JP2005089598A - Stabilized halogen-containing resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an inexpensive stabilizer that can substitute for a poisonous lead-based stabilizer used in a large amount in a halogen-containing resin, is non-toxic, has slight discoloration at an initial stage, at a middle stage and at a later stage and excellent heat stability and yet does not cause foaming in molding. <P>SOLUTION: A complex compound of a hydrocalumite having the molar ratio of Ca/Al of >2 and ≤10 and calcium hydroxide is used as the stabilizer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a stabilized halogen-containing resin composition containing a complex compound of calcium hydroxide and hydrocalumite. More specifically, a halogen-containing compound containing a novel stabilizer that can replace lead-based stabilizers and is non-toxic, inexpensive, non-foaming, and excellent in both early, intermediate, and late coloration and thermal stability. The present invention relates to a resin composition.

  Halogen-containing resins are unstable with respect to heat and light. Therefore, it is necessary to add a stabilizer before melt processing. As stabilizers, lead compounds, organotin compounds, Cd / Ba complex metal soaps, Ba / Zn complex metal soaps, Ca / Zn complex metal soaps, hydrotalcites and the like have been used. However, with increasing social needs for the safety of stabilizers, cadmium is almost never used, and lead-based compounds tend to be banned. Tin-based and Ba-based materials are also uneasy about safety, and only Ca / Zn-based materials and hydrotalcites are safe.

  Lead-based stabilizers must be replaced with other safe stabilizers due to toxicity, but there are problems in performance and price, and moldability (foaming), which is a bottleneck for substitution. The Ca / Zn system has poor thermal stability, and hydrotalcites have problems in foaming and cost during molding. Lead-based stabilizers still occupy a major part of stabilizers because they are excellent in almost all aspects except toxicity, such as initial coloration, thermal stability, low cost, and high electrical insulation. . Accordingly, the present inventor has developed a novel stabilizer that is non-toxic, inexpensive, non-foaming, good in initial coloration and thermal stability, a method for producing the same, and a stabilized halogen-containing resin composition containing the stabilizer. The purpose is to provide.

In the present invention, an aqueous solution of an aluminum salt or hydrocalumite is added to calcium hydroxide in an aqueous medium so that the final product Ca / Al molar ratio is more than 2 and 10 or less, and is reacted. Provided is a stabilized halogen-containing resin composition containing a composite compound of hydrocalumite and calcium hydroxide.

  Furthermore, this invention provides the stabilizer which uses this novel composite compound as an active ingredient, and its manufacturing method.

  According to the present invention, a halogen-containing resin stabilizer that is low in initial, intermediate, and late coloration, has excellent thermal stability, does not foam during molding, is non-toxic and inexpensive, and is a toxic lead-based stabilizer. Can be provided as an alternative.

Hydrocalumite is a well-known compound such as cement hydrate, and has the same layered structure and chemical composition as hydrotalcite (also called pyroaulite), but has a different crystal structure. ing. Heat stabilizer hydrotalcites for halogen-containing resins invented by the present inventors (trade name Alkamizer); Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .3H ₂ O [Japanese Patent Laid-Open No. 55-80445] In this case, Mg and Al are present in the same plane, and each has a six-coordinate bond by OH ⁻ . On the other hand, when the hydrocalumite is described by, for example, Ca ₄ A ₂ (OH) ₁₂ Cl ₂ .4H ₂ O, Ca is present slightly apart from the top and bottom of the Al surface, and 6 OH ⁻ And one H ₂ O coordinated to form a seven-coordinate bond. Therefore, both types can be distinguished by X-ray diffraction. (H.F.W. Taylor, MINERALOGICAL MAGAZINE, 39, 377, 1973)

Hydrocalumite has a larger number of peaks because of its poor crystal symmetry than hydrotalcite, and there is a relatively strong peak at, for example, about 2.9 mm, and it can be easily distinguished from hydrotalcite by its presence or absence. it can.

（但し式中、Ａ^ｎ−は１価および／または２価のアニオン、例えばＯＨ⁻，Ｃｌ⁻，Ｂｒ⁻，ＮＯ_３ ⁻，ＣＨ_３ＣＯＯ⁻，ＳＯ_４ ^２−，ＣＯ_３ ^２−を示し、ｍは０≦ｍ＜１２の範囲を示す）で表される。ハイドロカルマイト類としては、［化１］において、Ｃａはその１部を最大で２５％まで、ＭｇとかＺｎ等の２価金属で置換可能である。ＡｌもＦｅ^３＋等の３価金属で置換可能である。Ａ^ｎ−はイオン交換性であり、ｎ＝３以上の多価アニオンについても、ハイドロカルマイト類構造を取り得る。しかし本発明では、［化１］において、金属としては、着色性、熱安定性等の理由でＣａとＡｌを、Ａ^ｎ−としては１価のアニオンを、より好ましくはＣｌ⁻，ＮＯ_３ ⁻，ＯＨ⁻等の１価のアニオンを、特に好ましくはＯＨ⁻および／またはＣｌ⁻を選択して用いることが好ましい。その理由は、１価のアニオンの方が２価以上のアニオンよりも熱安定性が良く、その中でも特にＯＨ⁻とＣｌ⁻が最も良いためである。 The hydrocalumite used in the present invention has the following formula (1):

(However ^{Shikichu, A n-1} monovalent and / or divalent anions, for example _{^{OH -, Cl -, Br -}} , NO 3 -, CH 3 COO -, SO 4 2-, CO 3 2- are shown, m represents a range of 0 ≦ m <12). As hydrocalumite, in [Chemical Formula 1], one part of Ca can be replaced with a divalent metal such as Mg or Zn up to 25% at maximum. Al can also be replaced with a trivalent metal such as Fe ³⁺ . A ⁿ⁻ is ion-exchangeable and can take a hydrocalumite structure even for polyvalent anions of n = 3 or more. However, in the present invention, in the Chemical Formula 1], as the metal, coloring, and Ca and Al for reasons of thermal stability, ^etc., a monovalent anion as ^{A n-,} more preferably ^Cl -, NO ₃ ^- , OH ^- a monovalent anion such as, particularly preferably OH ^- it is preferable to select and use ^- and / or Cl. The reason is that the monovalent anion has better thermal stability than the divalent or higher anion, and among them, OH ^- and Cl ^- are the best.

  Hydrocalumite has the same level of thermal stability as hydrotalcite, but is inferior in terms of strong middle and late coloration. On the other hand, calcium hydroxide is superior in thermal stability to hydrotalcites, but has a disadvantage that coloring in the initial and intermediate periods is extremely strong.

Therefore, as a result of intensive studies, the present inventors have made a hydrocalumite type by reacting a part thereof with a water-soluble aluminum salt such as aluminum chloride or aluminum hydroxide based on calcium hydroxide. Discovered that when converted to crystals, or when calcium hydroxide and hydrocalumite are reacted in an aqueous medium, calcium hydroxide and hydrocalumite are complexed, and this compound produces unexpectedly good results. did. That is, the composite compound solves the problem of initial coloration of calcium hydroxide, exhibits improved initial, intermediate and late colorability over hydrotalcites and exhibits thermal stability superior to hydrotalcites. Moreover, it has been found that if it is dried at about 100 ° C. to 120 ° C., it exhibits extremely excellent properties that it does not foam during molding. Furthermore, the composite compound of the present invention exhibits characteristics that can be produced very economically. This is because the hydrotalcite production method in which a mixture of water-soluble magnesium and aluminum salt is coprecipitated with alkali and then hydrothermally treated is compared with the production method of the present invention using calcium hydroxide as a main raw material. This is because the cost becomes high.

（但し式中、Ａ^ｎ−およびｍは、［化１］のＡ^ｎ−とｍと同じであり、ｙの範囲は０＜ｙ≦１６，好ましくは２≦ｙ≦８，である。Ｃａ／Ａｌのモル比で示すと、その範囲は２を超え１０以下、好ましくは３〜６である）で表される。この複合化合物は、無毒性、着色性、熱安定性、非発泡性、価格等の全ての分野で優れており、従来困難であった鉛系安定剤の代替も可能である。［化２］において、水酸化カルシウムの割合は多くなるほど熱安定性は向上する傾向にあるが、多くなり過ぎると初期着色性および中、後期着色性が低下する。［化２］の複合化合物は微粒子で、且つ含ハロゲン樹脂中で高分散であることが好ましい。そのためには、アルコールを溶媒として、レーザー回析法で測定する粒度分布の累積５０％の平均２次粒子径が２μｍ以下、特には１μｍ以下であることが好ましい。 The presumed composition formula of the composite compound of the present invention showing the above-mentioned characteristics is the following formula (2).

(However ^{Shikichu, A n-} and m are the same as ^{A n-} and m in Chemical Formula 1], the range of y is 0 <y ≦ 16, preferably 2 ≦ y ≦ 8, .Ca / In terms of the molar ratio of Al, the range is more than 2 and 10 or less, preferably 3 to 6. This composite compound is excellent in all fields such as non-toxicity, coloring property, thermal stability, non-foaming property, price, and the like, and can replace a lead-based stabilizer which has been difficult in the past. In [Chemical Formula 2], as the proportion of calcium hydroxide increases, the thermal stability tends to be improved. However, if the amount is too large, the initial colorability and the intermediate colorability deteriorate. The composite compound of [Chemical Formula 2] is preferably fine particles and highly dispersed in the halogen-containing resin. For that purpose, the average secondary particle diameter of 50% cumulative particle size distribution measured by laser diffraction method using alcohol as a solvent is preferably 2 μm or less, particularly preferably 1 μm or less.

In order to improve dispersion in the halogen-containing resin, it is preferable to subject the composite compound of [Chemical Formula 2] to a surface treatment with 0.1 to 10% by weight of an anionic or nonionic surfactant. . The surface treatment can be carried out by adding the surfactant solution after stirring the aluminum compound, or by adding the surfactant after solid-liquid separation, washing with water, re-kneading, and dispersing the resulting composite compound. . The latter is preferred. In addition to the above-described wet method, the so-called dry method of adding a surfactant dissolved in alcohol or the like after stirring the powdered composite compound of the present invention after drying with a Henschel mixer or the like can also be carried out. A wet method is preferred.

  The composite compound of the present invention is produced by dispersing calcium hydroxide in water and stirring with an aqueous solution of an aluminum salt, such as an aqueous solution of aluminum chloride, nitrate, bromide, acetate, etc., or aluminum hydroxide, or It can be carried out by adding and reacting hydrocalumite represented by the formula (1). The calcium hydroxide used here is preferably slaked lime digested with quicklime, but synthetic calcium hydroxide obtained by coprecipitation with a water-soluble calcium salt such as calcium chloride and an alkali such as sodium hydroxide can also be used. The standard of the amount in the case of adding a water-soluble aluminum salt is a range of 11 or less exceeding at least 3 in terms of a Ca / Al molar ratio. The reason is that 1 mol of calcium hydroxide is consumed for the reaction of Al with respect to 1 mol of Al. Although there is no restriction | limiting in particular in reaction temperature, About 40-90 degreeC, Especially 50-80 degreeC is preferable. The reaction time is not particularly limited, but is about 5 minutes or longer, preferably 20 to 60 minutes. After the reaction, means such as water sieving, surface treatment, filtration, washing with water, drying, pulverization, and classification are appropriately selected and carried out to obtain a final product.

  The stabilized halogen-containing resin of the present invention comprises 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, particularly preferably 0.2 to 3 parts by weight per 100 parts by weight of the halogen-containing resin. The composite compound of the present invention represented by 2] is blended. The stabilized halogen-containing resin of the present invention comprises (a) 0.01 to 2 parts by weight, preferably 0.1 to 1 part by weight of a zinc compound, (b) 0.001 in addition to the composite compound of the present invention. -2 parts by weight, preferably 0.01-1 part by weight of β-diketone, and (c) 0.001-2 parts by weight, preferably 0.1-1 part by weight of polyhydric alcohols. It is preferable to use it.

  Examples of the zinc compound (a) used in the present invention include zinc salts of organic acids such as lauric acid, palmitic acid and stearic acid, and inorganic zinc compounds such as zinc oxide and zinc carbonate. Preferred is an organic acid salt of zinc. Zinc compounds are useful for preventing initial coloration and as a lubricant.

（式中、Ｒ_１およびＲ３は同一、または異なってもよく、３０個までの炭素原子を有する直鎖、または分枝状のアルキル、またはアルケニル基、アリール基、または脂環式基、Ｒ_２は水素、アルキル基、アルケニル基を表す）で表される化合物である。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。 The (b) β-diketone used in the present invention is a compound useful for preventing initial coloring, and is represented by the following general formula (3):

Wherein R ₁ and R 3 may be the same or different and are straight or branched alkyl, alkenyl, aryl, or alicyclic groups having up to 30 carbon atoms, R ₂ Represents a hydrogen, alkyl group or alkenyl group). Examples of such β-diketones that can be preferably used include dibenzoylmethane (DBM), stearoylbenzoylmethane (SBM), benzoylacetone, acetylacetone, and dehydroacetic acid.

  The (c) polyhydric alcohols used in the present invention are useful for improving thermal stability, and are polyhydric alcohols or partial esters of polyhydric alcohols with mono- or polycarboxylic acids. Examples of such compounds include mannitol, sorbitol, pentaerythritol, dipentaerythritol, trimethylolpropane and the like.

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-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride -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-acrylo Tolyl copolymer, vinyl chloride - various vinyl ether copolymers chlorine-containing synthetic resin. Blends of these chlorine-containing synthetic resins with each other or with other chlorine-free synthetic resins, 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 heat 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 alkyl gallate, phenol such as 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 paracresol, 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-ditertiary butylphenyl) propionyloxymethylene] methane.

  The blending amount of these additives can be appropriately selected. For example, about 0.01 to about 5 parts by weight of stabilizing aids, about 0.01 to about 2 parts by weight with respect to 100 parts by weight of the halogen-containing resin. Antioxidants are exemplified. The present invention contains other conventional additives such as plasticizers, lubricants, processing aids, weather resistance improvers, antistatic agents, antifogging agents, reinforcing agents, fillers, pigments, etc. 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. For example, 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. is adopted. it can.

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

300 g of commercially available high-purity quicklime (from Niimi, Okayama Prefecture) was added to 5 liters of water heated to about 70 ° C. with stirring by a Chemistrar, and stirring was continued for about 20 minutes to carry out a digestion reaction. Then, 5 liters containing 4 moles from the filtered slurry was taken through a 200-mesh sieve, stirred in a 10 liter reaction vessel. [Ca (OH) ₂ concentration was determined by neutralization titration with hydrochloric acid. To this slurry (about 40 ° C.), 1.6 liter of 0.5 mol aqueous solution of aluminum chloride was added and stirred for about 30 minutes to react. The reaction product was filtered under reduced pressure, washed with water, dispersed in water, heated to about 70 ° C., and 200 ml of an aqueous solution (about 70 ° C.) in which 6.7 g of sodium laurate (purity 90%) was dissolved. Was added with stirring, and stirring was continued for about 10 minutes to perform surface treatment. Then, after filtering under reduced pressure and washing with water, it was dried at about 120 ° C. for 10 hours and further pulverized with an atomizer.

As a result of measuring the X-ray diffraction pattern of the pulverized product, the interplanar spacing d considered to correspond to Cl-type hydrocalumites (powder X-ray file No. 35-105) (relative intensity 100, strongest peak) ), 3.92 Å (19), 3.80 Å (6), 2.88 Å (8), 2.32 Å (6). Apart from this, the main times of d = 4.91 Å (29), 3.11 Å (9), 2.63） (42), 1.929 Å (15), and 1.797 Å (11) corresponding to calcium hydroxide There was an analysis peak. After dissolving the pulverized product with nitric acid, Ca and Al were measured by chelate titration method, Cl was measured by Mohr method, and crystallization water (H ₂ O) was measured by TGA. The chemical composition ratio (molar ratio) was as follows. there were. Ca: Al: Cl: H ₂ O = 3.1: 1: 0.98: 1.05. Considering the result of X-ray diffraction together, the following composition formula is estimated. Ca ₄ Al ₂ (OH) ₁₂ [Cl _1.96 (OH) _0.04 ] · 2.1H ₂ O · 2.2Ca (OH) ₂ . The amount of lauric acid was 1.7% as a result of measurement by adding a nitric acid solution in which the sample was dissolved to ether, dispersing and extracting into the ether phase, and measuring the weight after drying. The BET specific surface area measured by the liquid nitrogen adsorption method was 12 m ² / g. The particle size distribution was measured by adding a pulverized powder to isopropyl alcohol, dispersing with ultrasonic waves for 5 minutes, and then using a laser diffraction particle size distribution analyzer. The average secondary particle size with a cumulative 50% was 0.97 μm.

In Example 1, it carried out like Example 1 except having changed the addition amount of aluminum chloride into 1.5 liters. The X-ray diffraction pattern of the obtained pulverized product was substantially the same as that of Example 1 except that the relative strength of calcium hydroxide to hydrocalumite was slightly increased. As a result of analysis, the chemical composition ratio was as follows. Ca: Al: Cl: H ₂ O = 4.3: 1: 0.90: 0.95. The estimated composition formula is as follows. _{Ca 4 Al 2 (OH) 12} Cl 1.8 (OH) 0.2 · 1.9H 2 O · 4.6Ca (OH) 2. The amount of lauric acid was 1.8%, the BET specific surface area was 14 m ² / g, and the average secondary particle size with a cumulative 50% was 1.2 μm.

In Example 1, it carried out like Example 1 except having changed the density | concentration and addition amount of aluminum chloride into 0.3 mol / liter and 2 liter, respectively. The X-ray diffraction pattern of the obtained pulverized product was substantially the same as Example 1 except that the relative intensity of the peak corresponding to calcium hydroxide was high. As a result of the analysis, the chemical composition was as follows. Ca: Al: Cl: H ₂ O = 5.55: 1: 0.90: 1.0. The estimated composition formula is as follows. _{Ca 4 Al 2 (OH) 12} Cl 1.8 (OH) 0.2 · 2H 2 O · 7.1Ca (OH) 2. The amount of lauric acid was 1.9%, the BET specific surface area was 10 m ² / g, and the average secondary particle size with a cumulative 50% was 1.1 μm.

Example 1 is the same as Example 1 except that 2 liters of a 0.4 mol / liter aluminum nitrate aqueous solution is used instead of aluminum chloride, and 7.4 g of sodium stearate (purity 90%) is used instead of sodium laurate. The same was done. The X-ray diffraction pattern of the obtained pulverized product has an interplanar spacing of d = 8.48 Å (relative intensity 100), 4.31 Å (30), 3.09 Å (10), 2.86 ， (10), 2. There were main diffraction peaks at 73 and 2.48 (8), which were considered as NO ₃ type hydrocalumites, and the rest were calcium hydroxide patterns. As a result of the analysis, the chemical composition ratio was as follows. Ca: Al: NO ₃ : H ₂ O = 4.1: 1: 0.85: 1.50. The composition formula estimated from this is Ca ₄ Al ₂ (OH) ₁₂ (NO ₃ ) _1.7 (OH) _0.3 · 3H ₂ O · 4.2Ca (OH) ₂ . The amount of stearic acid was 2.0%, the BET specific surface area was 15 m ² / g, and the average secondary particle size with a cumulative 50% was 1.2 μm.
[Comparative Example 1]

In Example 1, it carried out similarly except having changed the addition amount of aluminum chloride to 2.67 liters. The X-ray diffraction pattern of the pulverized product is 3.91 Å, 3.79 Å, 2.82 と し て, etc. including the strongest peak d = 7.83 Å, which corresponds to Cl-type hydrocalumite.
[Comparative Example 2]

In Example 1, calcium hydroxide was prepared in the same manner except that aluminum chloride was not added. The amount of lauric acid in this product was 1.6%, the BET specific surface area was 11 m ² / g, and the average secondary particle size with a cumulative 50% was 1.9 μm.

In Example 1, instead of aluminum chloride, hydrochloric acid was added to pH 7 to 272 ml of sodium aluminate aqueous solution (Al ₂ O ₃ = 18.8%, Na ₂ O = 19.4%) containing 1 mol of Al. Then, 99.6% purity aluminum hydroxide was added, heated to about 80 ° C., and reacted for 40 minutes with stirring. Thereafter, the treatment after the surface treatment was performed in the same manner as in Example 1 using sodium laurate. The X-ray diffraction pattern of the obtained pulverized product is considered to be due to OH type hydrocalumite (powder X-ray file No. 16-333) d = 7.83 Å (relative intensity 100), d = 3 It was a mixture of main diffraction such as .93 (20), d = 3.80 (10), d = 2.88 (13), d = 2.32 (9) and calcium hydroxide. The chemical composition ratio was as follows as a result of analysis. Ca: Al: H ₂ O = 2.0: 1: 7.5. The composition formula estimated from this is as follows. Ca ₄ Al ₂ (OH) ₁₄ 4H ₂ O.4Ca (OH) ₂ . The amount of lauric acid was 1.6%, the BET specific surface area was 11 m ² / g, and the average secondary particle size with a cumulative 50% was 0.98 μm.

After drying the composite compound of C ₄ AH ₁₂ system and calcium hydroxide obtained in Examples 1 to 5 in polyvinyl chloride with the following formulation at 120 ° C. for 1 hour, after mixing as a stabilizer, using an open roll And kneading at 165 ° C. for 3 minutes to prepare a sheet having a thickness of about 1 mm.
[Prescription] Polyvinyl chloride (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 700) 100 parts by weight Zinc stearate 0.2 parts by weight Stearoylbenzoylmethane 0.15 parts by weight Dipentaerythritol 1.0 part by weight Stabilizer 1.0 part by weight The sheet is 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 10-minute intervals, the degree of initial coloring and the time until blackening (thermal stabilization time) The presence or absence of foaming was visually evaluated. The results are shown in Table 1.
[Comparative Examples 3 to 5]

In Example 5, as a stabilizer, the Cl-type hydrocalumite obtained in Comparative Example 1 [Comparative Example 3], the calcium hydroxide obtained in Comparative Example 2 [Comparative Example 4], and a commercially available hydrotalcite of ALCAMIZER _{1; Mg 4 a l2 (OH} ) 12 CO 3 · 3H 2 O [ Comparative example 5], a except for using each 1 part by weight the same manner as in example 5, the performance as a stabilizer for polyvinyl chloride Table 1 shows the results of the evaluation.

  [Table 1] shows the following. Although calcium hydroxide is excellent in thermal stability, there is a problem that strong initial coloring occurs. On the other hand, hydrotalcites are good with little initial colorability, but are strongly colored reddish orange in the later stage. Hydrocalumite exhibits similar properties to hydrotalcite, but is colored red-orange in the middle and later stages. However, the composite compound of the present invention has no initial coloration, little coloration in the middle and later stages, good hue, excellent thermal stability, and no foaming property.

Claims (7)

The molar ratio of Ca / Al is in the range of more than 2 and 10 or less per 100 parts by weight of the halogen-containing resin.

[In the formula, A ⁿ⁻ represents a monovalent and / or divalent anion (n = 1 and / or 2), and m is in the following range, 0 ≦ m <12]. A stabilized halogen-containing resin composition comprising 0.01 to 10 parts by weight of a complex compound of oysters and calcium hydroxide. In Chemical Formula 1] as claimed in claim 1, the anion ^{A n-} is _{^{Cl -, NO 3 -, OH}} - of claim 1 wherein the monovalent main component at least one or more selected from among anion such as A stabilized halogen-containing resin composition. 2. The stabilized halogen-containing resin composition according to claim 1, wherein the composite compound has a Ca / Al molar ratio in the range of 3 to 6. 2. The stabilized halogen-containing resin composition according to claim 1, wherein the composite compound according to claim 1 is surface-treated with 0.01 to 10% by weight of an anionic or nonionic surfactant. . In addition to the composite compound, the following component (a) 0.01 to 2 parts by weight of an organic acid zinc (b) 0.001 to 2 parts by weight of a β-diketone (c) 0.001 to 2 The stabilized halogen-containing resin composition according to claim 1, further comprising at least one selected from polyhydric alcohols by weight. The molar ratio of Ca / Al is in the range of more than 2 and 10 or less, the following formula (1)

(However Shikichu, A ^n-represents a monovalent and / or divalent anion, m is 0 ≦ m <in the range of 12) enable the composite compound of hydrocalumite such as calcium hydroxide represented by A stabilizer for halogen-containing resins contained as a component. Calcium hydroxide is dispersed in an aqueous medium, and an aqueous solution of an aluminum salt, aluminum hydroxide, or hydrocalumite is added under stirring so that the final product has a Ca / Al molar ratio of more than 2 to 10 or less. The method for producing a composite compound of calcium hydroxide and hydrocalumite according to claim 1, wherein the reaction product is added and reacted, and the reaction product is separated and recovered by a method known per se.