JP2007277427A - Stabilized halogen-containing resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a stabilized halogen-containing resin composition that conquers dispersion failure, poor compatibility and volatility of a polyhydric alcohol in a resin, liable to cause a problem of plate-out and reduces its blended amount. <P>SOLUTION: A halogen-containing resin is stabilized by mixing at least one or more kinds of calcium hydroxide-based compounds of a calcium hydroxide-based solid solution and hydrocalumites with a polyhydric alcohol to give a mixture and heating the mixture to give a complex in which the polyhydric alcohol is adsorbed on and reacted with the calcium hydroxide-based compounds and adding the complex to the halogen-containing resin. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a stabilized halogen-containing resin composition and a stabilizer. More specifically, the present invention relates to a stabilized halogen-containing resin composition and a stabilizer containing a complex of a calcium hydroxide compound and a polyhydric alcohol.

  Polyhydric alcohols such as dipentaerythritol are essential for synergistically improving the thermal stability of halogen-containing resins such as polyvinyl chloride when used in combination with metal soaps such as calcium stearate and non-toxic stabilizers such as hydrotalcite. It is widely used as a stability aid close to.

  However, since the polyhydric alcohol has poor compatibility and dispersibility with the halogen-containing resin, it easily migrates to the surface of the molded body, causing plate-out. In addition, there is a problem that the stabilizer is expensive and has a large amount. Accordingly, an object of the present invention is to overcome the poor dispersion, incompatibility, and volatility of polyhydric alcohol in the resin, and to reduce the blending amount.

  The present invention provides the following formula (1)

（但し、式中、Ｍ^２＋はＭｇ，ＺｎおよびＣｕの２価金属の少なくとも１種以上、Ａ^ｎ−はｎ価のアニオンを示し、ｘ，ｙ，ｍおよびｎはそれぞれ次の範囲にある。０≦ｘ＜０．３，０≦ｙ＜０．４，０≦ｍ＜４，ｎは整数）で表される水酸化カルシウム、水酸化カルシウムに２価金属が固溶した水酸化カルシウム系固溶体および、ハイドロカルマイト類の少なくとも１種以上の水酸化カルシウム系化合物と多価アルコールとの複合体を含有する安定化された含ハロゲン樹脂組成物を提供する。

^{(Wherein, M 2+} is Mg, Zn and Cu 2 divalent metal of at least 1 or ^{more, A n-represents} an n-valent anion, certain x, y, m and n are each in the following ranges. Calcium hydroxide represented by 0 ≦ x <0.3, 0 ≦ y <0.4, 0 ≦ m <4, n is an integer), calcium hydroxide solid solution in which a divalent metal is dissolved in calcium hydroxide And the stabilized halogen-containing resin composition containing the composite_body | complex of the at least 1 sort (s) or more of calcium hydroxide type compound and polyhydric alcohol of hydrocalumite is provided.

  Furthermore, this invention provides the stabilizer which uses the composite_body | complex of this calcium hydroxide type compound and a polyhydric alcohol as an active ingredient.

  According to the present invention, it is possible to improve the initial colorability and thermal stability, reduce the blending amount of the polyhydric alcohol which is expensive and has a large blending amount, and also reduce the plate-out property.

  The calcium hydroxide compound used in the present invention is any one or more of calcium hydroxide, a calcium hydroxide solid solution in which at least one of Mg, Zn and Cu is dissolved, and a hydrocalumite in which Al is dissolved. Preferably, calcium hydroxide and calcium hydroxide solid solution are used. The calcium hydroxide-based solid solution is a compound having a calcium hydroxide crystal structure in which at least one divalent metal (Mg, Zn, Cu) is dissolved in calcium hydroxide.

（但し、式中、Ｍ^２＋はＭｇ、ＺｎおよびＣｕの少なくとも１種以上、好ましくはＺｎおよび／またはＣｕを示し、ｘは次の範囲にある。０＜ｘ＜０．３、好ましくは０＜ｘ≦０．２、特に好ましくは０＜ｘ≦０．１で表される。）

(Wherein M ²⁺ represents at least one of Mg, Zn and Cu, preferably Zn and / or Cu, and x is in the following range: 0 <x <0.3, preferably 0 < x ≦ 0.2, particularly preferably 0 <x ≦ 0.1.

  Hydrocalumite is represented by the following formula (3)

（但し、式中、Ｍ^２＋はＭｇ，ＺｎおよびＣｕの２価金属の少なくとも１種以上、Ａ^ｎ−はｎ価のアニオン、好ましくはＯＨ⁻および／またはＣＯ_３ ^２−を示し、ｘ，ｙ，ｍおよびｎはそれぞれ次の範囲にある。０≦ｘ＜０．３、好ましくは０≦ｘ＜０．２，０≦ｙ＜０．４、好ましくは０．２≦ｙ＜０．４，０≦ｍ＜４，ｎは整数）で表されるハイドロカルマイト：Ｃａ_４Ａｌ_２（ＯＨ）_１４・４Ｈ_２Ｏ［Ａ^ｎ−がＯＨ⁻である］と同じ結晶構造を有する層状化合物。

^{(Wherein, M 2+} is Mg, Zn and Cu 2 divalent metal of at least 1 or ^{more, A n-n-valent} anion, preferably OH ^- and / or _CO ^{3 2-} are shown, x, y , M and n are in the following ranges: 0 ≦ x <0.3, preferably 0 ≦ x <0.2, 0 ≦ y <0.4, preferably 0.2 ≦ y <0.4, 0 ≦ m <4, n is an integer) Hydrocalumite represented by: Ca ₄ Al ₂ (OH) ₁₄ · 4H ₂ O [A ⁿ⁻ is OH ⁻ ], the layered compound having the same crystal structure.

  The calcium hydroxide solid solution is produced by co-precipitation of Ca and an aqueous solution of at least one kind of chloride, nitrate, etc. of Mg, Zn and Cu and an alkali equivalent to this, for example, sodium hydroxide. Thereafter, conventional means such as filtration, washing with water, dehydration, drying, pulverization, and classification can be appropriately selected and used. As a production method other than the above, a method in which calcium hydroxide is used as a substitute for both components of alkali and Ca, and this is coprecipitated with an aqueous solution of at least one water-soluble salt of Mg, Zn and Cu can be applied. .

Hydrocalumite is produced by coprecipitation of calcium hydroxide with an aqueous solution of an aqueous salt of Al such as aluminum chloride or aluminum nitrate, or by heating a mixture of calcium hydroxide and aluminum hydroxide at about 60 ° C or higher. And a method of coprecipitation by adding an equivalent amount of alkali, for example, an aqueous sodium hydroxide solution, to a mixed aqueous solution of Al or a water-soluble salt of Al and a divalent metal M ²⁺ .

  The polyhydric alcohol used in the present invention is a polyhydric alcohol or a partial ester thereof, preferably a polyhydric alcohol. The polyhydric alcohol is an organic compound having two or more OH groups in the molecule, such as glycerin, xylitol, tris (hydroxyethyl) isocyanurate, mannitol, sorbitol, pentaerythritol, dipentaerythritol, tripentaerythritol, Examples thereof include trimethylolpropane and dipentaerythritol / adipic acid ester. Among these, pentaerythritol and dipentaerythritol are preferable, and dipentaerythritol is particularly preferable. A partial ester of a polyhydric alcohol is obtained by reacting at least one of these polyhydric alcohols with at least one mono- or polycarboxylic acid.

  The composite of the calcium hydroxide compound of the present invention and the polyhydric alcohol is preferably prepared by mixing both, preferably by mixing the fine powders of both uniformly, preferably by adding water or an alcohol solvent, and further mixing. Is mixed at 90 ° C. or higher under heating. Thereafter, it is preferably dried (90 ° C. or higher) and pulverized. By the above homogeneous mixing, preferably heating (drying) thereafter, the polyhydric alcohol is adsorbed or chemically bonded to the calcium hydroxide compound, and the composite of the present invention is obtained.

  It can be said from the following fact that the complex of the present invention is not a simple mixture of a polyhydric alcohol and a calcium hydroxide compound constituting the complex, but both interact. For example, when comparing the X-ray diffraction intensity between the case where calcium hydroxide and dipentaerythritol are simply mixed at 2: 1 and the case where the composite of the present invention is used, the diffraction intensity of dipentaerythritol is the composite of the present invention. In the body it has dropped to less than about half of the mixture. Further, when TG-DTA analysis is performed, dipentaerythritol has an endothermic peak at about 310 ° C. and the condensation reaction is reduced, whereas the complex of the present invention reacts and decreases at an endothermic peak temperature of about 220 ° C. Such a decrease in the condensation temperature of about 90 ° C. is hardly observed in calcium carbonate or hydrotalcite. The present invention was carried out by discovering that such a strong interaction with a polyhydric alcohol is a characteristic characteristic of the calcium hydroxide compound of the present invention.

  By forming the complex of the present invention, polyhydric alcohol is improved in its disadvantages of dispersibility in a halogen-containing resin, poor compatibility, and property of being easily plate-out. Since the dispersibility is improved, the heat stabilization effect is also improved. As a result, the amount can be reduced.

  The composition of the composite of the present invention is 0.1 to 1000 parts by weight, preferably 1 to 500 parts by weight, particularly preferably 5 to 200 parts by weight of polyhydric alcohol with respect to 100 parts by weight of the calcium hydroxide compound. .

  Although the calcium hydroxide compound used in the present invention can be used as it is, it is preferable to treat the calcium hydroxide compound with 0.1 to 10% by weight of an anionic surfactant or the like. Examples of the surface treatment agent include higher fatty acids, alkali metal salts or alkaline earth metal salts or zinc salts of higher fatty acids, phosphate esters, silane-based or titanium-based or aluminum-based coupling agents, preferably higher fatty acids and the like. Examples include alkali metal salts.

The calcium hydroxide compound used in the present invention preferably has small primary particles and secondary particles. Preferably the BET specific surface area related to primary particles is 1~40m ² / g, particularly preferably from 5 to 20 m ² / g. As for the secondary particle size, an average secondary particle size of 50% cumulative is preferably 2 μm or less, particularly preferably 1 μm or less.

  The surface treatment can be carried out by a known wet method or dry method. The wet method is performed by dispersing a calcium hydroxide compound in water or alcohol, and then adding a solution obtained by dissolving or dispersing the surface treatment agent in water or alcohol with stirring. The dry method can be carried out by adding a calcium hydroxide compound dissolved or dispersed in water or alcohol with stirring using a Henschel mixer or the like.

  In addition to the composite of the present invention, the stabilized halogen-containing resin composition of the present invention comprises (a) 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight of hydrotalcite, Li, At least one stabilizer selected from metal soaps of alkali metals or alkaline earth metals such as Na, K, Mg, Ca, magnesium hydroxide, magnesium oxide and organotin stabilizers, (b) 0.01 to 2 parts by weight, preferably 0.1 to 1 part by weight of an organic acid, for example, zinc salts such as lauric acid, palmitic acid and stearic acid, (c) 0.001 to 2 parts by weight, preferably 0. 01-1 part by weight of β-diketone represented by the following general formula (4),

（式中、Ｒ_１およびＲ_３は同一、または異なっていてもよく、３０個までの炭素原子を有する直鎖、または分枝状のウルキル基、アルケニル基を表す）このようなβ−ジケトン類の中で好ましく用いられる物として、例えばジベンゾイルメタン（ＤＢＭ）、ステアロイルベンゾイルメタン（ＳＢＭ）、ベンゾイルアセトン、アセチルアセトン、デヒドロ酢酸等を挙げることができる。

(Wherein R ₁ and R ₃ may be the same or different and represent a straight-chain or branched ulalkyl group or alkenyl group having up to 30 carbon atoms) such β-diketones Among these, preferred examples include dibenzoylmethane (DBM), stearoylbenzoylmethane (SBM), benzoylacetone, acetylacetone, and dehydroacetic acid.

  Examples of the halogen-containing resin used in the present invention are as follows. Polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, chloride Vinyl-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-alrilonitrile copolymer, vinyl chloride-butadiene copolymer, chloride Vinyl-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer , Vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-arriloni Lil copolymer, vinyl chloride - various vinyl ether copolymers chlorine-containing synthetic resin. Blends of these chlorine-containing synthetic resins or with other synthetic resins not containing chlorine, block copolymers, graft copolymers, and the like.

Other conventional additives can be blended in the resin composition of the present invention. Examples of such other additives include the following. Phosphite stabilizers such as bisphenol A tetra C _12-15 alkyl diphosphite, tridecyl phosphite, trilauryl phosphite, tris (monophenyl) phosphite. Epoxy stabilization aids such as epoxidized vegetable oils, epoxidized oleic acid esters, and epoxidized erucic acid esters. Sulfur-containing compound-based stabilizing aids such as thiodipropionic acid and diethylthiodipropionic acid ester. Phenol stabilizers such as phenols such as alkyl gallate and alkylated phenol, and styrenated phenol. Α-amino acids such as glycine, alanine, leucine, isoleucine, glycinamide, histidine ethyl ester, tryptophan benzyl ester, and functional derivatives thereof. Styrenated harlacresol, 2,6-ditertiary butyl-4-methylphenol, butylated anisole, 4,4'-methylenebis (6-tertiarybutyl-3-methylphenol), 2,2'methylenebis ( 6-tertiarybutyl-4-methylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-ditertiarybutyl-4-hydroxybenzyl) benzene, tetrakis [3- Antioxidants such as (4-hydroxy-3,5-tertiarybutylphenyl) propionyloxymethylene] methane.

  The amount of these additives can be appropriately selected. For example, about 0.01 to about 5 parts by weight of a stabilizing aid and about 0.01 to about 2 parts by weight of an oxidizing agent are added to 100 parts by weight of the halogen-containing resin. An inhibitor is exemplified. In the present invention, other conventional additives such as plasticizers, lubricants, processing aids, weather resistance improvers, antistatic agents, antifogging agents, reinforcing agents, fillers, pigments and the like are blended in addition to the above additives. May be. In the present invention, mixing and kneading of the halogen-containing resin, the additive of the present invention, and other additives may be performed by a conventional method capable of mixing both uniformly. For example, any mixing and kneading means such as a single-screw or twin-screw extruder, a roll, and a Banbury mixer can be adopted. There are no particular restrictions on the molding method, and any molding means such as injection molding, extrusion molding, blow molding, press molding, rotational molding, calendar molding, sheet forming molding, transfer molding, laminate molding, vacuum molding, etc. can be employed. .

  Hereinafter, based on an Example, this invention is demonstrated in detail. In the following examples,% means% by weight.

Add 300 g of high-purity quicklime to 5 liters of warm water (about 60 ° C.) under stirring, continue stirring for about 20 minutes to obtain calcium hydroxide, adjust the temperature to about 70 ° C., and then 12 g of stearic acid with a purity of 98% Was added to about 200 ml of water together with about 2 g of sodium hydroxide, and the solution dissolved by heating at about 70 ° C. was added with stirring to perform surface treatment. Then, it was water-sieved with a 200 mesh wire mesh. From the slurry after water sieving, 100 g of surface-treated calcium hydroxide was put into a container having a capacity of 2 liters, and 30 g of dipentaerythritol powder was added with stirring, and stirring was continued for 20 minutes. Then, after cooling to room temperature, it filtered, dried at 120 degreeC for 8 hours, and pulverized with the atomizer. (A part of the slurry after water sieving, filtered, dried, and pulverized had BET = 14 m ² / g, 50% cumulative average secondary particle size = 0.87 μm.) Cumulative cumulative 50 % Average secondary particle diameter was 0.92 μm. The composite was subjected to thermal analysis at a heating rate of 10 ° C./min, atmosphere N ₂ = 150 ml / min, O ₂ = 50 ml / min, and the endothermic peak temperature at which the weight decreased (condensation polymerization occurred) was measured. Is shown in Table 1. This composite was blended with polyvinyl chloride as a stabilizer and dipentaerythritol with the following formulation, mixed, and then kneaded at 165 ° C. for 3 minutes using an open roll to prepare a sheet having a thickness of about 1 mm.
[Formulation 1] Polyvinyl chloride (manufactured by Shin-Etsu Chemical, molecular weight 700) 100 parts by weight
Zinc stearate 0.2 parts by weight
Stearoyl benzoylmethane 0.15 parts by weight
Stabilizer 1.0 parts by weight
Polyhydric alcohol 0.2-1.0 parts by weight This sheet was cut into a size of about 3 cm × 3 cm to make a test piece, put in a gear oven controlled at 185 ° C., taken out at intervals of 10 minutes, and 10 minutes later Table 1 shows the results of visual evaluation using the initial coloration as the initial coloration and the time (minutes) until blackening as the thermal stabilization time.

[Comparative Example 1]
The surface-treated calcium hydroxide prepared in Example 1 was mixed with the same dipentaerythritol and other ingredients used in Example 1 according to Formula 1 as a stabilizer, and then as in Example 1. Were processed and evaluated. The results are shown in Table 1.

[Comparative Example 2]
200 g of commercially available hydrotalcite (trade name: Alkamizer 1) was placed in a 2 liter beaker, 100 ml of ethyl alcohol and 60 g of dipentaerythritol were added thereto, and the mixture was uniformly mixed for about 20 minutes with a chemistor. It put into the oven of 120 degreeC, and it grind | pulverized after drying for about 5 hours. Table 1 shows the results obtained by blending this product as the stabilizer of Formula 1 and dipentaerythritol, preparing test pieces, and evaluating them.

[Comparative Example 3]
In Comparative Example 1, evaluation was performed in the same manner as in Comparative Example 1 except that calcium stearate was used instead of calcium hydroxide. The results are shown in Table 1.

Instead of the calcium hydroxide composite of Example 1, a calcium hydroxide solid solution having a BET specific surface area of 10 m ² / g and an average secondary particle diameter of 50% and a cumulative secondary particle diameter of 0.72 μm; Ca _0.98 Zn _0.02 ( OH) ₂ was used in the same manner as in Example 1 except that a complex obtained by mixing, drying (100 ° C.) and grinding in the same weight of dipentaerythritol and ethanol solvent was used. The evaluation results are shown in Table 1. The solid solution was prepared by adding 500 ml of water in which 0.04 mol of zinc chloride was dissolved to 2 mol of slaked lime while stirring and dispersing in 4 liters of water, and then raising the temperature to about 70 ° C. Then, 200 ml of warm water (about 70 ° C.) in which 4 g of sodium stearate was dissolved was added for surface treatment, followed by filtration, washing with water, drying and grinding.

[Comparative Example 4]
Table 1 shows the evaluation results when using a calcium hydroxide solid solution and dipentaerythritol at the same ratio in Example 2 and using the other components according to Formula 1 just mixed with other components.

200 g of pentaerythritol is mixed with 500 g of calcium hydroxide having a BET specific surface area of 16 m ² / g and an average secondary particle diameter of 0.67 μm with a cumulative 50%, and these are put into a container of 2 liters capacity. About 500 g was added and heated to about 95 ° C. with stirring, and this condition was maintained for about 20 minutes. Thereafter, filtration, drying (at 100 ° C. for 8 hours), and pulverization were performed. Except for using the obtained composite powder as a stabilizer and a polyhydric alcohol, they were mixed in accordance with Formula 1 and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 4]
Table 1 shows the evaluation results when the calcium hydroxide and pentaerythritol used in Example 3 are mixed at the same ratio and the others are simply mixed according to Formula 1.

In Example 2, a synthesized calcium hydroxide solid solution; Ca _0.98 Cu _0.02 (OH) ₂ was used except that cupric nitrate was used in place of zinc chloride. Table 1 shows the results of evaluation using 20% pentaerythritol instead of dipentaerythritol for this solid solution. The BET specific surface area of this solid solution was 9 m ² / g, and the average secondary particle size with a cumulative 50% was 1.0 μm.

[Comparative Example 5]
Table 1 shows the evaluation results when the calcium hydroxide solid solution used in Example 4 and pentaerythritol are used in the same ratio, and the others are simply mixed according to Formula 1.

  In Example 2, a polyvinyl chloride sheet having a thickness of about 1 mm was prepared in the same manner as in Example 2 except that 30 parts by weight of dioctyl phthalate and 0.1 part by weight of carbon black were further added to Formulation 1. . This sheet was cut into 5 cm × 5 cm, put into a 200 ml capacity beaker, 200 ml of deionized water, sealed with a wrap, and allowed to stand in an oven at 70 ° C. for 24 hours. As a result of taking out the test piece and visually observing the degree of whitening of the surface, the surface was black and no white protrusion was observed. Therefore, there was no plate-out.

[Comparative Example 6]
In Example 5, it carried out similarly to Example 5 using the hydrotalcite used in the comparative example 2 instead of the calcium hydroxide type compound. The test piece taken out from the beaker was entirely covered with white folding material and had a high plate-out property.

Claims (8)

Following formula (1)

^{(Wherein, M 2+} is Mg, indicates at least one or more kind of divalent metals Zn and ^{Cu, A n-represents} an n-valent anion, x, y, m and n are each the following ranges At least one of calcium hydroxide, calcium hydroxide solid solution, and hydrocalumite represented by 0 ≦ x <0.3, 0 ≦ y <0.4, 0 ≦ m <4, and n is an integer) The stabilized halogen-containing resin composition which uses the composite of the above calcium hydroxide type compound and a polyhydric alcohol as an active ingredient. 2. The stabilized halogen-containing resin composition according to claim 1, wherein the composition of the composite is 100: 0.1 to 1000 by weight ratio of the calcium hydroxide compound and the polyhydric alcohol. The stabilized halogen-containing resin composition according to claim 1, wherein the composition of the composite is 100: 5 to 200 by weight ratio of the calcium hydroxide compound and the polyhydric alcohol. The calcium hydroxide compound according to claim 1 is represented by the following formula (2):

(Wherein, M ²⁺ represents at least one of divalent metals of Mg, Zn and Cu, and x represents the following range: 0 ≦ x <0.3) 2. The stabilized halogen-containing resin composition according to claim 1, which is a solid solution of calcium hydroxide. The stabilized halogen-containing resin composition according to claim 1, wherein the polyhydric alcohol according to claim 1 is dipentaerythritol. The stabilized halogen-containing resin composition according to claim 1, wherein the polyhydric alcohol according to claim 1 is pentaerythritol. 2. The stabilized halogen-containing resin composition according to claim 1, wherein the calcium hydroxide compound of claim 1 is surface-treated with a higher fatty acid or an alkali metal salt of the higher fatty acid. Following formula (1)

^{(Wherein, M 2+} is Mg, indicates at least one or more kind of divalent metals Zn and ^{Cu, A n-represents} an n-valent anion, x, y, m and n are each the following ranges At least one of calcium hydroxide, calcium hydroxide solid solution, and hydrocalumite represented by 0 ≦ x <0.3, 0 ≦ y <0.4, 0 ≦ m <4, and n is an integer) A stabilizer for a halogen-containing resin comprising as an active ingredient a complex obtained by mixing and adsorbing 0.1 to 1000 parts by weight of a polyhydric alcohol to 100 parts by weight of the above calcium hydroxide compound.