JPWO2006118325A1 - Resin composition - Google Patents

Abstract

An object of the present invention is to provide a resin composition having excellent long-term thermal stability and excellent initial colorability, and a molded product comprising the same. The present invention relates to (A) 0.001 part by weight or more and less than 0.1 part by weight of the following formula (1) Ca (OH) 2-nx (An-) x (1) with respect to 100 parts by weight of the synthetic resin. (Wherein n represents an integer of 1 to 4, x represents a number of 0.001 to 0.2, and An- represents an anion derived from a silicon compound, an aluminum compound, or a mixture thereof). This is a resin composition containing calcium hydroxide (A component) and (B) 0.1 to 10 parts by weight of hydrotalcite (B component).

Description

  The present invention relates to a resin composition containing a stabilizer. More specifically, the present invention relates to a resin composition containing solid solution calcium hydroxide and hydrotalcite as stabilizers. The present invention also relates to a molded article comprising the resin composition.

Synthetic resins, particularly halogen-containing resins, are unstable with respect to heat and light. Therefore, lead compounds, organotin compounds, and composite organics such as Cd / Ba, Ba / Zn, and Ca / Zn are used as stabilizers. Acid salts and the like have been used. However, the toxicity of these stabilizers and pollution of the global environment by these stabilizers has become a problem, and various types of stabilizers based on calcium hydroxide, which are safer and cheaper, have been developed for synthetic resins. (See Patent Documents 1 and 2).
However, since calcium hydroxide has a high solubility of quicklime in water, it is easy to grow crystals, has a small specific surface area (see Patent Document 3), and has a limited halogen trapping property. In addition, when calcium hydroxide stabilizer is blended with synthetic resin, there is a disadvantage that thermal stability is inferior and initial colorability is very poor compared with the case where lead compound and organic tin compound are blended with synthetic resin. .
Despite these drawbacks, calcium hydroxide is highly safe and inexpensive, so it has been expected to be used as a stabilizer for synthetic resins, and its improvement has been desired.
Japanese Patent Laid-Open No. 6-316662 JP-A-11-193336 JP 2001-127301 A

An object of the present invention is to provide a resin composition having excellent long-term thermal stability and excellent initial colorability, and a molded product comprising the same.
The present inventor has found that combining calcium hydroxide in which a silicon compound, an aluminum compound or a mixture thereof is dissolved and hydrotalcite can impart excellent thermal stability to a synthetic resin even in a small amount. The present invention has been completed.
That is, the present invention is based on 100 parts by weight of synthetic resin.
(A) 0.001 weight part or more and less than 0.1 weight part of following formula (1)
Ca (OH) _2-nx (A ⁿ⁻ ) _x (1)
(However, where n is an integer of 1 to 4, x is an anion derived from the number of 0.001 to ^{0.2, A n-silicon} compound, an aluminum compound or a mixture thereof.)
And (B) 0.1 parts by weight or more and 10 parts by weight or less of hydrotalcite (component B).
Moreover, this invention is a molded article which consists of the said resin composition.

で表されるものが好ましい。
前記式（２）において、Ａ^ｎ−はｎ価のアニオンを示す。ｎは、１〜４の整数が好ましい。より好ましくは１または２である。具体例としては、ＣｌＯ_４ ⁻、ＳＯ_４ ^２−およびＣＯ_３ ^２−が挙げられるが、ＣＯ_３ ^２−が好ましい。
また前記式（２）において（ｙ＋ｚ）は１であり、ｘは０．１≦ｘ≦０．５を満足し、好ましくは０．２≦ｘ≦０．４を満足する値である。
さらにｙは、０．５≦ｙ≦１を満足し、好ましくは０．７≦ｙ≦１を満足する値である。さらにｚは、０≦ｚ≦０．５を満足し、好ましくは０≦ｚ≦０．３を満足する値である。ｍは、０≦ｍ＜１を満足し、好ましくは０≦ｍ≦０．７を満足する値である。
Ｂ成分は、レーザー回折散乱法で測定された平均２次粒子径が２μｍ以下であること、つまりほとんどの粒子が２次凝集していない１次粒子であることが好ましく、さらに好ましくは平均２次粒子径が０．４〜１．０μｍの粒子である。
さらにＢ成分は、ＢＥＴ法により測定された比表面積が１〜３０ｍ^２／ｇであることが好ましく、さらに好ましくは５〜２０ｍ^２／ｇである。
Ｂ成分を製造する方法や条件は何等制限されない。Ｂ成分を得るための原料および製造条件はそれ自体公知であり、基本的には、公知の方法に従って製造することができる（例えば特公昭４６−２２８０号公報およびその対応する米国特許第３６５０７０４号明細書；特公昭４７−３２１９８号公報およびその対応する米国特許第３８７９５２５号明細書；特公昭５０−３００３９号公報；特公昭４８−２９４７７号公報；特公昭５１−２９１２９号公報等を参照）。
Ｂ成分を工業的規模で多量に生産するために使用される原料は、アルミニウム源として硫酸アルミニウムおよび塩化アルミニウム、アルミン酸ソーダ、および水酸化アルミニウム、マグネシウム源として海水、塩化マグネシウム（ブライン、イオン苦汁）、水酸化マグネシウム、酸化マグネシウムさらにアルカリ源としては、工業用の苛性ソーダが適しており、天然の石灰は精製が困難でありあまり好ましくない。さらに炭酸イオンの原料としては工業用の炭酸ソーダまたは炭酸ガスを使用できる。
Ｂ成分は焼成して使用することも可能である。焼成温度は、好ましくは２００℃以上、さらに好ましくは２３０℃以上である。
Ｂ成分は表面処理されたものが好ましい。表面処理剤は、Ａ成分の水酸化カルシウムの表面処理剤と同じものを同じ方法で適用することができる。
Ｂ成分は合成樹脂１００重量部に対して、０．１重量部以上で１０重量部以下、好ましくは０．２重量部以上で７重量部以下、さらに好ましくは０．５重量部以上で６重量部以下である。
なお、Ａ成分およびＢ成分中に鉄化合物、マンガン化合物等を多く含んでいると、樹脂に配合した場合、樹脂の耐熱劣化性を悪くするので、鉄化合物およびマンガン化合物の合計含有量が金属（Ｆｅ＋Ｍｎ）に換算して０．０２重量％以下が望ましい。
＜合成樹脂＞
合成樹脂は、通常、成形品として使用されるものであればよい。その例としてはポリエチレン、ポリプロピレン、エチレン／プロピレン共重合体、ポリブテン、ポリ−４−メチルペンテン−１等の如きＣ_２〜Ｃ_８オレフィン（α−オレフィン）の重合体もしくは共重合体、これらオレフィンとジエンとの共重合体類、エチレン−アクリレート共重合体、ポリスチン、ＡＢＳ樹脂、ＡＡＳ樹脂、ＡＳ樹脂、ＭＢＳ樹脂、エチレン／塩ビ共重合体樹脂、エチレン酢ビコポリマー樹脂、エチレン−塩ビ−酢ビグラフト重合樹脂、塩化ビニリデン、ポリ塩化ビニル、塩素化ポリエチレン、塩素化ポリプロピレン、塩ビプロピレン共重合体、酢酸ビニル樹脂、フェノキシ樹脂、ポリアセタール、ポリアミド、ポリイミド、ポリカーボネート、ポリスルホン、ポリフェニレンオキサイド、ポリフェニレンサルファイド、ポリエチレンテレフタレート、ポリブチレンテレフタレート、メタクリル樹脂等の熱可塑性樹脂、さらに、エポキシ樹脂、フェノール樹脂、メラミン樹脂、不飽和ポリエステル樹脂、アルキド樹脂、尿素樹脂等の熱硬化性樹脂およびＥＰＤＭ、ブチルゴム、イソプレンゴム、ＳＢＲ、ＮＢＲ、クロロスルホン化ポリエチレン、ＮＩＲ、ウレタンゴム、ブタジエンゴム、アクリルゴム、シリコーンゴム、フッ素ゴム等の合成ゴムを例示することが出来る。
本発明の樹脂組成物は、これらの合成樹脂と安定剤とをロールなどで混練することにより製造することができる。
合成樹脂がポリ塩化ビニルであることが好ましい。
本発明の樹脂組成物は、上記成分以外にも慣用の他の添加剤を配合してもよい。このような添加剤としては、例えば酸化防止剤、帯電防止剤、顔料、発泡剤、可塑剤、充填剤、補強剤、有機ハロゲン難燃剤、架橋剤、光安定剤、紫外線吸収剤、滑剤等を例示できる。
＜成形品＞
本発明は上記樹脂組成物からなる成形品を包含する。該成形品として、チューブ、パイプ、継手、フィルム、電線用ケーブル被覆材、窓枠、食品用包装容器、電子機器用の筐体または部品、自動車用部品等が挙げられる。Hereinafter, the present invention will be specifically described.
<Calcium hydroxide: A component>
A component used for this invention is following formula (1).
Ca (OH) _2-nx (A ⁿ⁻ ) _x (1)
It is calcium hydroxide represented by these.
Wherein n is an integer of 1 to 4, x is the number of 0.001 to ^{0.2, A n-silicon} compound, an aluminum compound or mixtures thereof derived from (hereinafter, it is referred to as additive) Represents an anion. Therefore, n is the valence of the anion, x is the content of the anion, and nx is the product of these.
As A ^n- monovalent anion ^{_{(n = 1), SiO (}} OH) 3 -, Al (OH) 4 - and the like. Examples of the divalent anion (n = 2) include SiO ₂ (OH) ₂ ²⁻ and Si ₂ O ₆ (OH) ₆ ²⁻ . Examples of the tetravalent anion (n = 4) include SiO ₄ ⁴⁻ and Si ₄ O ₈ (OH) ₄ ⁴⁻ . Among these, SiO (OH) ₃ ⁻ , SiO ₂ (OH) ₂ ²⁻ , and Al (OH) ₄ ⁻ are preferable. As A ^n-, can be simultaneously with a plurality of kinds of anions in the compound of formula (1). In this case, the sum of the product of the valence and content of each anion is represented by nx.
x is in the range of 0.001 to 0.2, preferably 0.005 to 0.15, and more preferably 0.01 to 0.1.
That is, the A component is calcium hydroxide formed by dissolving a silicon compound, an aluminum compound, or a mixture thereof.
As the silicon-based compound, at least one silicon-based compound selected from the group consisting of alkali silicate, silicate, hydrous silicic acid, anhydrous silicic acid, crystalline silicic acid (for example, quartz), and organic silicon-based compound is preferable. Silica (silicon dioxide) is particularly preferable. As the organosilicon compound, tetraethoxysilane, tetramethoxysilane, polymethoxysilane, silane coupling agent and the like are preferable.
As the aluminum compound, at least one aluminum compound selected from the group consisting of an aluminum salt, crystalline aluminum hydroxide and amorphous aluminum hydroxide is preferable.
A component is natural lime or synthetic lime. The component A preferably has a chlorine element content of 0.05% by weight or less and a sodium element content of 20 ppm or less. The sodium element content is measured by an atomic absorption method, and the chlorine element content is measured by an absorptiometric method.
The A component has an average secondary particle diameter measured by a laser diffraction scattering method of preferably 0.1 to 10 μm, more preferably 0.1 to 7 μm, and still more preferably 0.5 to 7 μm. A component, BET method specific surface area is preferably 5 to 40 m ² / g, more preferably 10 to 30 m ² / g.
The component A is suitable for use as a synthetic resin stabilizer because the crystal growth is suppressed in the production process and has fine crystals, so that the specific surface area is large and the activity is high, and the acid neutralization and halogen capture properties are large. be able to.
Component A is contained in an amount of 0.001 part by weight or more and less than 0.1 part by weight with respect to 100 parts by weight of the synthetic resin.
(Method for producing component A)
A component is in the presence of a silicon-based compound, an aluminum-based compound or a mixture thereof,
(I) digesting calcium oxide in water, or
(Ii) It can be produced by reacting a water-soluble calcium salt with an alkali metal hydroxide.
That is, the calcium hydroxide of the present invention can be produced by digestion reaction of quick lime (calcium oxide) in water containing a silicon compound, an aluminum compound, or a mixture (additive) thereof. Suitably, the quicklime is supplied to the water containing 10 to 60 ° C, preferably 30 to 60 ° C, containing the additive while stirring to cause a digestion reaction. By adding quicklime, the reaction temperature rises due to self-generated heat and reaches, for example, 90 ° C. or higher. When produced by the digestion method, calcium hydroxide having an average secondary particle size of 1.0 to 7 μm is obtained.
Second, it can be produced in the presence of an additive during the reaction of an aqueous solution of a water-soluble calcium salt and an aqueous solution of an alkali metal hydroxide. That is, an aqueous solution of a water-soluble calcium salt such as calcium chloride or calcium nitrate and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide in the presence of a silicon compound, an aluminum compound or a mixture thereof. It can manufacture by making it react. At this time, it is preferable that the alkali metal hydroxide aqueous solution has an alkali amount equivalent to calcium or more (preferably 1.05 to 1.3 times equivalent).
After the reaction, the white precipitate obtained is preferably heat-aged at about 60 to 150 ° C., preferably about 80 to 120 ° C. for 0.5 to 4 hours, and surface-treated with an anionic surfactant or the like. Then, it can manufacture by selecting, performing filtration, water washing, drying, grinding | pulverization, classification, etc. suitably. When produced by a reaction method, calcium hydroxide having an average secondary particle size of about 0.5 to 2 μm is obtained.
Thirdly, it is also possible to add a silicon-based compound, an aluminum-based compound or a mixture thereof to a calcium hydroxide particle suspension obtained by adding quick lime to water and digesting it, and aging to obtain an A component. is there.
The additive is preferably present in a proportion of 0.01 to 7% by weight, more preferably 0.05 to 7% by weight, and still more preferably 0.1 to 7% by weight with respect to the calcium hydroxide formed. When the content is less than 0.01% by weight, the specific surface area of the calcium hydroxide compound to be produced becomes small. If it exceeds 7% by weight, the solid solubility limit in calcium hydroxide may be exceeded.
In these production methods, it is not clear how the additive increases the BET surface area of the calcium hydroxide particles, but it seems that the additive acts as a crystal growth inhibitor and controls crystal growth.
Accordingly, the component A is present in the presence of a silicon compound, an aluminum compound, or a mixture thereof.
(I) digesting calcium oxide in water, or
(Ii) It can also be referred to as calcium hydroxide obtained by reacting a water-soluble calcium salt with an alkali metal hydroxide.
According to the above method, calcium hydroxide having a high specific surface area can be obtained, but further high quality calcium hydroxide can be obtained by further aging the reaction mixture after the reaction. In this aging, the reaction mixture is preferably 60 to 170 ° C., more preferably 80 to 120 ° C., more preferably 90 to 100 ° C., for 5 minutes to 3 hours, preferably 10 minutes to 2 hours, more preferably 20 It can be carried out for minutes to 1 hour.
Furthermore, after completion of the reaction or after completion of aging, the calcium hydroxide obtained may be pulverized in a suspension by a pulverizing means such as a wet ball mill. By pulverizing, particles having an average secondary particle size of less than 2 μm can be obtained.
If desired, the component A can be surface treated with a surface treating agent known per se. The surface treatment can improve compatibility with a resin or the like.
Examples of such surface treatment agents include (a) higher fatty acids, (b) alkali metal salts of higher fatty acids, (c) sulfates of higher alcohols, (d) anionic surfactants, (e) phosphate esters, (F) Coupling agent (silane, titanate, aluminum), (g) polyhydric alcohol fatty acid ester, and (h) silicon compound, phosphorus compound, aluminum compound, inorganic acid and organic acid Examples include compounds selected from the group.
Examples of those preferably used as the surface treatment agent are as follows.
(A) a higher fatty acid having 10 or more carbon atoms such as stearic acid, erucic acid, palmitic acid, lauric acid, behenic acid;
(B) an alkali metal salt of the higher fatty acid;
(C) sulfate esters of higher alcohols such as stearyl alcohol and oleyl alcohol;
(D) Polyethylene glycol ether sulfate, amide bond sulfate, ester bond sulfate, ester bond sulfonate, amide bond sulfonate, ether bond sulfonate, ether bond alkylaryl sulfonate, ester bond alkylaryl sulfonic acid Anionic surfactants such as salts and amide-linked alkylaryl sulfonates;
(E) orthophosphoric acid and mono- or diesters such as oleyl alcohol and stearyl alcohol, or a mixture of both, and their acid forms or phosphate esters such as alkali metal salts or amine salts;
(F) Vinylethoxysilane, vinyl-tris (2-methoxy-ethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Silane coupling agents such as γ-glycidoxypropyltrimethoxysilane and γ-mercaptopropyltrimethoxysilane; isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-aminoethyl-amino) Ethyl) titanate, titanate coupling agents such as isopropyltridecylbenzenesulfonyl titanate; aluminum coupling agents such as acetoalkoxyaluminum diisopropylate;
(G) Fatty acid esters of polyhydric alcohols such as glycerol monostearate and glycerol monooleate.
(H) SiO (OH) ₃ ⁻ , Al (OH) ₄ ⁻ , Cl ⁻ , NO ₃ ⁻ , H ₂ PO ₄ ⁻ , C ₆ H ₇ O ₇ ⁻ , SiO ₂ (OH) ₂ ²⁻ , Si ₂ O ₆ (OH) ₆ ²⁻ , HPO ₄ ²⁻ , C ₆ H ₆ O ₇ ²⁻ , PO ₄ ³⁻ , C ₆ H ₅ O ₇ ³⁻ , SiO ₄ ⁴⁻ or Si ₄ O ₈ (OH) ₄ ^{4 -} silicon compound having a like, phosphorus compounds, aluminum-based compounds.
The surface treatment of the component A can be carried out by a known wet method or a dry method. For example, as a wet method, a surface treatment agent may be added in a liquid or emulsion form to a slurry of calcium hydroxide particles and mechanically mixed sufficiently at a temperature up to about 100 ° C. As a dry method, the calcium hydroxide particles may be stirred with a mixer such as a Henschel mixer, and the surface treatment agent may be added in a liquid, emulsion, or solid form and mixed well with heating or non-heating. The addition amount of the surface treatment agent can be appropriately selected, but is preferably about 10% by weight or less based on the weight of the calcium hydroxide particles.
The surface-treated calcium hydroxide particles can be made into a final product form by appropriately selecting and implementing means such as water washing, dehydration, granulation, drying, pulverization, and classification, if necessary.
<Hydrotalcite: B component>
The resin composition of the present invention contains hydrotalcite as the B component in addition to the A component. Hydrotalcite may be synthetic or natural.
Hydrotalcite is expressed by the following formula (2)

The thing represented by these is preferable.
In the formula (2), A ⁿ⁻ represents an n-valent anion. n is preferably an integer of 1 to 4. More preferably, it is 1 or 2. Specific examples include ClO ₄ ⁻ , SO ₄ ²⁻ and CO ₃ ²⁻ , with CO ₃ ²⁻ being preferred.
In the formula (2), (y + z) is 1, and x satisfies 0.1 ≦ x ≦ 0.5, and preferably satisfies 0.2 ≦ x ≦ 0.4.
Furthermore, y is a value that satisfies 0.5 ≦ y ≦ 1, and preferably satisfies 0.7 ≦ y ≦ 1. Furthermore, z is a value that satisfies 0 ≦ z ≦ 0.5, and preferably satisfies 0 ≦ z ≦ 0.3. m is a value that satisfies 0 ≦ m <1 and preferably satisfies 0 ≦ m ≦ 0.7.
Component B preferably has an average secondary particle diameter of 2 μm or less measured by a laser diffraction scattering method, that is, primary particles in which most of the particles are not secondary aggregated, and more preferably an average secondary particle Particles having a particle size of 0.4 to 1.0 μm.
Furthermore, the B component preferably has a specific surface area measured by the BET method of 1 to 30 m ² / g, more preferably 5 to ²⁰ m ² / g.
The method and conditions for producing the B component are not limited at all. The raw materials and production conditions for obtaining the component B are known per se, and can basically be produced according to known methods (for example, Japanese Patent Publication No. 46-2280 and the corresponding US Pat. No. 3,650,704). (See Japanese Patent Publication No. 47-32198 and its corresponding US Pat. No. 3,879,525; Japanese Patent Publication No. 50-30039; Japanese Patent Publication No. 48-29477; Japanese Patent Publication No. 51-29129).
Raw materials used to produce B component in large quantities on an industrial scale are aluminum sulfate and aluminum chloride as aluminum sources, sodium aluminate and aluminum hydroxide, seawater as magnesium source, magnesium chloride (brine, ionic bitter) Further, magnesium hydroxide, magnesium oxide, and an alkali source are suitable for industrial caustic soda, and natural lime is not preferred because it is difficult to purify. Furthermore, industrial sodium carbonate or carbon dioxide can be used as a raw material for carbonate ions.
The component B can be used after firing. The firing temperature is preferably 200 ° C. or higher, more preferably 230 ° C. or higher.
The component B is preferably surface-treated. The same surface treatment agent as the surface treatment agent for calcium hydroxide as the component A can be applied by the same method.
Component B is 0.1 parts by weight or more and 10 parts by weight or less, preferably 0.2 parts by weight or more and 7 parts by weight or less, more preferably 0.5 parts by weight or more and 6 parts by weight or more with respect to 100 parts by weight of the synthetic resin. Or less.
If the A component and the B component contain a large amount of iron compound, manganese compound, etc., when blended in the resin, the heat deterioration resistance of the resin is deteriorated. Therefore, the total content of the iron compound and the manganese compound is a metal ( It is preferably 0.02% by weight or less in terms of Fe + Mn).
<Synthetic resin>
The synthetic resin may be any resin that is usually used as a molded product. Examples thereof include polymers or copolymers of C _{2 to} C ₈ olefins (α-olefins) such as polyethylene, polypropylene, ethylene / propylene copolymers, polybutene, poly-4-methylpentene-1, and the like. Copolymers with dienes, ethylene-acrylate copolymers, polystyrene, ABS resins, AAS resins, AS resins, MBS resins, ethylene / vinyl chloride copolymer resins, ethylene vinyl acetate copolymer resins, ethylene vinyl chloride vinyl acetate graft polymerizations Resin, vinylidene chloride, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, vinyl chloride propylene copolymer, vinyl acetate resin, phenoxy resin, polyacetal, polyamide, polyimide, polycarbonate, polysulfone, polyphenylene oxide, polyphenylene sulfide Thermoplastic resins such as polyethylene terephthalate, polybutylene terephthalate, methacrylic resin, and epoxy resins, phenolic resins, melamine resins, unsaturated polyester resins, alkyd resins, urea resins, and EPDM, butyl rubber, isoprene rubber, Examples thereof include synthetic rubbers such as SBR, NBR, chlorosulfonated polyethylene, NIR, urethane rubber, butadiene rubber, acrylic rubber, silicone rubber, and fluorine rubber.
The resin composition of the present invention can be produced by kneading these synthetic resins and stabilizers with a roll or the like.
The synthetic resin is preferably polyvinyl chloride.
The resin composition of the present invention may contain other conventional additives in addition to the above components. Examples of such additives include antioxidants, antistatic agents, pigments, foaming agents, plasticizers, fillers, reinforcing agents, organic halogen flame retardants, crosslinking agents, light stabilizers, ultraviolet absorbers, lubricants, and the like. It can be illustrated.
<Molded product>
The present invention includes a molded article comprising the above resin composition. Examples of the molded article include tubes, pipes, joints, films, cable covering materials for electric wires, window frames, food packaging containers, casings or parts for electronic devices, automobile parts, and the like.

合成例５ ＣＨ３９の合成
２ｍ^３容の反応槽に４ＮのＮａＯＨ ３６０Ｌと、水ガラス（３９８ｇ／Ｌ）を表３に示す量を入れ、さらに４ｍｏｌ／ＬのＣａＣｌ_２ １６５Ｌを入れ、４０℃で５分間反応させた。得られた反応物をろ過、乾燥し、粉砕し、固溶水酸化カルシウムＣＨ３９を調製した。ＣＨ３９の組成および物性の測定結果は、表４のとおりであった。
合成例６ ＣＨ４０の合成
合成例５の水ガラスの代わりに、合成非晶質シリカ（ＳｉＯ_２＝９３重量％）を表３に示す量だけ用いたほかは、合成例５と同じ方法で固溶水酸化カルシウムＣＨ４０を調製した。ＣＨ４０の組成および物性の測定結果は、表４の通りであった。
合成例７ ＣＨ４２の合成
合成例５の水ガラスの代わりに、テトラエトキシシラン（ＳｉＯ_２＝２８重量％）を表３に示す量だけ用いたほかは、合成例５と同じ方法で固溶水酸化カルシウムＣＨ４２を調製した。ＣＨ４２の組成および物性の測定結果は、表４の通りであった。

合成例８ ＨＴ１の合成
精製ブライン（ＭｇＣｌ_２＝３１２．１ｇ／Ｌ）を濃度調整用タンクに移し、硫酸アルミニウム（Ａｌ_２Ｏ_３＝１０６．８ｇ／Ｌ）を加えてＭｇ濃度１．９５ｍｏｌ／ＬおよびＡｌ濃度０．８４７ｍｏｌ／Ｌの混合水溶液（Ａ）を作った。次に苛性ソーダ（４８．７％）を別の濃度調整用タンクに移し、炭酸ソーダ粉末（Ｎａ_２ＣＯ_３＝９９．９％）および水を加えてＮａＯＨ ３ｍｏｌ／ＬおよびＮａ_２ＣＯ_３０．２３ｍｏｌ／Ｌを含む水溶液（Ｂ）を作った。
混合水溶液（Ａ）１．１８Ｌに対し水溶液（Ｂ）２．２Ｌの割合で、予め水を入れた反応槽に、攪拌下に滞留時間が６０分となるように同時注加してハイドロタルサイトの反応スラリーを得た。この反応スラリー８００Ｌを採取し、加熱熟成するためオートクレーブ中で１７０℃×６時間攪拌しながら維持させた。冷却後スラリーを表面処理槽に移し、攪拌しながら８０℃まで加温し、予め８０℃の温水５０Ｌに溶かしたステアリン酸ソーダ（Ｃ_１７Ｈ_３６ＣＯＯＮａ＝９３．４％）２ｋｇを徐々に投入し３０分間攪拌を維持して表面処理を完了した。固形物を濾別、洗浄し、熱風乾燥機にて乾燥後ハンマーミル粉砕してサンプルとした。
得られたＨＴ１を分析した結果、組成式は
Ｍｇ_０．７Ａｌ_０．３（ＯＨ）_２（ＣＯ_３）_０．１５・０．５Ｈ_２Ｏであった。
組成および物性の測定結果を表５に示す。
合成例９ ＨＴ２の合成
合成例８において、原料中、精製ブラインの代わりにイオン苦汁、および塩化亜鉛を用いたほかは、全く同様な装置を用い同様に反応した。すなわち、イオン苦汁（ＭｇＣｌ_２＝１６８．２ｇ／Ｌ）を濃度調整用タンクに移し、塩化亜鉛（ＺｎＣｌ_２＝５７２．７ｇ／Ｌ）、硫酸アルミニウム（Ａｌ_２Ｏ_３＝１０６．８ｇ／Ｌ）を加えてＭｇ濃度１．０５ｍｏｌ／Ｌ、Ｚｎ濃度０．４２ｍｏｌ／ＬおよびＡｌ濃度０．６３ｍｏｌ／Ｌの混合水溶液を作る。この時、混合槽で硫酸カルシウムの沈殿を生じるので濾別し（Ａ）液とする。次に苛性ソーダ（ＮａＯＨ４８．７％）を別の濃度調整用タンクに移し、炭酸ソーダ粉末（Ｎａ_２ＣＯ_３＝９９．９％）、および水を加えてＮａＯＨ３ｍｏｌ／Ｌ、Ｎａ_２ＣＯ_３ ０．２２５ｍｏｌ／Ｌ水溶液（Ｂ）を作る。
（Ａ）液１Ｌに対し（Ｂ）液１．４Ｌの割合で、予め水を入れた反応槽に、攪拌下に滞留時間が６０分となるように同時注加してＨＴの反応スラリーを得た。
この反応スラリー８００Ｌを採取し、加熱熟成するためオートクレーブ中で１４０℃×６時間攪拌しながら維持させた。冷却後スラリーを表面処理槽に移し、攪拌しながら８０℃まで加温し、予め８０℃の温水５０Ｌに溶かしたステアリン酸ソーダ １．３ｋｇを徐々に投入し、３０分間攪拌を維持して表面処理を完了した。固形物を濾別、洗浄し、再乳化後噴霧乾燥しサンプルとした。
得られたＨＴ２の合成を分析した結果、組成式は
Ｍｇ_０．５Ｚｎ_０．２Ａｌ_０．３（ＯＨ）_２（ＣＯ_３）_０．１５・０．５５Ｈ_２Ｏであった。
組成および物性の測定結果を表５に示す。
合成例１０ ＨＴ３の合成
合成例８で得られたハイドロタルサイトＨＴ１を２４０℃で焼成しハイドロタルサイトＨＴ３を調製した。組成および物性の測定結果を表５に示す。
合成例１１ ＨＴ４の合成
合成例９で得られたＨＴ２を２４０℃で焼成しハイドロタルサイトＨＴ４を調製した。組成および物性の測定結果を表５に示す。

実施例１〜１０および比較例１〜７
固溶水酸化カルシウムＣＨ３９、ＣＨ２３、ハイドロタルサイトＨＴ１およびＨＴ２、並びに非固溶カルシウムＣＨＣＥ３を安定剤として、下記に示す配合組成（Ａ）の樹脂組成物を調製し、該樹脂組成物をロールを用いて１８０℃×５分間混練し、０．７ｍｍのロールシートを作成した。安定剤の組成は表６に示す。
熱安定性は、このシートを５ｃｍ×８ｃｍのサイズに切り取り、１９０℃ギアオーブン中に入れて１０分毎に取り出し評価した。評価は、着色によって現れた樹脂の劣化度により行い、一定の黒さに黒化した時間を測定するとともに、熱安定性初期の色を評価した。結果を表６に示す。
配合組成（Ａ）
ポリ塩化ビニル（重合度７００） １００ＰＨＲ
ステアリン酸亜鉛 ０．３ＰＨＲ
ステアロイルベンゾイルメタン ０．２ＰＨＲ
ジペンタエリスリトール ０．２ＰＨＲ
安定剤 １．０ＰＨＲ

実施例１１〜１３および比較例８〜１１
固溶水酸化カルシウムＣＨ３９、ハイドロタルサイトＨＴ２および非固溶カルシウムＣＨＣＥ３を安定剤とし、下記に示す配合組成（Ｂ）の樹脂組成物を調製し、該樹脂組成物をロールを用いて１８０℃×５分間混練し、０．７ｍｍのロールシートを作成した。熱安定性を実施例１と同様の方法で評価した。安定剤の組成、結果を表７に示す。
配合組成（Ｂ）
ポリ塩化ビニル（重合度１０００） １００ＰＨＲ
ジベンゾイルメタン ０．１ＰＨＲ
ジペンタエリスリトール ０．２ＰＨＲ
Ｄキシオール Ｇ３２ ０．２ＰＨＲ
ステアリン酸亜鉛 ０．８ＰＨＲ
ステアリン酸カルシウム ０．４ＰＨＲ
メタブレンＰ−５０１ ０．５ＰＨＲ
白艶華ＣＣＲ（炭酸カルシウム、
白石カルシウム製） ４．０ＰＨＲ
安定剤 １．０ＰＨＲ

実施例１４〜１９および比較例１２〜１７
固溶水酸化カルシウムＣＨ２２、ＣＨ４０、ＣＨ４２、ハイドロタルサイトＨＴ１、および非固溶カルシウムＣＨＣＥ３を安定剤として、下記に示す配合組成（Ｃ）の樹脂組成物を調製し、該樹脂組成物をロールを用いて１８０℃×５分間混練し、０．７ｍｍのロールシートを作成した。熱安定性を実施例１と同様の方法で評価した。安定剤の組成、結果を表８に示す。
配合組成（Ｃ）
ポリ塩化ビニル（重合度１０００） １００ＰＨＲ
ジベンゾイルメタン ０．１ＰＨＲ
ジペンタエリスリトール ０．２ＰＨＲ
Ｄキシオール Ｇ３２（コグニス製） ０．２ＰＨＲ
ステアリン酸亜鉛 ０．６ＰＨＲ
ステアリン酸カルシウム ０．２ＰＨＲ
重質炭酸カルシウム ３．０ＰＨＲ
安定剤 ０．５ＰＨＲ

実施例２０〜４５および比較例１８〜２３
固溶水酸化カルシウムＣＨ３９、ＣＨ２３、ＣＨ２６、ＣＨ４０、ＣＨ４２、ハイドロタルサイトＨＴ１、ＨＴ２、ＨＴ３、ＨＴ４および非固溶カルシウムＣＨＣＥ３を安定剤として、下記に示す配合組成（Ｄ）の樹脂組成物を調製し、該樹脂組成物をロールを用いて１８０℃×５分間混練し、０．７ｍｍのロールシートを作成した。熱安定性を実施例１と同様の方法で評価した。安定剤の組成、結果を表９に示す。
配合組成（Ｄ）
ポリ塩化ビニル（重合度１３００） １００ＰＨＲ
ＤＯＰ（ジオクチルフタレート） ５０ＰＨＲ
ステアリン酸亜鉛 ０．６ＰＨＲ
安定剤 ０．５ＰＨＲ

実施例４６〜５４および比較例２４
固溶水酸化カルシウムＣＨ３９、ハイドロタルサイトＨＴ１およびＨＴ２を安定剤として、下記に示す配合組成（Ｄ−１）の樹脂組成物を調製し、該樹脂組成物をロールを用いて１８０℃×５分間混練し、０．７ｍｍのロールシートを作成した。熱安定性を実施例１と同様の方法で評価した。安定剤の組成、結果を表１０に示す。
配合組成（Ｄ−１）
ポリ塩化ビニル（重合度１３００） １００ＰＨＲ
ジオクチルフタレート ５０ＰＨＲ
ステアリン酸亜鉛 ０．４ＰＨＲ
安定剤 １．６ＰＨＲ

実施例５５〜６３および比較例２５
固溶水酸化カルシウムＣＨ３９、ハイドロタルサイトＨＴ１およびＨＴ２を安定剤として、下記に示す配合組成（Ｄ−２）の樹脂組成物を調製し、該樹脂組成物をロールを用いて１８０℃×５分間混練し、０．７ｍｍのロールシートを作成した。熱安定性を実施例１と同様の方法で評価した。安定剤の組成、結果を表１１に示す。
配合組成（Ｄ−２）
ポリ塩化ビニル（重合度１３００） １００ＰＨＲ
ジオクチルフタレート ５０ＰＨＲ
ステアリン酸亜鉛 ０．４ＰＨＲ
安定剤 ４．０ＰＨＲ

実施例６４〜７１および比較例２６
固溶水酸化カルシウムＣＨ３９、ハイドロタルサイトＨＴ１およびＨＴ２を安定剤として、下記に示す配合組成（Ａ−１）の樹脂組成物を調製し、該樹脂組成物をロールを用いて１８０℃×５分間混練し、０．７ｍｍのロールシートを作成した。熱安定性を実施例１と同様の方法で評価した。安定剤の組成、結果を表１２に示す。
配合組成（Ａ−１）
ポリ塩化ビニル（重合度７００） １００ＰＨＲ
ステアリン酸亜鉛 ０．３ＰＨＲ
ステアロイルベンゾイルメタン ０．２ＰＨＲ
ジペンタエリスリトール ０．２ＰＨＲ
安定剤 ３．０ＰＨＲ

実施例７２〜７９および比較例２７
固溶水酸化カルシウムＣＨ３９、ハイドロタルサイトＨＴ１およびＨＴ２を安定剤として、下記に示す配合組成（Ａ−２）の樹脂組成物を調製し、該樹脂組成物をロールを用いて１８０℃×５分間混練し、０．７ｍｍのロールシートを作成した。熱安定性を実施例１と同様の方法で評価した。安定剤の組成、結果を表１３に示す。
配合組成（Ａ−２）
ポリ塩化ビニル（重合度７００） １００ＰＨＲ
ステアリン酸亜鉛 ０．３ＰＨＲ
ステアロイルベンゾイルメタン ０．２ＰＨＲ
ジペンタエリスリトール ０．２ＰＨＲ
安定剤 ６．０ＰＨＲ

［発明の効果］
本発明によれば、比表面積が大きく高活性であり、酸中和性やハロゲン捕捉性が大きい固溶水酸化カルシウムと、ハイドロタルサイトとを組み合わせることにより、合成樹脂に優れた熱安定性および初期着色性を付与する安定剤組成物が提供される。
本発明の樹脂組成物および成形品は、熱安定性、特に長期熱安定性に優れ、初期着色性が優れている。Hereinafter, the present invention will be described in detail by way of examples.
In the following examples, (1) average secondary particle diameter, (2) BET specific surface area, (3) SiO ₂ analysis, (4) Al ₂ O ₃ , (5) metal analysis, The method was performed.
(1) Average secondary particle size;
Measurement was performed by a laser diffraction scattering method using a MICROTRAC particle size analyzer SPA type [LEEDS &amp; manufactured by NORTHROUP INSTRUMENTS]. That is, 700 mg of sample powder was added to 70 ml of water, and after 3 minutes of dispersion treatment with ultrasonic waves (manufactured by NISSEI, MODEL US-300, current of 300 μA), 2 to 4 ml of the dispersion was taken and 250 ml of degassed. In addition to the sample chamber of the particle size analyzer containing water, the analyzer was activated and the suspension was circulated for 8 minutes, and then the particle size distribution was measured. The measurement was performed twice in total, and the arithmetic average value of the 50% cumulative secondary particle diameter obtained for each measurement was calculated to obtain the average secondary particle diameter of the sample.
(2) BET specific surface area;
It was measured by the liquid nitrogen adsorption method. That is, it measured using the liquid nitrogen adsorption method apparatus (NOVA2000 by Yuasa Ionics). 0.5 g of the sample powder was accurately weighed in a dedicated cell for measurement, and pretreated for 30 minutes at 105 ° C. under a vacuum degree of 10 mTorr or less (apparatus: Flovac Degasser manufactured by Yuasa Ionics). After the pretreatment, the cell was cooled and placed in the measuring device room to measure the specific surface area.
(3) analysis of SiO ₂ ;
Analyzed by spectrophotometry. That is, 0.5 g of the sample powder was accurately weighed into a platinum crucible, and 2 g of boric acid and 3 g of anhydrous sodium carbonate were added and mixed. After melting at 950 ° C. for 2 hours, it was cooled, dissolved in 40 ml of diluted hydrochloric acid, and ion exchanged water was added to make 250 ml. 25 ml of the solution was taken, transferred to a 100 ml volumetric flask, 5 ml of ammonium molybdate solution (10% solution) was added, and ion-exchanged water was further added to make 100 ml to obtain a measurement solution. The determination was performed by measuring the absorbance at 420 nm using a spectrophotometer device (double beam spectrophotometer 150-20 type manufactured by Hitachi, Ltd.).
(4) Analysis of Al ₂ O ₃ ;
Analysis was performed by chelation method. That is, 0.5 g of sample powder was accurately weighed in a 100 ml beaker, 20 ml of diluted hydrochloric acid and 15 ml of perchloric acid were added, and the mixture was heated at 150 to 200 ° C. for 30 minutes. After heating, cooling water was added and insoluble matter was filtered and washed with a quantitative filter paper. The filtrate and the washing solution were combined to make exactly 250 ml to obtain a measurement solution. Take 25 ml of the measurement solution and add ion-exchanged water to adjust the pH to 3.0. The indicator Cu-PAN solution was added to the pH adjustment solution for measurement, and titrated with a 0.01 mol / l-EDTA2Na solution while heating until boiling. The end point of the titration was a point where the color did not turn orange or yellow even when heated for 1 minute or longer.
(5) Metal analysis 0.5 g of sample powder was accurately weighed in a 100 ml beaker, and 10 ml of diluted hydrochloric acid was added and dissolved by heating. After cooling, it was transferred to a 100 ml volumetric flask and ion exchanged water was added to make 100 ml to obtain a measurement solution. Quantification was performed by measuring the absorbance at Mn = 257.610 nm and Fe = 259.940 nm using an ICP emission spectroscopic analyzer (SPS 1500VR manufactured by Seiko Instruments Inc.).
Synthesis Examples 1 and 2 Synthesis of CH22 and 23 In a 2 m ³ volume reactor, 360 L of 4 N NaOH and water glass (398 g / L) were added in the amounts shown in Table 1, and 165 L of 4 mol / L CaCl ₂ was further added. The reaction was carried out at 40 ° C. for 5 minutes. The obtained reaction product was filtered, dried and pulverized to obtain solid solution calcium hydroxides CH22 and 23. Table 2 shows the measurement results of the composition and physical properties of CH22 and 23.
Synthesis Example 3 Synthesis of CH26 In a 2 m ³ volume reactor, 360 L of 4N NaOH and sodium aluminate (323 g / L) shown in Table 1 were added, and 4 mol / L of Cacl ₂ 165 L was further added at 40 ° C. The reaction was allowed for 5 minutes. The obtained reaction product was filtered, dried and pulverized to obtain a solid solution calcium hydroxide CH26. The measurement results of the composition and physical properties of CH26 are shown in Table 2.
Synthesis Example 4 _H 2 O 1m ³ reactor, the synthesis 2m ³ of CH29 and water glass (398 g / L) placed in the amounts shown in Table 1 and the temperature was adjusted in the reaction vessel to 60 ° C.. Thereafter, 27 kg of quicklime was further added. By adding quicklime, the temperature rises to about 90 ° C. due to heat of digestion. In this state, the reaction was performed for 30 minutes. The obtained reaction product was filtered, dried and pulverized to obtain a solid solution calcium hydroxide CH29. Table 2 shows the measurement results of the composition and physical properties of CH29.
And NaOH 360 L of 4N in a reaction vessel of synthetic 2m ³ volumes of Reference Example 1 _CHCE3, and CaCl 2 (4mol / L) 165L react 5 minutes at 40 ° C., filtered, dried, pulverized, non-soluble hydroxide Calcium CHCE3 was obtained. Table 2 shows the measurement results of the composition and physical properties of CHCE3.

Synthesis Example 5 Synthesis of CH39 In a 2 m ³ volume reaction vessel, 360 N of 4N NaOH and water glass (398 g / L) were added in the amounts shown in Table 3, and 165 L of 4 mol / L CaCl ₂ was added. Reacted for 1 minute. The obtained reaction product was filtered, dried and pulverized to prepare a solid solution calcium hydroxide CH39. Table 4 shows the measurement results of the composition and physical properties of CH39.
Synthesis Example 6 Synthesis of CH40 In place of the water glass of Synthesis Example 5, synthetic amorphous silica (SiO ₂ = 93 wt%) was used in the same manner as in Synthesis Example 5 except that only the amount shown in Table 3 was used. Calcium hydroxide CH40 was prepared. The measurement results of the composition and physical properties of CH40 are shown in Table 4.
Synthesis Example 7 Synthesis of CH42 Solid solution hydroxylation was performed in the same manner as in Synthesis Example 5 except that tetraethoxysilane (SiO ₂ = 28 wt%) was used in the amount shown in Table 3 instead of the water glass of Synthesis Example 5. Calcium CH42 was prepared. The measurement results of the composition and physical properties of CH42 are shown in Table 4.

Synthesis Example 8 Synthesis of HT1 Purified brine (MgCl ₂ = 312.1 g / L) was transferred to a concentration adjustment tank, and aluminum sulfate (Al ₂ O ₃ = 106.8 g / L) was added thereto to add a Mg concentration of 1.95 mol / L. A mixed aqueous solution (A) having an Al concentration of 0.847 mol / L was prepared. Next, caustic soda (48.7%) was transferred to another tank for concentration adjustment, sodium carbonate powder (Na ₂ CO ₃ = 99.9%) and water were added, and NaOH 3 mol / L and Na ₂ CO ₃ 0.23 mol were added. An aqueous solution (B) containing / L was prepared.
Hydrotalcite was simultaneously poured into a reaction tank in which water was previously added at a ratio of 2.2 L of aqueous solution (B) to 1.18 L of mixed aqueous solution (A) so that the residence time was 60 minutes with stirring. The reaction slurry was obtained. 800 L of this reaction slurry was sampled and maintained with stirring in an autoclave at 170 ° C. for 6 hours for heating and aging. After cooling, the slurry was transferred to a surface treatment tank, heated to 80 ° C. with stirring, and 2 kg of sodium stearate (C ₁₇ H ₃₆ COONa = 93.4%) dissolved in 50 L of hot water at 80 ° C. was gradually added. Stirring was maintained for 30 minutes to complete the surface treatment. The solid matter was separated by filtration, washed, dried with a hot air dryer, and then pulverized with a hammer mill to prepare a sample.
As a result of analyzing the obtained HT1, the composition formula was Mg _0.7 Al _0.3 (OH) ₂ (CO ₃ ) _0.15 · 0.5H ₂ O.
The measurement results of the composition and physical properties are shown in Table 5.
Synthesis Example 9 Synthesis of HT2 In Synthesis Example 8, the reaction was performed in the same manner except that ion bitter and zinc chloride were used instead of purified brine in the raw material. That is, ion bitter (MgCl ₂ = 168.2 g / L) is transferred to a concentration adjusting tank, and zinc chloride (ZnCl ₂ = 572.7 g / L) and aluminum sulfate (Al ₂ O ₃ = 106.8 g / L) are added. In addition, a mixed aqueous solution having an Mg concentration of 1.05 mol / L, a Zn concentration of 0.42 mol / L, and an Al concentration of 0.63 mol / L is prepared. At this time, precipitation of calcium sulfate occurs in the mixing tank, so it is filtered and used as the liquid (A). Next, caustic soda (NaOH 48.7%) was transferred to another tank for concentration adjustment, and sodium carbonate powder (Na ₂ CO ₃ = 99.9%) and water were added to add NaOH ₃ mol / L, Na ₂ CO ₃ 0.225 mol. / L Aqueous solution (B) is made.
(A) The reaction slurry of HT was obtained by simultaneously pouring into a reaction tank in which water was previously added at a ratio of 1.4 L of (B) liquid to 1 L of liquid so that the residence time was 60 minutes under stirring. It was.
800 L of this reaction slurry was sampled and maintained with stirring in an autoclave at 140 ° C. for 6 hours for heating and aging. After cooling, the slurry is transferred to a surface treatment tank, heated to 80 ° C. while stirring, 1.3 kg of sodium stearate previously dissolved in 50 L of warm water at 80 ° C. is gradually added, and stirring is maintained for 30 minutes to perform surface treatment. Completed. The solid was separated by filtration, washed, re-emulsified and spray-dried to obtain a sample.
Analysis of the synthesis of the resulting HT2, composition formula was _{Mg 0.5 Zn 0.2 Al 0.3 (OH} ) 2 (CO 3) 0.15 · 0.55H 2 O.
The measurement results of the composition and physical properties are shown in Table 5.
Synthesis Example 10 Synthesis of HT3 Hydrotalcite HT1 obtained in Synthesis Example 8 was calcined at 240 ° C. to prepare hydrotalcite HT3. The measurement results of the composition and physical properties are shown in Table 5.
Synthesis Example 11 Synthesis of HT4 HT2 obtained in Synthesis Example 9 was calcined at 240 ° C. to prepare hydrotalcite HT4. The measurement results of the composition and physical properties are shown in Table 5.

Examples 1-10 and Comparative Examples 1-7
Using the solid solution calcium hydroxide CH39, CH23, hydrotalcite HT1 and HT2, and non-solid solution calcium CHCE3 as stabilizers, a resin composition having the following composition (A) is prepared, and the resin composition is rolled. And kneaded at 180 ° C. for 5 minutes to prepare a 0.7 mm roll sheet. The composition of the stabilizer is shown in Table 6.
The thermal stability was evaluated by taking out this sheet into a size of 5 cm × 8 cm, putting it into a 190 ° C. gear oven, and taking it out every 10 minutes. The evaluation was performed based on the degree of deterioration of the resin that appeared due to coloring, and the time for blackening to a certain black was measured, and the initial color of thermal stability was evaluated. The results are shown in Table 6.
Composition (A)
Polyvinyl chloride (degree of polymerization 700) 100PHR
Zinc stearate 0.3PHR
Stearoylbenzoylmethane 0.2PHR
Dipentaerythritol 0.2PHR
Stabilizer 1.0PHR

Examples 11-13 and Comparative Examples 8-11
Using the solid solution calcium hydroxide CH39, hydrotalcite HT2 and non-solid solution calcium CHCE3 as stabilizers, a resin composition having the following composition (B) is prepared, and the resin composition is heated at 180 ° C. using a roll. The mixture was kneaded for 5 minutes to prepare a 0.7 mm roll sheet. Thermal stability was evaluated in the same manner as in Example 1. Table 7 shows the composition and results of the stabilizer.
Composition (B)
Polyvinyl chloride (degree of polymerization 1000) 100PHR
Dibenzoylmethane 0.1PHR
Dipentaerythritol 0.2PHR
D-Xiol G32 0.2PHR
Zinc stearate 0.8PHR
Calcium stearate 0.4PHR
METABLEN P-501 0.5PHR
White gloss flower CCR (calcium carbonate,
4.0PHR made of calcium Shiraishi)
Stabilizer 1.0PHR

Examples 14-19 and Comparative Examples 12-17
Using the solid solution calcium hydroxide CH22, CH40, CH42, hydrotalcite HT1, and non-solid solution calcium CHCE3 as stabilizers, a resin composition having the following composition (C) is prepared, and the resin composition is rolled. And kneaded at 180 ° C. for 5 minutes to prepare a 0.7 mm roll sheet. Thermal stability was evaluated in the same manner as in Example 1. Table 8 shows the composition and results of the stabilizer.
Composition (C)
Polyvinyl chloride (degree of polymerization 1000) 100PHR
Dibenzoylmethane 0.1PHR
Dipentaerythritol 0.2PHR
D-Xiol G32 (manufactured by Cognis) 0.2PHR
Zinc stearate 0.6PHR
Calcium stearate 0.2PHR
Heavy calcium carbonate 3.0PHR
Stabilizer 0.5PHR

Examples 20-45 and Comparative Examples 18-23
A resin composition having the following composition (D) is prepared using solid solution calcium hydroxide CH39, CH23, CH26, CH40, CH42, hydrotalcite HT1, HT2, HT3, HT4 and non-solid solution calcium CHCE3 as stabilizers. The resin composition was kneaded at 180 ° C. for 5 minutes using a roll to prepare a 0.7 mm roll sheet. Thermal stability was evaluated in the same manner as in Example 1. The composition of the stabilizer and the results are shown in Table 9.
Composition (D)
Polyvinyl chloride (degree of polymerization 1300) 100PHR
DOP (dioctyl phthalate) 50PHR
Zinc stearate 0.6PHR
Stabilizer 0.5PHR

Examples 46-54 and Comparative Example 24
Using the solid solution calcium hydroxide CH39, hydrotalcite HT1 and HT2 as stabilizers, a resin composition having the following composition (D-1) is prepared, and the resin composition is heated at 180 ° C. for 5 minutes using a roll. It knead | mixed and created the roll sheet of 0.7 mm. Thermal stability was evaluated in the same manner as in Example 1. Table 10 shows the composition and results of the stabilizer.
Formulation composition (D-1)
Polyvinyl chloride (degree of polymerization 1300) 100PHR
Dioctyl phthalate 50PHR
Zinc stearate 0.4PHR
Stabilizer 1.6PHR

Examples 55-63 and Comparative Example 25
Using solute calcium hydroxide CH39, hydrotalcite HT1 and HT2 as stabilizers, a resin composition having the following composition (D-2) is prepared, and the resin composition is heated at 180 ° C. for 5 minutes using a roll. It knead | mixed and created the roll sheet of 0.7 mm. Thermal stability was evaluated in the same manner as in Example 1. Table 11 shows the composition and results of the stabilizer.
Composition (D-2)
Polyvinyl chloride (degree of polymerization 1300) 100PHR
Dioctyl phthalate 50PHR
Zinc stearate 0.4PHR
Stabilizer 4.0PHR

Examples 64-71 and Comparative Example 26
Using the solid solution calcium hydroxide CH39, hydrotalcite HT1 and HT2 as stabilizers, a resin composition having the following composition (A-1) is prepared, and the resin composition is heated at 180 ° C. for 5 minutes using a roll. It knead | mixed and created the roll sheet of 0.7 mm. Thermal stability was evaluated in the same manner as in Example 1. Table 12 shows the composition and results of the stabilizer.
Composition (A-1)
Polyvinyl chloride (degree of polymerization 700) 100PHR
Zinc stearate 0.3PHR
Stearoylbenzoylmethane 0.2PHR
Dipentaerythritol 0.2PHR
Stabilizer 3.0PHR

Examples 72-79 and Comparative Example 27
Using the solid solution calcium hydroxide CH39, hydrotalcite HT1 and HT2 as stabilizers, a resin composition having the following composition (A-2) is prepared, and the resin composition is heated at 180 ° C. for 5 minutes using a roll. It knead | mixed and created the roll sheet of 0.7 mm. Thermal stability was evaluated in the same manner as in Example 1. The composition and results of the stabilizer are shown in Table 13.
Composition (A-2)
Polyvinyl chloride (degree of polymerization 700) 100PHR
Zinc stearate 0.3PHR
Stearoylbenzoylmethane 0.2PHR
Dipentaerythritol 0.2PHR
Stabilizer 6.0PHR

[The invention's effect]
According to the present invention, a combination of a solid solution calcium hydroxide having a large specific surface area, high activity, acid neutralization and halogen scavenging, and hydrotalcite provides excellent thermal stability and A stabilizer composition that provides initial colorability is provided.
The resin composition and molded product of the present invention are excellent in thermal stability, particularly long-term thermal stability, and excellent in initial colorability.

  The calcium hydroxide of the present invention is useful as a synthetic resin stabilizer as an acid neutralizing agent, a halogen scavenger and the like. Moreover, since the resin composition of the present invention is excellent in thermal stability and initial colorability, it can be used in various molding fields.

Claims (9)

For 100 parts by weight of synthetic resin,
(A) 0.001 weight part or more and less than 0.1 weight part of following formula (1)
^{_{Ca (OH) 2-nx (}} A n-) x (1)
(However, where n is an integer of 1 to 4, x is an anion derived from the number of 0.001 to ^{0.2, A n-silicon} compound, an aluminum compound or a mixture thereof.)
And (B) 0.1 part by weight or more and 10 parts by weight or less of hydrotalcite (component B). A ^{n- _{is, SiO (OH) 3 -,}} Al (OH) 4 -, SiO 2 (OH) 2 2-, Si 2 O 6 (OH) 6 2-, C 6 H 6 O 7 2-, SiO 4 The resin composition according to claim 1, which is ^4- , Si ₄ O ₈ (OH) ₄ ^4-, or a mixture thereof. A ^{n- _{is, SiO (OH) 3 -,}} SiO 2 (OH) 2 2-, Al (OH) 4 - or resin composition according to claim 1, wherein a mixture thereof. The resin composition according to claim 1, wherein the component A is calcium hydroxide having an average secondary particle diameter measured by a laser diffraction scattering method of 0.1 to 10 μm. The resin composition according to claim 1, wherein the component A is calcium hydroxide having a BET specific surface area of 5 to 40 m ² / g. The resin composition according to claim 1, wherein the synthetic resin is polyvinyl chloride. B component is the following formula (2)

(In the formula, A ⁿ⁻ is ClO ₄ ⁻ , SO ₄ ²⁻ , CO ₃ ²⁻ , or a mixture thereof. N is 1 or 2. x, y, z, and m are y + z = 1, 0.1 ≦ x ≦ 0.5, 0.5 ≦ y ≦ 1, 0 ≦ z ≦ 0.5, and 0 ≦ m <1.)
The resin composition according to claim 1, which is a hydrotalcite represented by: The resin composition according to claim 1, wherein the component B is hydrotalcite baked at 200 ° C. or higher. A molded article comprising the resin composition according to claim 1.