 3 minutes by cooling (3.1 MPa).

The electrical resistance (electric insulation) was measured using the obtained sheet. A resin press sheet having a thickness of 1.0 mm was manufactured, stored in a desiccator at 30 ° C.-60% for one day, and the volume resistivity value (Ω · cm) was measured according to JIS K6723.

The thermal stability test was performed by the gear-aging test machine (The 102-SHF-77S by Yasuda Seiki Seisakusho, Ltd.). The pressed sheet was cut into 30 × 30 mm sides, the test piece was placed on a glass plate, and tested at 190 ° C. for 200 minutes, taking out 2 pieces / samples every 10 minutes to print paper. Affixed.

The coloring level of the press sheet and the thermal stability test piece was defined at the following 1-7 levels.

Level 1 Almost No Pigmentation

Level 2 Dim Brown

Level 3 brown

Part 4 of level 4 is carbonization

All Level 5 carbonization and blackening

Next, embodiment is described.

Example 1:

(Preparation of Hydrotalcite Compound Particle Powder)

A slurry of 26.9 g of magnesium oxide 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 soda carbonate crystal was dissolved in pure water, and further 58.3 mL of caustic soda (12 N) and pure water were added. The alkaline solution was added to a slurry in which magnesium oxide and aluminum sulfate octahydrate were mixed previously, the temperature was raised to 80 ° C, and the mixture was 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.

Then, this reaction slurry was made 67 degreeC, stirring, and pH was adjusted to 10.3. In this state, a solution obtained by dissolving 2.3 g of soda palmitic acid in hot water (80 ° C.) was added. It was aged for 0.7 hours. After filtration, water was washed with 2 L of an aqueous solution of a light caustic soda of pH 11.5 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 11.0 m 2 / g.

(Production and Evaluation of Chlorine-Containing Resin Composition)

Using the said hydrotalcite-type compound particle | grains, it was set as the following chlorine containing resin compositions (soft composition).

Chlorine-containing resin composition 100 phr

DOP 55 phr

Zinc stearate 0.6 phr

3.0 phr of the sample

The roll kneading was performed at 158 degreeC for 5 minutes, and the compression molding press process was performed at 158 degreeC. The time of level 3 of the obtained sheet was 80 minutes, and the time of level 5 was 120 minutes.

Example 2:

(Preparation of Hydrotalcite Compound Particle Powder)

141.0 g of magnesium sulfate hydrochloride crystal, 41.5 g of zinc sulfate hydrochloride crystal, and 69.4 g of aluminum sulfate hydrochloride crystal were dissolved in pure water. Separately, 30.6 g of soda carbonate crystals were dissolved in pure water, and additionally 152.4 mL of caustic soda (12 N) and pure water were added. The alkaline solution was previously added to an aqueous solution of magnesium sulfate hydrochloride crystals, zinc sulfate hydrochloride crystals, and aluminum sulfate tetrahydrochloride, 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.

Subsequently, this reaction slurry was made 65 degreeC, stirring, and pH was adjusted to 10.1. In this state, a solution obtained by dissolving 2.5 g of sodium stearate in hot water (80 ° C.) was added. It was aged for 0.6 hours. After filtration, water was washed with 2 L of an aqueous solution of light caustic soda at pH 11 of 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.

(Production and Evaluation of Chlorine-Containing Resin Composition)

Using the said hydrotalcite-type compound particle | grains, it was set as the following chlorine containing resin compositions (soft composition).

Chlorine-containing resin composition 100 phr

DOP 55 phr

Zinc stearate 0.6 phr

3.0 phr of the sample

The roll kneading was performed at 158 degreeC for 5 minutes, and the compression molding press process was performed at 158 degreeC. The time of level 3 of the obtained sheet was 75 minutes, and the time of level 5 was 115 minutes.

Example 3:

(Preparation of Hydrotalcite Compound Particle Powder)

176.3 g of magnesium sulfate hydrochloride crystal and 69.4 g of aluminum sulfate hydrochloride crystal were dissolved in pure water. Separately, 30.6 g of soda carbonate crystals were dissolved in pure water, and additionally 152.4 mL of caustic soda (12 N) and pure water were added. The alkaline solution was added to an aqueous solution in which MgSO4 crystals and aluminum sulfate 8H4 were mixed, and the temperature was raised 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.

Subsequently, this reaction slurry was made 65 degreeC, stirring, and pH was adjusted to 11.2. In this state, the solution which melt | dissolved 1.9 g of lauric acid soda by boiling water (80 degreeC) was thrown in. It was aged for 0.8 hours. After filtration, water was washed with 2 L of an aqueous solution of light caustic soda of pH 12.5 at 45 ° C, 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.

(Production and Evaluation of Chlorine-Containing Resin Composition)

Using the said hydrotalcite type compound particle | grain, it was set as the following chlorine containing resin compositions (semi-hard composition).

Chlorine-containing resin composition 100 phr

DOP 20 phr

Zinc stearate 0.8 phr

3.5 phr of the sample

Roll kneading was carried out at 178 ° C for 5 minutes, and compression molding press treatment was performed at 178 ° C. The time of level 3 of the obtained sheet was 75 minutes, and the time of level 5 was 115 minutes.

Example 4:

(Preparation of Hydrotalcite Compound Particle Powder)

101.9 g of magnesium chloride hexahydrate crystal, 26.0 g of zinc chloride monohydrate crystal, and 80.5 g of aluminum chloride hexahydrate crystal were dissolved in pure water. Separately, 35.7 g of soda carbonate crystal was dissolved in pure water, and further 136.1 mL of caustic soda (12 N) and pure water were added. The alkaline solution was previously added to an aqueous solution of magnesium chloride hexahydrate salt crystal, zinc chloride monohydrate crystal, and aluminum chloride hexahydrate salt, and 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.

Subsequently, while stirring this reaction slurry, it was made into 70 degreeC, and pH was adjusted to 9.9. In this state, a solution obtained by dissolving 2.5 g of soda palmitic acid in hot water (80 ° C.) was added. It was aged for 0.7 hours. After filtration, water was washed with 2 L of an aqueous solution of light caustic soda at pH 11 of 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.

(Production and Evaluation of Chlorine-Containing Resin Composition)

Using the said hydrotalcite-type compound particle | grains, it was set as the following chlorine containing resin compositions (soft composition).

Chlorine-containing resin composition 100 phr

DOP 55 phr

Zinc stearate 0.6 phr

3.0 phr of the sample

The roll kneading was performed at 158 degreeC for 5 minutes, and the compression molding press process was performed at 158 degreeC. The time of level 3 of the obtained sheet was 75 minutes, and the time of level 5 was 120 minutes.

Example 5:

(Preparation of Hydrotalcite Compound Particle Powder)

141.0 g of magnesium chloride hexahydrate crystal and 74.3 g of aluminum chloride hexahydrate crystal were dissolved in pure water. Separately, 32.9 g of soda carbonate crystals were dissolved in pure water, and further 163.5 mL of caustic soda (12 N) and pure water were added. The alkaline solution was previously added to an aqueous solution in which 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.

Subsequently, while stirring this reaction slurry, it was made into 70 degreeC, and pH was adjusted to 10.9. In this state, the solution which melt | dissolved 2.0 g of lauric acid soda in boiling water (80 degreeC) was thrown in. It was aged for 0.9 hours. After filtration, water was washed with 2 L of an aqueous solution of light caustic soda at pH 12 of 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.

(Production and Evaluation of Chlorine-Containing Resin Composition)

Using the said hydrotalcite-type compound particle | grains, it was set as the following chlorine containing resin compositions (soft composition).

Chlorine-containing resin composition 100 phr

DOP 55 phr

Zinc stearate 0.6 phr

3.0 phr of the sample

The roll kneading was performed at 158 degreeC for 5 minutes, and the compression molding press process was performed at 158 degreeC. The time of level 3 of the obtained sheet was 90 minutes, and the time of level 5 was 110 minutes.

Example 6:

(Preparation of Hydrotalcite Compound Particle Powder)

149.8 g of magnesium nitrate hexate crystal, 25.0 g of zinc nitrate hexate crystal, and 125.0 g of aluminum nitrate hexate crystal were dissolved in pure water. Separately, 35.7 g of soda carbonate crystals were dissolved in pure water, and further, 126.4 mL of caustic soda (12 N) and pure water were added. The alkaline solution was added to an aqueous solution in which magnesium nitrate hexahydrate salt crystal, zinc nitrate hexahydrate salt crystal, and aluminum nitrate hexahydrate salt were mixed in advance, and the temperature was raised to 90 ° C, followed by stirring 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.

Subsequently, this reaction slurry was made 62 degreeC, stirring, and pH was adjusted to 10.0. In this state, a solution obtained by dissolving 2.5 g of sodium stearate in hot water (80 ° C.) was added. It was aged for 0.6 hours. After filtration, water was washed with 2 L of an aqueous solution of light caustic soda at pH 11.5 of 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.

(Production and Evaluation of Chlorine-Containing Resin Composition)

Using the said hydrotalcite-type compound particle | grains, it was set as the following chlorine containing resin compositions (soft composition).

Chlorine-containing resin composition 100 phr

TOTM 60 phr

Zinc stearate 0.7 phr

3.3 phr of the sample

The roll kneading was performed at 162 degreeC for 5 minutes, and the compression molding press process was performed at 162 degreeC. The time of level 3 of the obtained sheet was 80 minutes, and the time of level 5 was 110 minutes.

Example 7:

(Preparation of Hydrotalcite Compound Particle Powder)

171.2 g of magnesium nitrate hexahydrate crystal and 125.0 g of aluminum nitrate 9 hydrochloride crystal were dissolved in pure water. Separately, 35.7 g of soda carbonate crystals were dissolved in pure water, and further, 126.4 mL of caustic soda (12 N) and pure water were added. The alkaline solution was previously added to an aqueous solution in which magnesium nitrate hexate crystals and aluminum nitrate hexate were mixed to raise the temperature 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.

Subsequently, this reaction slurry was made 62 degreeC, stirring, and pH was adjusted to 10.0. In this state, a solution obtained by dissolving 2.5 g of sodium stearate in hot water (80 ° C.) was added. It was aged for 0.6 hours. After filtration, water was washed with 3 L of an aqueous solution of light caustic soda at pH 11 of 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.

(Production and Evaluation of Chlorine-Containing Resin Composition)

Using the said hydrotalcite-type compound particle | grains, it was set as the following chlorine containing resin compositions (soft composition).

Chlorine-containing resin composition 100 phr

DOP 55 phr

Zinc stearate 0.6 phr

3.0 phr of the sample

The roll kneading was performed at 158 degreeC for 5 minutes, and the compression molding press process was performed at 158 degreeC. The time of level 3 of the obtained sheet was 80 minutes, and the time of level 5 was 115 minutes.

Example 8:

(Preparation of Hydrotalcite Compound Particle Powder)

176.3 g of magnesium sulfate hydrochloride crystal and 69.4 g of aluminum sulfate hydrochloride crystal were dissolved in pure water. Separately, 30.6 g of soda carbonate crystal was dissolved in pure water, and additionally 152.4 mL of caustic soda (12 N) and pure water were added. The alkaline solution was added to an aqueous solution in which MgSO4 crystals and aluminum sulfate 8H4 were mixed, and the temperature was raised 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.

Subsequently, this reaction slurry was 65 degreeC stirring, and pH was adjusted to 11.9. In this state, the solution which melt | dissolved 1.9 g of sodium laurate in boiling water (80 degreeC) was thrown in. It was aged for 0.8 hours. After filtration, water was washed with 2 L of an aqueous solution of light caustic soda at pH 13 of 40 ° C, 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.

(Production and Evaluation of Chlorine-Containing Resin Composition)

Using the said hydrotalcite type compound particle | grain, it was set as the following chlorine containing resin compositions (semi-hard composition).

Chlorine-containing resin composition 100 phr

DOP 20 phr

Zinc stearate 0.8 phr

3.5 phr of the sample

Roll kneading was carried out at 178 ° C for 5 minutes, and compression molding press treatment was performed at 178 ° C. The time of level 3 of the obtained sheet was 75 minutes, and the time of level 5 was 110 minutes.

Example 9:

(Preparation of Hydrotalcite Compound Particle Powder)

101.9 g of magnesium chloride hexahydrate crystal, 26.0 g of zinc chloride monohydrate crystal, and 80.5 g of aluminum chloride hexahydrate crystal were dissolved in pure water. Separately, 35.7 g of soda carbonate crystal was dissolved in pure water, and further 136.1 mL of caustic soda (12 N) and pure water were added. The alkaline solution was previously added to an aqueous solution of magnesium chloride hexahydrate salt crystal, zinc chloride monohydrate crystal, and aluminum chloride hexahydrate salt, and 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.

Subsequently, this reaction slurry was adjusted to 70 ° C. while stirring, and the pH was adjusted to 11.7. In this state, a solution obtained by dissolving 2.5 g of soda palmitic acid in hot water (80 ° C.) was added. It was aged for 0.7 hours. After filtration, water was washed with 2 L of an aqueous solution of a light caustic soda at pH 13 of 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.

(Production and Evaluation of Chlorine-Containing Resin Composition)

Using the said hydrotalcite-type compound particle | grains, it was set as the following chlorine containing resin compositions (soft composition).

Chlorine-containing resin composition 100 phr

DOP 55 phr

Zinc stearate 0.6 phr

3.0 phr of the sample

The roll kneading was performed at 158 degreeC for 5 minutes, and the compression molding press process was performed at 158 degreeC. The time of level 3 of the obtained sheet was 75 minutes, and the time of level 5 was 110 minutes.

Example 10:

(Preparation of Hydrotalcite Compound Particle Powder)

141.0 g of magnesium chloride hexahydrate crystal and 74.3 g of aluminum chloride hexahydrate crystal were dissolved in pure water. Separately, 32.9 g of soda carbonate crystals were dissolved in pure water, and further 203.5 mL of caustic soda (12 N) and pure water were added. The alkaline solution was added to an aqueous solution in which magnesium chloride hexahydrate crystal and aluminum chloride hexahydrate were mixed in advance, and then an aqueous solution in which 4.50 g of calcium chloride dihydrate crystal was dissolved was added thereto, and the temperature was raised to 75 ° C. Stir at 75 ° C for 15 h. The total amount was 1 L, which was transferred to an autoclave and aged with stirring at 170 ° C. for 9 hours.

Subsequently, while stirring this reaction slurry, it was made into 70 degreeC, and pH was adjusted to 10.9. In this state, the solution which melt | dissolved 2.0 g of lauric acid soda in boiling water (80 degreeC) was thrown in. It was aged for 0.9 hours. After filtration, water was washed with 2 L of an aqueous solution of light caustic soda at pH 12 of 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.

(Production and Evaluation of Chlorine-Containing Resin Composition)

Using the said hydrotalcite-type compound particle | grains, it was set as the following chlorine containing resin compositions (soft composition).

Chlorine-containing resin composition 100 phr

DOP 55 phr

Zinc stearate 0.6 phr

3.0 phr of the sample

The roll kneading was performed at 158 degreeC for 5 minutes, and the compression molding press process was performed at 158 degreeC. The time of level 3 of the obtained sheet was 90 minutes, and the time of level 5 was 110 minutes.

Example 11:

(Preparation of Hydrotalcite 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 soda carbonate crystal was dissolved in pure water, and further 136.1 mL of caustic soda (12 N) and pure water were added. The alkaline solution was previously added to an aqueous solution of magnesium chloride hexahydrate salt crystal, zinc chloride monohydrate crystal, and aluminum chloride hexahydrate salt, and 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. Then, 1.4 g of zinc oxide was added and mixed.

Subsequently, this reaction slurry was adjusted to 70 ° C. while stirring, and the pH was adjusted to 11.7. In this state, a solution obtained by dissolving 2.5 g of soda palmitic acid in hot water (80 ° C.) was added. It was aged for 0.7 hours. After filtration, water was washed with 2 L of an aqueous solution of light caustic soda of pH 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.

(Production and Evaluation of Chlorine-Containing Resin Composition)

Using the said hydrotalcite-type compound particle | grains, it was set as the following chlorine containing resin compositions (soft composition).

Chlorine-containing resin composition 100 phr

DOP 55 phr

Zinc stearate 0.6 phr

3.0 phr of the sample

The roll kneading was performed at 158 degreeC for 5 minutes, and the compression molding press process was performed at 158 degreeC. The time of level 3 of the obtained sheet was 80 minutes, and the time of level 5 was 110 minutes.

Comparative Example 1:

(Preparation of Hydrotalcite Compound Particle Powder)

A slurry of 26.9 g of magnesium oxide 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 soda carbonate crystal was dissolved in pure water, and further 58.3 mL of caustic soda (12 N) and pure water were added. The alkaline solution was added to a slurry in which magnesium oxide and aluminum sulfate octahydrate were mixed previously, the temperature was raised to 80 ° C, and the mixture was 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.

Subsequently, while stirring this reaction slurry, it was 72 degreeC and adjusted pH to 8.9. In this state, a solution obtained by dissolving 2.3 g of soda palmitic acid in hot water (80 ° C.) was added. It was aged for 0.7 hours. After filtration, water 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.

(Production and Evaluation of Chlorine-Containing Resin Composition)

Using the said hydrotalcite-type compound particle | grains, it was set as the following chlorine containing resin compositions (soft composition).

Chlorine-containing resin composition 100 phr

DOP 55 phr

Zinc stearate 0.6 phr

3.0 phr of the sample

The roll kneading was performed at 158 degreeC for 5 minutes, and the compression molding press process was performed at 158 degreeC. The time of level 3 of the obtained sheet was 50 minutes, and the time of level 5 was 90 minutes.

Comparative Example 2:

(Preparation of Hydrotalcite Compound Particle Powder)

176.3 g of magnesium sulfate hydrochloride crystal and 69.4 g of aluminum sulfate hydrochloride crystal were dissolved in pure water. Separately, 30.6 g of soda carbonate crystals were dissolved in pure water, and additionally 152.4 mL of caustic soda (12 N) and pure water were added. The alkaline solution was added to an aqueous solution in which MgSO4 crystals and aluminum sulfate 8H4 were mixed, and the temperature was raised 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.

Subsequently, this reaction slurry was made 65 degreeC, stirring, and pH was adjusted to 9.0. In this state, the solution which melt | dissolved 1.9 g of sodium laurate in boiling water (80 degreeC) was thrown in. It was aged for 0.8 hours. After filtration, water was washed with 15 L of 45 ° C. pure water and dried at 125 ° C. for 8 hours. The specific surface area of the obtained sample was 9.5 m 2 / g.

(Production and Evaluation of Chlorine-Containing Resin Composition)

Using the said hydrotalcite type compound particle | grain, it was set as the following chlorine containing resin compositions (semi-hard composition).

Chlorine-containing resin composition 100 phr

DOP 20 phr

Zinc stearate 0.8 phr

3.5 phr of the sample

Roll kneading was carried out at 178 ° C for 5 minutes, and compression molding press treatment was performed at 178 ° C. The time of level 3 of the obtained sheet was 55 minutes, and the time of level 5 was 95 minutes.

Comparative Example 3:

(Preparation of Hydrotalcite Compound Particle Powder)

101.9 g of magnesium chloride hexahydrate crystal, 26.0 g of zinc chloride monohydrate crystal, and 80.5 g of aluminum chloride hexahydrate crystal were dissolved in pure water. Separately, 35.7 g of soda carbonate crystal was dissolved in pure water, and further 136.1 mL of caustic soda (12 N) and pure water were added. The alkaline solution was previously added to an aqueous solution of magnesium chloride hexahydrate salt crystal, zinc chloride monohydrate crystal, and aluminum chloride hexahydrate salt, and 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.

Subsequently, this reaction slurry was adjusted to 70 ° C. while stirring, and the pH was adjusted to 9.1. In this state, a solution obtained by dissolving 2.5 g of soda palmitic acid in hot water (80 ° C.) was added. It was aged for 0.7 hours. After filtration, water was washed with 16 L of 45 ° C. pure water, and dried at 125 ° C. for 8 hours. The specific surface area of the obtained sample was 9.5 m 2 / g.

(Production and Evaluation of Chlorine-Containing Resin Composition)

Using the said hydrotalcite-type compound particle | grains, it was set as the following chlorine containing resin compositions (soft composition).

Chlorine-containing resin composition 100 phr

DOP 55 phr

Zinc stearate 0.6 phr

3.0 phr of the sample

The roll kneading was performed at 158 degreeC for 5 minutes, and the compression molding press process was performed at 158 degreeC. The time of level 3 of the obtained sheet was 60 minutes, and the time of level 5 was 95 minutes.

Comparative Example 4:

(Preparation of Hydrotalcite Compound Particle Powder)

171.2 g of magnesium nitrate hexahydrate crystal and 125.0 g of aluminum nitrate 9 hydrochloride crystal were dissolved in pure water. Separately, 35.7 g of soda carbonate crystals were dissolved in pure water, and further, 126.4 mL of caustic soda (12 N) and pure water were added. The alkaline solution was previously added to an aqueous solution in which magnesium nitrate hexate crystals and aluminum nitrate hexate were mixed to raise the temperature 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.

Subsequently, this reaction slurry was made 62 degreeC, stirring, and pH was adjusted to 8.6. In this state, a solution obtained by dissolving 2.5 g of sodium stearate in hot water (80 ° C.) was added. It was aged for 0.6 hours. After filtration, water 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.

(Production and Evaluation of Chlorine-Containing Resin Composition)

Using the said hydrotalcite-type compound particle | grains, it was set as the following chlorine containing resin compositions (soft composition).

Chlorine-containing resin composition 100 phr

DOP 55 phr

Zinc stearate 0.6 phr

3.0 phr of the sample

The roll kneading was performed at 158 degreeC for 5 minutes, and the compression molding press process was performed at 158 degreeC. The time of level 3 of the obtained sheet was 60 minutes, and the time of level 5 was 85 minutes.

Comparative Example 5:

(Preparation of Hydrotalcite Compound Particle Powder)

176.3 g of magnesium sulfate hydrochloride crystal and 69.4 g of aluminum sulfate hydrochloride crystal were dissolved in pure water. Separately, 30.6 g of soda carbonate crystals were dissolved in pure water, and further 122.4 mL of caustic soda (12 N) and pure water were added. The alkaline solution was added to an aqueous solution in which MgSO4 crystals and aluminum sulfate 8H4 were mixed, and the temperature was raised 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.

Subsequently, this reaction slurry was 65 degreeC stirring, and pH was adjusted to 7.4. In this state, the solution which melt | dissolved 1.9 g of sodium laurate in boiling water (80 degreeC) was thrown in. It was aged for 0.8 hours. After filtration, water was washed with 15 L of 45 ° C. pure water and dried at 125 ° C. for 8 hours. The specific surface area of the obtained sample was 9.7 m 2 / g.

(Production and Evaluation of Chlorine-Containing Resin Composition)

Using the said hydrotalcite type compound particle | grain, it was set as the following chlorine containing resin compositions (semi-hard composition).

Chlorine-containing resin composition 100 phr

DOP 20 phr

Zinc stearate 0.8 phr

3.5 phr of the sample

Roll kneading was carried out at 178 ° C for 5 minutes, and compression molding press treatment was performed at 178 ° C. The time of level 3 of the obtained sheet was 60 minutes, and the time of level 5 was 95 minutes.

Industrial availability

By using the hydrotalcite particle powder according to the present invention, in the chlorine-containing resin composition material, electrical insulation, coloring and thermal stability of the resin composition can be improved. This enables deployment to more applications.

Claims (7)

Mg-Al- or Mg-Zn-Al-based hydrotalcite compound particle powder, wherein the total value of the soluble anions is 70 ppm or less. The hydrotalcite-type compound particle powder according to claim 1, wherein the sodium contained is 700 ppm or less, Mg-Al-based or Mg-Zn-Al-based hydrotalcite-type compound particle powder. The chlorine-containing resin stabilizer for stabilizing the chlorine-containing resin composition using the hydrotalcite-type compound particle powder of Claim 1 or 2. The hydrotalcite-type compound particle powder of Claim 1 or 2 is contained in chlorine-containing resin, The chlorine-containing resin composition characterized by the above-mentioned. A method for producing the hydrotalcite-type compound particle powder according to claim 1 or 2, wherein the slurry after producing and maturing the hydrotalcite-type compound particles is adjusted to pH 9.5 to 12, and then washed and dried. A method for producing a hydrotalcite compound particle powder, characterized by the above-mentioned. The production process according to claim 5, wherein the washing step is further washed with water after washing with a light aqueous alkali solution. The production method according to claim 6, wherein the temperature of the pale aqueous alkali solution and / or water used in the washing step is 30 to 90 ° C.