JP4106508B2 - Chlorine-containing resin composition - Google Patents

Description

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【発明の効果】
本発明に係る塩素含有樹脂組成物は、熱安定性、着色性に優れ、しかも電気絶縁性に優れることから、電線被覆用途の塩素含有樹脂組成物として好適である。[0001]
BACKGROUND OF THE INVENTION
The present invention provides a chlorine-containing resin composition having excellent thermal stability and colorability and improved electrical insulation.
[0002]
[Prior art]
As is well known, there are various compounds in addition to clay minerals and the like in the layered compounds. Among them, layered double hydroxides such as hydrotalcite have various ions and molecules between the layers. Etc. can be inserted, and thus an anion exchange function can be expressed.
[0003]
In general, the structure of hydrotalcite is described in Journal of Chemical Society of Japan, 1995 (8), p622-628,
"[M²⁺ _1-xM³⁺ _x(OH)₂]_x ⁺[An⁻ _{x / n}・ YH₂O]_x ⁻Where M²⁺Mg²⁺, Co²⁺, Ni²⁺, Zn²⁺Divalent metal ions such as M³⁺Al³⁺, Fe³⁺, Cr³⁺Trivalent metal ions such as An⁻Is OH⁻, Cl⁻, CO₃ ^2-, SO₄ ^2-X is generally in the range of 0.2 to 0.33. The crystal structure has a laminated structure composed of a two-dimensional basic layer in which octahedral brucite units having a positive charge are arranged and an intermediate layer having a negative charge. It is said that.
[0004]
Hydrotalcite has been used for various applications utilizing its anion exchange function, such as ion exchange materials, adsorbents, deodorants, and the like. In addition, it is used for a variety of applications such as stabilizers for resins such as polyethylene, polypropylene, and chlorine-containing resins (typically vinyl chloride resin), as well as paints, various catalysts, agricultural films, and inks.
[0005]
In particular, among hydrotalcite-type particle powders, Mg as a divalent metal ion²⁺Al as a trivalent metal ion³⁺Mg-Al-based hydrotalcite-type particle powders having a high molecular weight are the most attracting attention because they are stable. In addition, examples of the hydrotalcite-type particle powder include iron-based hydrotalcite-type particle powder (Japanese Patent Application Laid-Open No. 9-227127). When used as a stabilizer for a chlorine-containing resin as compared with Mg—Al-based hydrotalcite-type particle powder, it is difficult to say that the thermal stability is sufficient.
[0006]
As a method for producing hydrotalcite, a metal salt aqueous solution containing divalent metal ions and trivalent metal ions constituting the basic layer and a carbonate aqueous solution containing carbonate ions constituting the intermediate layer are mixed, and the temperature is changed. In general, the pH value is controlled to obtain a coprecipitation reaction. In addition to the reaction at normal pressure, a method obtained by a hydrothermal reaction using an autoclave is also known.
[0007]
As the hydrotalcite-type particle powder for resin kneading, a particle powder having a large plate surface diameter and an appropriate thickness is required in consideration of dispersibility during resin kneading. Special reaction conditions such as hydrothermal synthesis are required for the production of large hydrotalcite particle powders.
[0008]
At present, hydrotalcite-type particle powder is attracting attention as a chlorine-containing resin stabilizer among the above-mentioned various uses. Chlorine-containing resins are used in a wide variety of applications because they have good physical and chemical properties. In particular, chlorine-containing resins are widely used as wire coating materials compared to rubber, polyolefin, etc., because they have excellent electrical insulation, arc resistance, tracking resistance, and voltage resistance. .
[0009]
However, chlorine-containing resins are susceptible to thermal degradation and oxidative degradation, and have various drawbacks such as reduced elongation during long-term use, and have the disadvantage of being unusable as a wire coating material. .
[0010]
Accordingly, lead-based compounds such as tribasic lead sulfate and lead stearate have been frequently used as stabilizers for chlorine-containing resins for wire coating applications. However, in recent years, when environmental considerations are required, those that do not contain toxic metals have been desired, and hydrotalcite-type particle powders that have almost no toxicity and excellent function as stabilizers are chlorinated. It has been proposed to be used as a stabilizer for a resin containing resin (Japanese Patent Laid-Open Nos. 55-80445, 57-80444, 57-147552, 58-122951). ).
[0011]
As a chlorine-containing resin composition for covering electric wires, it is required to have excellent thermal stability and high electrical insulation. In addition, white or light-colored wire coatings are required to have little thermal discoloration during processing, that is, good colorability. As a stabilizer for a chlorine-containing resin composition that satisfies the above characteristics, the hydrotalcite-type particle powder has a large plate surface diameter, an appropriate thickness, and a higher ability to capture chlorine ions. is needed.
[0012]
[Problems to be solved by the invention]
A chlorine-containing resin composition that is excellent in thermal stability and colorability and that has improved electrical insulation is currently most demanded, but a chlorine-containing resin composition that satisfies this requirement has not yet been obtained. .
[0013]
That is, the techniques described in the above publications contain hydrotalcites and zinc compounds, β-diketones, polyhydric alcohol compounds, perchlorates and the like as chlorine-containing resin stabilizers. In the chlorine-containing resin composition, it is intended to improve thermal stability, colorability, electrical insulation and the like. However, a satisfactory stabilizing effect was not obtained, and it was difficult to say that thermal stability, colorability and electrical insulation were sufficient.
[0014]
Therefore, it is a technical object of the present invention to obtain a chlorine-containing resin composition that is excellent in thermal stability and colorability and has high electrical insulation.
[0015]
[Means for solving the problems]
The technical problem can be achieved by the present invention as follows.
[0016]
That is, the present invention has a plate surface diameter of 0.1 to 1.0 μm, a thickness of 0.02 to 0.08 μm, and calcium in a molar ratio of 0. Mg-Al-based hydrotalcite-type particle powder containing 01 to 0.20, wherein the particle powder has a heat resistance time measured by the following measurement method of 4 hours or more. A chlorine-containing resin composition comprising hydrotalcite-type particle powder as a chlorine-containing resin stabilizer.
{Circle around (1)} Hydrotalcite-type particle powder and additives were mixed in a vinyl chloride resin at the following composition ratio, and 50 g of the resulting mixture was kneaded using a hot roll to obtain a kneaded sheet. The kneading conditions are a kneading temperature of 155 ° C., a roll gap of 0.75 mm, and a kneading time of 3 minutes.
Hydrotalcite-type particle powder: 3 parts by weight
Vinyl chloride resin (degree of polymerization 1300)
(Product name: TK-1300, manufactured by Shin-Etsu Chemical): 100 parts by weight,
Diethylhexyl phthalate (DOP, manufactured by Daihachi Chemical): 50 parts by weight,
Calcium stearate (primary reagent): 2 parts by weight
Zinc stearate (primary reagent): 0.4 parts by weight
1,3 diphenyl-1,3-propanedione (primary reagent): 0.2 parts by weight,
Diethyl phosphite (primary reagent): 0.5 parts by weight.
{Circle around (2)} The obtained kneaded sheet was pressed with a hot press to prepare a sheet piece (thickness 1.5 mm). The pressurizing conditions are a press temperature of 160 ° C. and a press pressure of 100 kg / cm.²The press time is 1 minute, the press gap is 1.5 mm, and the processing amount is 35 g.
(3) The obtained sheet piece (20 mm × 20 mm) is put in an oven at 180 ° C. in air and a heat resistance test is performed. The time when the entire sheet piece turns black is defined as the heat resistant time.
[0017]
Moreover, this invention is a chlorine containing resin composition for electric wire coating | blending which mix | blended 1.5-10 weight part of said chlorine containing resin stabilizers with respect to 100 weight part of chlorine containing resin.
[0018]
The configuration of the present invention will be described in more detail as follows.
[0019]
First, the Mg—Al hydrotalcite type particle powder in the present invention will be described.
[0020]
The Mg—Al-based hydrotalcite-type particle powder in the present invention has a plate shape, a plate surface diameter of 0.1 to 1.0 μm, and a thickness of 0.02 to 0.08 μm.
[0021]
When the plate surface diameter of the Mg—Al hydrotalcite type particle powder in the present invention is less than 0.1 μm, the dispersibility when kneaded into the resin is insufficient. If it exceeds 1.0 μm, it is difficult to produce industrially. Preferably it is 0.2-0.8 micrometer.
[0022]
When the thickness of the Mg—Al hydrotalcite type particle powder in the present invention is less than 0.02 μm, the dispersibility when kneaded into the resin is insufficient. If it exceeds 0.08 μm, it is difficult to produce industrially. Preferably it is 0.025-0.075 micrometer.
[0023]
The Mg—Al-based hydrotalcite-type particle powder in the present invention contains calcium in a molar ratio of 0.01 to 0.20 with respect to the total number of moles of Mg and Al.
[0024]
When the calcium content of the Mg—Al hydrotalcite-type particle powder in the present invention is less than 0.01 and more than 0.20 in terms of the molar ratio with respect to the total number of moles of Mg and Al, The plate surface diameter of the Al-based hydrotalcite-type particle powder cannot be made sufficiently large. A preferable range of the calcium content is 0.03 to 0.15 in terms of a molar ratio with respect to the total number of moles of Mg and Al.
[0025]
In the present invention, the Mg—Al hydrotalcite type particle powder has a heat resistance time of 4 when a resin sheet prepared by mixing 3 parts by weight of the particle powder with 100 parts by weight of vinyl chloride resin is heated at 180 ° C. It's over time.
When the heat resistant time is less than 4 hours, the heat resistance of the resin is not sufficient when used as a stabilizer for a chlorine-containing resin. Preferably it is 5 hours or more.
[0026]
The composition formula of the Mg—Al hydrotalcite-type particle powder in the present invention is as follows.
[0027]
[Mg_xCa_y] ・ Al_z・ (OH)₂・ A^n- _p・ MH₂O
0.2 ≦ z / (x + z) ≦ 0.6,
0.01 ≦ y / (x + z) ≦ 0.20,
x + y + z = 1
p = (2 (x + y-1) + 3z) / n,
A: n-valent anion, m> 0.
[0028]
In the present invention, the ratio of Mg and Al content in the Mg-Al hydrotalcite-type particle powder is such that z / (x + z) is 0.2 to 0 when Al / (Mg + Al) = z / (x + z). .6. When z / (x + z) is less than 0.2 (Mg: Al = 4: 1) and more than 0.6 (Mg: Al = 2: 3), the single phase of the hydrotalcite-type particle powder is It is difficult to obtain. A preferable range of z / (x + z) is 0.2 to 0.56.
[0029]
The sum of x, y, and z is 1.
[0030]
Anions (A) contained in the Mg-Al hydrotalcite type particle powder in the present invention^n-) Types are hydroxide ions (OH)⁻), Carbonate ion (CO₃ ^2-) And sulfate ions (SO₄ ^2-And the like, and particularly preferably carbonate ion.
[0031]
In the present invention, the Mg—Al hydrotalcite type particle powder preferably has a plate ratio (plate surface diameter / thickness) of 2 to 15, more preferably 2 to 13, and a BET specific surface area value of 8 to 90 m.²/ G is preferred, more preferably 8 to 70 m.²/ G.
[0032]
Next, a method for producing the Mg—Al hydrotalcite particle powder in the present invention will be described.
[0033]
The Mg—Al-based hydrotalcite type particle powder in the present invention is a mixture of an alkaline aqueous solution containing anions, a magnesium salt aqueous solution and an aluminum salt aqueous solution, and a calcium salt aqueous solution is added to the mixed aqueous solution, and the pH value is 10-14. It can be obtained by aging for 2 to 24 hours in a temperature range of 60 to 105 ° C.
[0034]
The alkaline aqueous solution containing anions in the present invention is preferably a mixed alkaline aqueous solution of an aqueous solution containing anions and an aqueous alkali hydroxide solution.
[0035]
As an aqueous solution containing an anion, a sodium carbonate aqueous solution is preferable. As the aqueous alkali hydroxide solution, an aqueous sodium hydroxide solution is preferable.
[0036]
As the magnesium salt aqueous solution in the present invention, a magnesium sulfate aqueous solution, a magnesium chloride aqueous solution, a magnesium nitrate aqueous solution and the like can be used, and a magnesium sulfate aqueous solution and a magnesium chloride aqueous solution are preferable.
[0037]
As the aluminum salt aqueous solution in the present invention, an aluminum sulfate aqueous solution, an aluminum chloride aqueous solution, an aluminum nitrate aqueous solution and the like can be used, and an aluminum sulfate aqueous solution and an aluminum chloride aqueous solution are preferable.
[0038]
The mixing order of the aqueous alkali solution, magnesium salt aqueous solution and aluminum salt aqueous solution containing anions is not particularly limited, and each aqueous solution may be mixed simultaneously. Preferably, an aqueous solution in which a magnesium salt aqueous solution and an aluminum salt aqueous solution are mixed in advance is added to an alkaline aqueous solution containing anions.
[0039]
Moreover, when adding each aqueous solution, you may carry out either when adding this aqueous solution at once, adding when dividing | segmenting twice or more, or adding continuously.
[0040]
The calcium salt aqueous solution in the present invention is added to a mixed solution of an alkaline aqueous solution containing an anion, a magnesium salt aqueous solution and an aluminum salt aqueous solution.
[0041]
As the calcium salt aqueous solution in the present invention, a calcium chloride aqueous solution, a calcium nitrate aqueous solution and the like can be used, and a calcium chloride aqueous solution is preferable.
[0042]
The addition amount of the calcium salt aqueous solution is 0.01 to 0.20 in molar ratio with respect to the total number of moles of Mg and Al, and preferably 0.03 to 0.15.
[0043]
In the present invention, the concentration of the magnesium salt in the reaction solution obtained by mixing the aqueous alkali solution, magnesium salt aqueous solution, aluminum salt aqueous solution and calcium salt aqueous solution containing anions is preferably 0.1 to 1.5 mol / l, more preferably 0. 0.1-1.2 mol / l, aluminum salt is preferably 0.03-1.0 mol / l, more preferably 0.04-0.8 mol / l, calcium salt is 0.001-0.2 mol / l. More preferably, 0.01 to 0.15 mol / l, an anion is preferably 0.05 to 1.4 mol / l, more preferably 0.06 to 1.2 mol / l, and an alkali hydroxide aqueous solution is used. 0.5-8 mol / l is preferable, More preferably, it is 0.8-6 mol / l.
[0044]
The temperature during the ripening reaction in the present invention is 60 to 105 ° C, preferably 80 to 105 ° C. A hydrotalcite type particle powder is produced even at a temperature lower than 60 ° C., but a hydrotalcite type particle powder having a large plate surface diameter cannot be obtained. When the temperature exceeds 105 ° C., a pressure vessel such as an autoclave is required, which is not economical.
[0045]
The pH value during the ripening reaction in the present invention is 10 to 14, preferably 11 to 14. When the pH value is less than 10, a hydrotalcite-type particle powder having a large plate surface diameter and an appropriate thickness cannot be obtained.
[0046]
The reaction time of the ripening reaction in the present invention is preferably 2 to 24 hours. When the aging time is less than 2 hours, it is difficult to obtain hydrotalcite-type particle powder having a large plate surface diameter and an appropriate thickness. Aging over 24 hours is not economical.
[0047]
After completion of the ripening reaction, Mg—Al hydrotalcite-type particle powder can be obtained by washing with water and drying by a conventional method.
[0048]
Next, the chlorine-containing resin composition according to the present invention will be described.
[0049]
The thermal stability of the chlorine-containing resin composition according to the present invention is 200 minutes or more when measured according to JIS K 6723. Preferably, it is 400 minutes to 1000 minutes. When the thermal stability is less than 200 minutes, it is not preferable as a chlorine-containing resin composition.
[0050]
The electrical resistivity of the chlorine-containing resin composition according to the present invention is such that the volume resistivity measured according to JIS K 6723 is 5.0 × 10.¹³~ 1.0 × 10¹⁶Ω · cm. Volume resistivity is 5.0 × 10¹³If it is less than 1, it is not preferable as a chlorine-containing resin composition for electric wire coating.
[0051]
The chlorine-containing resin composition according to the present invention comprises 1.5 to 10 parts by weight of the Mg-Al hydrotalcite-type particle powder, 30 to 90 parts by weight of a plasticizer, with respect to 100 parts by weight of the chlorine-containing resin. Contains other stabilizers and additives.
[0052]
In addition, as hydrotalcite-type particle powder, if necessary, use is made of a surface coating with a surface coating made of at least one selected from silicon hydroxide or silicon oxide, rosins, organosilane compounds, and higher fatty acids. May be. The hydrotalcite-type particle powder surface-treated with the surface coating is improved in dispersibility in the chlorine-containing resin.
[0053]
The coating amount of silicon hydroxide or silicon oxide is SiO to Mg-Al hydrotalcite-type particle powder.₂0.05-50 weight% is preferable in conversion, More preferably, it is 0.05-45 weight%.
[0054]
The coating amount with rosins is 0.2 to 25.0% by weight in terms of C with respect to the Mg—Al hydrotalcite type particle powder.
[0055]
The coating amount with the organosilane compound is 0.2 to 18.0% by weight in terms of C with respect to the Mg—Al-based hydrotalcite type particle powder.
[0056]
The coating amount with the higher fatty acid is 0.2 to 20.0% by weight in terms of C with respect to the Mg—Al hydrotalcite particle powder.
[0057]
Examples of the chlorine-containing resin include polyvinyl chloride, copolymers based on vinyl chloride, chlorinated polyethylene, polyvinylidene chloride, chlorinated polypropylene, chlorinated polyvinyl chloride, and mixtures thereof. Vinyl is preferred. The polymerization degree of polyvinyl chloride is preferably 1000 to 1500.
[0058]
When the content of the hydrotalcite-type particle powder is less than 1.5 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. In addition, if hydrotalcite-type particle powder is added in a larger amount than necessary, there is a risk that foaming may occur, and there is a possibility that it may adversely affect electrical insulation and other required characteristics.
[0059]
As the plasticizer, a trimetrite ester plasticizer, a phthalate ester plasticizer, a polyester plasticizer, and the like are preferable.
[0060]
Examples of the trimetrate ester plasticizer include trioctyl trimellitate, tri-n-octyl-n-decyl trimellitate, and the like.
[0061]
Examples of the phthalate ester plasticizer include diisononyl phthalate, di-2-ethylhexyl phthalate, and dinonyl phthalate.
[0062]
Polyester plasticizers include polypropylene / adipate, polypropylene / sebacate and the like.
[0063]
When the content of the plasticizer is less than 30 parts by weight, a resin composition satisfying flexibility as a wire coating application cannot be obtained. If it exceeds 90 parts by weight, the effect of imparting flexibility is saturated, so there is no point in adding more than necessary.
[0064]
As other stabilizers, zinc compounds, β-diketones, phosphites, polyhydric alcohol compounds, higher fatty acids, epoxy compounds and the like are preferable. In view of the synergistic effect with the hydrotalcite-type particle powder, a zinc compound is particularly preferable.
[0065]
As the zinc compound, zinc stearate, zinc laurate, zinc ricinoleate and the like can be used. Preferably, it is zinc stearate.
[0066]
The addition amount of the zinc compound is preferably 0.2 to 2.5 parts by weight with respect to 100 parts by weight of the chlorine-containing resin.
[0067]
Examples of β-diketones include dibenzoylmethane, stearoylbenzoylmethane, and dehydroacetic acid.
[0068]
Examples of phosphites include alkyl allyl phosphate and trialkyl phosphate.
[0069]
Examples of the polyhydric alcohol compound include dipentaerythritol, pentaerythritol, glycerin, diglycerin, trimethylolpropane and the like.
[0070]
As the higher fatty acid, stearic acid, lauric acid, oleic acid and the like can be used. Preferably, it is stearic acid.
[0071]
Examples of the epoxy compound include epoxidized linseed oil and epoxidized soybean oil.
[0072]
As other additives, antioxidants, electrical resistance improvers, gelation accelerators, extenders, flame retardants, lubricants, fungicides, and the like are used.
[0073]
As the antioxidant, phenolic compounds, amine compounds, phosphoric acid compounds and the like can be used.
[0074]
Examples of phenolic compounds include 2,6-di-tert-butyl-paracresol, 2,4,6-tri-tert-butylphenol, styrenated phenol, and the like.
[0075]
Examples of amine compounds include phenyl-β-naphthylamine and N, N′-diphenyl-p-phenylenediamine.
[0076]
Examples of the phosphoric acid compound include triphenyl phosphite, diphenyl decyl phosphite, and phenyl isodecyl phosphite.
[0077]
Examples of the electrical resistance improver include clay, mica, aluminum oxide, and barium titanate.
[0078]
Examples of the gelation accelerator include those obtained by changing the terminal of the polyester to an OH group, acrylonitrile-styrene copolymer, methyl methacrylate styrene copolymer, and the like.
[0079]
Examples of the bulking agent include calcium carbonate, silica, glass beads, mica, and glass fiber.
[0080]
Examples of the flame retardant include inorganic flame retardants such as antimony trioxide, aluminum hydroxide, and zinc borate, bromine-containing organic flame retardants, and halogen-containing phosphate ester flame retardants.
[0081]
Examples of the lubricant include calcium stearate, magnesium stearate, barium stearate and the like.
[0082]
Examples of the antifungal agent include triclosan, orthoside, sun isol 100, sun isol 300 and the like.
[0083]
When the chlorine-containing resin composition according to the present invention is colored as necessary, a pigment may be added.
[0084]
A method for producing the chlorine-containing resin composition according to the present invention will be described.
[0085]
The chlorine-containing resin composition according to the present invention can be obtained by an ordinary production method. For example, when a kneaded sheet for wire coating is obtained, the chlorine-containing resin, the hydrotalcite-type particle powder, and the above various stable products It is obtained by mixing a predetermined amount of an agent and an additive, kneading the mixture using a hot roll to obtain a kneaded sheet, and then pressurizing with a hot press. The kneading temperature of the hot roll is preferably 145 to 180 ° C. As for the press temperature of a hot press, 150-190 degreeC is preferable.
[0086]
DETAILED DESCRIPTION OF THE INVENTION
A typical embodiment of the present invention is as follows.
[0087]
The plate surface diameter of the hydrotalcite-type particle powder is shown as an average value measured from an electron micrograph.
[0088]
The thickness of the hydrotalcite-type particle powder is “X-ray diffractometer RAD-2A (manufactured by Rigaku Corporation)” (tube: Fe, tube voltage: 40 kV, tube current: 20 mA, goniometer: wide-angle gonio) Meter, sampling width: 0.010 °, scanning speed: 0.5 ° / min, divergence slit: 1 °, scattering slit: 1 °, light receiving slit: 0.30 mm), and (003) of hydrotalcite particles ) This is a value calculated from Scherrer's equation from the diffraction peak curve of the crystal plane.
[0089]
The hydrotalcite-type particle powder was identified by X-ray diffraction measurement. X-ray diffraction measurement was performed using the X-ray diffractometer at a diffraction angle 2θ of 5 to 90 °.
[0090]
Composition formula in Mg-Al hydrotalcite-type particle powder
[Mg_xCa_y] ・ Al_z・ (OH)₂・ A^n- _p・ MH₂O
The indices x, y, and z were determined by dissolving Mg-Al hydrotalcite-type particle powder with an acid and measuring it with “Plasma Emission Spectrometer SPS4000 (Seiko Electronics Co., Ltd.)”.
[0091]
In addition, anion (A^n-) As CO₃ ^2-When used, the carbon content (% by weight) was measured by a carbon sulfur analyzer: EMIA-2200 (manufactured by HORIBA).
[0092]
The heat resistance time of the Mg-Al hydrotalcite-type particle powder in the vinyl chloride resin was evaluated by the method described above.
[0093]
The thermal stability of the chlorine-containing resin composition was measured according to JIS K 6723 by preparing a sheet having a thickness of 1 mm at a hot roll temperature of 160 ° C. and a hot press temperature of 160 ° C. in the above production method.
[0094]
The electrical insulation of the chlorine-containing resin composition was evaluated by measuring the volume resistivity of the above sheet according to JIS K 6723.
[0095]
The colorability of the chlorine-containing resin composition was determined by visually observing the color tone of the sheet. In addition, evaluation of coloring property is as follows.
A: Extremely excellent
B: Excellent
C: Slightly inferior
D: Inferior
[0096]
<Production of Mg-Al-based hydrotalcite-type particle powder>
CO₃ ^2-500 ml of an aqueous sodium carbonate solution having an ion concentration of 0.875 mol / l and 3 l of an aqueous sodium hydroxide solution (pH value = 14.2) of 5.308 mol / l are mixed, maintained at 60 ° C., and stirred in a reaction vessel. Keep it. To this was added a mixed solution of 500 ml of a 3.75 mol / l magnesium sulfate aqueous solution and 500 ml of a 0.625 mol / l aluminum sulfate aqueous solution, and then 200 ml of a 0.75 mol / l calcium chloride aqueous solution was added to make the total volume 5 l. . While stirring the reaction vessel, the mixture was aged at pH value of 12.5 and 95 ° C. for 18 hours to form a white precipitate. The white precipitate was filtered, washed with water, and dried at 60 ° C. to obtain white particle powder. As a result of identifying this white particle powder, it was recognized that it was a hydrotalcite type particle powder.
[0097]
The obtained Mg—Al-based hydrotalcite-type particle powder has an average plate surface diameter of 0.40 μm, a thickness of 0.0605 μm, and a BET specific surface area of 11.6 m.²/ G.
[0098]
3 parts by weight of the Mg—Al hydrotalcite-type particle powder was mixed at the composition ratio of claim 1 to prepare a kneaded sheet. The heat resistance time at 180 ° C. of the obtained sheet piece was 6 hours.
[0099]
<Production of chlorine-containing resin composition>
In the vinyl chloride resin, the Mg-Al hydrotalcite-type particle powder and the additive were mixed in the following composition ratio, and 50 g of the obtained mixture was kneaded using a hot roll to obtain a kneaded sheet. The kneading conditions are a kneading temperature of 160 ° C., a roll gap of 0.75 mm, and a kneading time of 3 minutes.
Hydrotalcite-type particle powder: 4.6 parts by weight
Vinyl chloride resin (degree of polymerization 1300)
(Product name: Kane Beer S1003, Kaneka Chemical Co., Ltd.): 100 parts by weight,
Trioctyl trimellitate: 48 parts by weight,
Zinc stearate (primary reagent): 0.8 part by weight
Stearic acid (primary reagent): 0.4 parts by weight
Dibenzoylmethane: 0.2 parts by weight,
Dipentaerythritol: 0.2 part by weight,
Calcium stearate (primary reagent): 0.1 parts by weight,
Phenolic antioxidant: 0.5 parts by weight
Calcium carbonate (first grade reagent): 16 parts by weight,
Antimony trioxide (primary reagent): 5 parts by weight
Gelling accelerator: 2 parts by weight.
The obtained kneaded sheet is subjected to pressure treatment with a hot press to produce a kneaded sheet for electric wire coating. The pressurizing conditions are a press temperature of 160 ° C. and a press pressure of 100 kg / cm.²The press time is 1 minute, the press gap is 1.0 mm, and the processing amount is 35 g.
[0100]
The obtained kneaded sheet has a thermal stability of 511 minutes, a visual evaluation of colorability of A, and a volume resistivity of 12.8 × 10.¹³It was Ω · cm.
[0101]
[Action]
The important point in the present invention is that the chlorine-containing resin composition according to the present invention is excellent in thermal stability, colorability and electrical insulation as a chlorine-containing resin composition for wire coating.
[0102]
The reason why the chlorine-containing resin composition according to the present invention is excellent in thermal stability is that the Mg-Al hydrotalcite-type particle powder according to the present invention has a high chlorine scavenging ability, A chlorine-containing resin composition containing hydrotalcite-type particle powder is also considered to have high thermal stability.
[0103]
In addition, the Mg—Al-based hydrotalcite-type particle powder according to the present invention has a feature that it is difficult to cause zinc burning. Therefore, a large amount of zinc compound can be blended in the chlorine-containing resin composition. Since zinc compounds such as zinc stearate have a high thermal stability improving effect and are inexpensive, it is advantageous that they can be blended in a large amount. Moreover, a zinc compound shows a synergistic effect and colorability is improved by combined use with a barium salt and a calcium salt.
[0104]
The reason why the chlorine-containing resin composition according to the present invention is excellent in electrical insulation is not yet clear, but since the anion exchange capacity of the Mg-Al hydrotalcite particle powder according to the present invention is high, the chlorine-containing resin composition The present inventor presumes that the decomposition product anion released from the product and serving as a charge carrier is absorbed by the hydrotalcite-type particle powder to improve the electrical resistance.
[0105]
【Example】
Next, examples and comparative examples are given.
[0106]
Example 1
In the same manner as in the embodiment of the invention, an Mg-Al hydrotalcite type particle powder was obtained.
[0107]
Example 2
Suspension 1.5 l (concentration: 56.7 g / l) containing the Mg—Al hydrotalcite type particle powder obtained in Example 1 was heated to 70 ° C., and No. 3 water glass 8.9 g Was gradually added and aged for 60 minutes after completion of the addition. Subsequently, it was filtered, washed with water, dried and pulverized to obtain Mg—Al-based hydrotalcite-type particle powder whose surface was coated with silicon hydroxide or silicon oxide.
[0108]
Example 3
500 g of Mg-Al hydrotalcite-type particle powder and 15 g of natural rosin whose surface obtained in Example 2 was coated with silicon hydroxide or silicon oxide were placed in a Henschel mixer and pulverized and mixed for 5 minutes. Thus, an Mg—Al hydrotalcite particle powder whose particle surface was further coated with natural rosin was obtained.
[0109]
Example 4
500 g of Mg—Al-based hydrotalcite-type particle powder and 2.5 g of decyltrimethoxysilane whose surfaces obtained in Example 2 were coated with silicon hydroxide or silicon oxide were placed in a Henschel mixer for 5 minutes. The mixture was pulverized and mixed to obtain a Mg—Al hydrotalcite-type particle powder whose particle surface was further coated with decyltrimethoxysilane.
[0110]
Examples 5-9, Comparative Examples 1-5
Except for changing the concentration of magnesium compound, aluminum compound, sodium carbonate, alkaline aqueous solution, calcium salt addition, calcium salt concentration, aging temperature, type of surface treatment agent, and addition amount, In the same manner as in Examples 3 and 4, Mg-Al hydrotalcite-type particle powders whose particle surfaces were coated with various surface treatment agents were obtained. In Comparative Example 5, an Mg-Al hydrotalcite-type particle powder was obtained using an autoclave.
[0111]
Comparative Example 6 is a commercially available Mg—Al-based hydrotalcite-type particle powder (plate surface diameter 0.25 μm, thickness 0.0610 μm, plate ratio 4.1, specific surface area 9.2 m.²/ G), Alkamizer 1 (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.).
[0112]
The production conditions at this time are shown in Table 1, and various properties of the obtained Mg-Al hydrotalcite-type particle powder are shown in Table 2.
[0113]
Examples 10-22, Comparative Examples 7-15
Using Mg-Al hydrotalcite type particle powders of Examples 1 to 9 and Comparative Examples 1 to 6, the addition amount of hydrotalcite type particle powder, the addition amount of zinc stearate, the addition amount of calcium stearate, di A vinyl chloride resin kneaded sheet for electric wire coating was obtained in the same manner as in the above embodiment except that the amount of pentaerythritol added was variously changed. Table 3 shows the composition and evaluation results of the kneaded sheet. In addition, the numerical value of a compounding composition represents a weight part number.
[0114]
Example 23
In the same manner as in the previous embodiment, the Mg-Al hydrotalcite type particle powder of Example 3 and the additive were mixed in the following composition ratio in vinyl chloride resin, and diisononyl phthalate was used as a plasticizer. Thus, a vinyl chloride resin kneaded sheet for wire coating was obtained.
Hydrotalcite-type particle powder: 3.5 parts by weight
Vinyl chloride resin (degree of polymerization 1300)
(Product name: Kane Beer S1003, Kaneka Chemical Co., Ltd.): 100 parts by weight,
Diisononyl phthalate: 50 parts by weight,
Zinc stearate (primary reagent): 1.2 parts by weight
Dibenzoylmethane: 0.2 parts by weight,
Phenolic antioxidant: 0.2 parts by weight,
Clay: 0 parts by weight
Calcium carbonate (first grade reagent): 16 parts by weight,
[0115]
Examples 24-28, Comparative Examples 16-18
Using Mg-Al hydrotalcite type particle powders of Examples 3 and 4, various addition amounts of hydrotalcite type particle powder, addition amount of zinc stearate, addition amount of clay, addition amount of calcium carbonate Except having been made, it carried out similarly to Example 23, and obtained the vinyl chloride resin kneading sheet for an electric wire coating | covering application. Table 4 shows the composition and evaluation results of the kneaded sheet. In addition, the numerical value of a compounding composition represents a weight part number.
[0116]
[Table 1]

[0117]
[Table 2]

[0118]
[Table 3]

[0119]
[Table 4]

[0120]
【The invention's effect】
The chlorine-containing resin composition according to the present invention is suitable as a chlorine-containing resin composition for electric wire coating because it is excellent in thermal stability and colorability and also in electrical insulation.

Claims (2)

The plate surface diameter is 0.1 to 1.0 μm, the thickness is 0.02 to 0.08 μm, and calcium is contained in a molar ratio of 0.01 to 0.20 with respect to the total number of moles of Mg and Al. Mg-Al-based hydrotalcite-type particle powder, and the heat resistance time of the particle powder measured by the following measurement method is 4 hours or longer. A chlorine-containing resin composition to be included as an agent.
{Circle around (1)} Hydrotalcite-type particle powder and additives were mixed in a vinyl chloride resin at the following composition ratio, and 50 g of the resulting mixture was kneaded using a hot roll to obtain a kneaded sheet. The kneading conditions are a kneading temperature of 155 ° C., a roll gap of 0.75 mm, and a kneading time of 3 minutes.
Hydrotalcite-type particle powder: 3 parts by weight
Vinyl chloride resin (degree of polymerization 1300)
(Product name: TK-1300, manufactured by Shin-Etsu Chemical): 100 parts by weight,
Diethylhexyl phthalate (DOP, manufactured by Daihachi Chemical): 50 parts by weight,
Calcium stearate (primary reagent): 2 parts by weight
Zinc stearate (primary reagent): 0.4 parts by weight
1,3 diphenyl-1,3-propanedione (primary reagent): 0.2 parts by weight,
Diethyl phosphite (primary reagent): 0.5 parts by weight.
(2) The obtained kneaded sheet was subjected to pressure treatment with a hot press to obtain a sheet piece (thickness: 1.5 mm). The pressurization conditions are a press temperature of 160 ° C., a press pressure of 100 kg / cm ² , a press time of 1 minute, a press gap of 1.5 mm, and a throughput of 35 g.
(3) The obtained sheet piece (20 mm × 20 mm) is put in an oven at 180 ° C. in air and a heat resistance test is performed. The time when the entire sheet piece turns black is defined as the heat resistant time. A chlorine-containing resin composition for electric wire coating, comprising 1.5 to 10 parts by weight of the chlorine-containing resin stabilizer according to claim 1 with respect to 100 parts by weight of chlorine-containing resin.